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A CLEAN TECHNOLOGY PHOSPHORIC ACID PROCESS

S. van der Sluis
TR diss 1550

V» T T' * ' fiy & ^

A CLEAN

TECHNOLOGY PHOSPHORIC ACID PROCES

■Tl

iu» l f S "

A CLEAN TECHNOLOGY PHOSPHORIC ACID PROCESS

Proefschrift ter verkrijging van de graad van doctor aan de Technische Universiteit Delft, op gezag van de Rector Magnificus, Prof.dr. J . M . Dirken, in het openbaar te verdedigen ten overstaan van een commissie aangewezen door het College van Dekanen op 11 juni 1987 te 14.00 uur

door

Sierd van der Sluis

scheikundig ingenieur geboren te Oudemirdum

Delft University Press/1987

TR diss 1550

Dit proefschrift is goedgekeurd door de promotoren: Prof .dr.ir. G.M. van Rosmalen Prof.ir. J.A. Wesselingh

Copyright ©1987 by S. van der Sluis No part of this book may be reproduced in any form by print, photoprint, microfilm or any other means without written permission from the publisher: Delft University Press, Delft, The Netherlands.

Voor Ineke en onze kinderen

VOORWOORD Dit proefschrift is mede tot stand gekomen door de inzet van veel personeel,

materieel en geld door de overheid en DSM, waarvoor ik hen hierbij bedank. De te onmisbare vinden in bijdragen een van vele afstudeerders, stagiairs, bijvakkers en

omscholers,

vaste medewerkers en collega's zijn in een aantal gevallen al terug co-auteurschap van een artikel of in woorden van dank, die

daarbij vermeld staan. Zij, die om wat voor reden dan ook, daar niet bij genoemd zijn, wil ik hierbij alsnog bedanken voor hun inzet en bijdragen. Een want Tevens de speciaal woord van dank is op zijn plaats voor mijn collega Tjien T. Tjioe, zonder past zijn adviezen en hulp was dit proefschrift zeker nu nog niet tot

stand gekomen. mij een woord van dank voor de ondersteuning, die de werknemers en van ik dag de Technische Universiteit Delft, van DSM Meststoffen B.V. en de grote op groep medewerkers en medewerksters bedanken die, diensten wil

van DSM Research B.V. mij gegeven hebben. Bovenal onbezoldigd, fosforzuur Tenslotte gemaakt rond te en nacht klaar stonden om, in continu dienst, proeven met het laboratorium schaal uit te voeren en hen, die daarbij

fabriekje

weliswaar thuis bleven, maar dag en nacht oproepbaar waren. wil ik die mensen bedanken, die het op welke manier dan ook, mogelijk hebben kijken om en bij via verschillende fosforzuur fabrieken over de hele wereld het houden van lezingen op binnen- en buitenlandse

congressen en symposia, enige internationale ervaring op te doen.

CONTENTS

1. 1.1. 1.2. 1.3. 1.3.1. 1.3.2. 1.3.3. 1.3.3.1. 1.3.3.2. 1.3.3.3. I.3.3.I. 1.1)

INTRODUCTION General aspects of phosphoric acid The phosphate ore Phosphoric acid production processes Introduction of process routes The dry processes The wet processes General procedure Acidulation with hydrochloric acid Acidulation with nitric acid Acidulation with sulphuric acid Impurities in relation to the applications of the calcium sulphate byproduct

7 7 7 11 11 11 12 12 13 14 16

19 21 21

1.5 1.6

Aim of this study Literature

2.

SCOPE OF THIS INVESTIGATION

24

3. 3.1. 3.2. 3.3. 3.4. 3.4.1. 3.4.2. 3.4.3. 3.4.4. 3.4.5. 3.5. 3.6. 3.7.

OVERVIEW OF THE CTPA PROCESS Summary Introduction Objective of the study Description of the CTPA process Introduction to the process The digestion stage The crystallisation stages The filtration stages The fluoride removal Simplified process flowsheet and mass balance Conclusions Literature

28 28 29 32 32 32 33 37 41 46 50 52 53

2

1 4 . 4.1. 4.2. 4.3. 4.4. 4.5. 4.6. 4.6.1. 4.6.2. 4.6.3. 4.7. 4.8. 4.9. 4.10. 4.11.
5.

THE DIGESTION OF PHOSPHATE ORE IN PHOSPHORIC ACID Summary Introduction The d i g e s t i o n s t a g e of the CTPA process Experimental Results Discussion I n f l u e n c e of the phosphoric a c i d c o n c e n t r a t i o n I n f l u e n c e of the temperature Conclusion A k i n e t i c model of the d i g e s t i o n process Determination of the m a s s t r a n s f e r c o e f f i c i e n t s Conclusive remarks Nomenclature Literature
CRYSTALLISATION OF CALCIUM SULPHATE HEMIHYDRATE

56 56 56 57 59 60 62 62 63 63 63 66 68 68 69
70

5.1. 5.2. 5.3. 5.4. 5.4.1. 5.4.2. 5.4.3. 5.5. 5.6. 6. 6.1. 6.2. 6.3. 6.3.1. 6.3-2. 6.3.3. 6.4. 6.5. 6.6.

Summary Introduction Experimental Results and discussion The hemihydrate crystals Incorporation of phosphate ions Incorporation of cadmium ions Conclusions Literature THE FILTRATION OF CALCIUM SULPHATE HEMIHYDRATE Introduction Theory of filtration Experimental Equipment Chemicals Procedure Results and discussion Nomenclature Literature -

70 70 72 71 74 77 80 84 84 86 86 87 90 90 91 91 91 97 97

FLUORIDE DISTRIBUTION COEFFICIENTS (G/L) IN WET PHOSPHORIC ACID PROCESSES Summary Introduction Literature survey Model development General remarks Calculation of the activity coefficients Calculation of the hydrogen ion concentration in phosphoric acid Determination of an expression for the fluoride distribution coefficients Experimental Chemicals Equipment Procedure Analyses Results and discussion Conclusions Nomenclature Literature Appendix: Conversion of w$ into molalities MASS AND HEAT BALANCES OF THE CTPA PROCESS Introduction Process description General approach Digestion of phosphate ore Cadmium removal Crystallisation of calcium sulphate hemihydrate (HH) Recrystallisation of HH to gypsum Solid-Liquid separation Fluoride removal Combined mass and heat balances for each stage Discussion and conclusion Literature Appendices The solubility of HH and DH 107 111 111 111 11 2 113 114 120 121 122 124 125 125 126 126 127 129 130 131 131 132 132 147 149 151 151 105 98 98 98 100 102 102 103

4

8.6.2. 8.6.2.1 8.6.2.2 8.6.3. 8.6.1. 8.6.1.1. 8.6.1.2. 8.6.5. 8.6.5.1. 8.6.5.2. 8.6.5.3. 8.6.5.1. 8.6.5.5. 8.6.5.6. 8.6.5.7. 8.6.5.8. 8.6.6. 8.6.6.1. 8.6.6.2. 8.6.6.3. 8.6.6.1. 8.6.6.5. 8.6.6.6. 8.6.6.7. 8.6.6.8. 8.6.6.9. 8.6.6.10. 8.6.6.11. 8.6.7. 8.6.7.1. 8.6.7.2. 8.6.7.3. 8.6.8. 8.6.8.1. 8.6.8.2. 8.6.8.3. 8.6.8.1. 8.6.9.

Incorporation in HH and DH Incorporation in calcium sulphate hemihydrate Incorporation in calcium sulphate dihydrate Vapour pressure of the PpO^-H^O system Fluoride distribution coefficients Liquid-gas Liquid-solid Density correlations Phosphoric acid Sulphuric acid CDHP solutions *V 0 1 -^2S0H~H2° m i x t u r e s Calcium sulphate hemihydrate (HH) Calcium sulphate dihydrate (DH) The phosphate ore Water Heat capacities and heat contents Phosphoric acid Sulphuric acid CDHP solutions H POjj-H SO^-H 0 mixtures Calcium sulphate hemihydrate (HH) Calcium sulphate dihydrate (DH) The Phosphate ore Water Water vapour Carbon dioxide Other compounds Enthalpies of reaction Digestion of phosphate ore Crystallisation of calcium sulphate hemihydrate Recrystallisation of HH into gypsum Heat of mixing in the H P0.-H SO.-H 0 system General procedure Binary heat of mixing in the H^O^-H-O sytem Binary heat of mixing in the H ^ O ^ - H ^ sytem Binary heat of mixing in the H^PO^-H SO. system Total mass and heat balances of the CTPA process 5

151 151 152 152 153 153 151 155 155 155 155
1

56 156 156 156 156 157 157 157 157 158 158 158 159 159 159 159 160 160 160 160 160 161 161 163 163 163 161

9. 9.1. 9.2. 9.2.1 9.2.2. 9.2.3. 9.2.1. 9.2.4.1. 9.2.1.2. 9.2.1.3. 9.2.1.1. 9.2.5. 9.3. 9.3.1. 9.3.2. 9.3.3. 9.3.1. 9.3.5. 9.1. 9.5. 9.6. 9.6.1. 9.6.2. 9.6.2.1. 9.6.2.2. 9.6.2.3. 9.6.3. SUMMARY SAMENVATTING PUBLICATIONS

THE BENCH-SCALE PLANT Introduction Experimental Process conditions Chemicals Equipment Procedures Safety Startup procedure Working procedure Stop procedure Analyses Results and discussion The performance of the bench-scale run The cadmium incorporation in HH The phosphate incorporation in HH The permeability of the filter cakes Additional results Conclusions Literature Appendices Service round Pressure filter procedures The precoat procedure The filter procedure The filter change procedure The HH washing procedure

175 175 176 176 177 177 180 180 181 183 183 181 185 185 187 188 189 191 193 193 191 191 195 195 195 195 196

198 200 202

1. INTRODUCTION 1.1. General aspects of phosphoric acid Phosphoric acid is an important intermediate chemical product. It is mainly used for the manufacturing of fertilisers, as demonstrated in table 1. » 1000 tons P_0C Fertilisers Detergents Animal feed Food and beverages Surface treatment Water treatment Dentistry, tooth pastes Fire extinguisher Others Total 32 ,000 1,590 1 , 180 . 240 230 90 80 40 110 35,600 percentage 90 4.5 3.3 0.7 0.6 0.25 0.22 0.11 0.3 100

Table 1: World phosphate consumption and application in 1980 [1]. To meet steadily production the food needs for of the increasing world population, there is a fertilisers. The phosphoric acid

growing

demand

phosphate

is directly linked to the phosphate fertiliser consumption, which is
<!■ 5

expected to rise from 30.7 million tons P-O,- in 1982, to about 41.7 million tons P-0,- in 1990. This represents an increase of the phosphoric acid production from about 19.7 million tons P_0C in 1982 to 27.8 million tons P.O.- in 1990 [3].
£ 0 2 5

1.2. The phosphate ore According
P

to

Becker important

[1], about 200 known minerals contain more than 1 w$ minerals for the phosphoric acid industry are those
in wnicn

2°5' belonging X can

The

most

to the apatite group, with the general formula Ca. 0(P°i|)6X2'

be fluoride, chloride or hydroxide [12]. Because the fluoride ion is the

smallest of the three, fluoroapatite is commonly believed to be the most stable.

7

The

phosphate other

rock

normally

not

only contains the apatite mineral, but also

several feldspar

minerals, such as calcite, dolomite, pyrite, kaolinite, quartz,

and fluorite [14]. Phosphate rock deposits are located in abundance in

nearly all parts of the world. The phosphate rocks can be divided in two groups, depending on their origin: - sedimentary phosphate rock - igneous phosphate rock Igneous with vulcanic rock phosphate phosphate activity. mainly rock is crystallised from magma and thus found in areas Its availability of is therefore limited. The igneous consists rock fluoroapatite, in which calcium is partly were formed by precipitation this of

replaced by barium and strontium and chloride partly substitutes fluoride. Sedimentary dissolved and rock phosphate from deposits phosphates prehistoric seas [32]. During process the

phosphate rock was subjected to an interaction with water of varying temperature impurity content. A large number of these impurities became included in the by either In this coprecipitation way phosphate or by incorporation with a large in the apatite crystal variety in impurity rocks

lattice. found mainly replaced to

composition and concentration were created. Most sedimentary phosphate rocks are be more than a million years old [27]. The sedimentary phosphate rock of fluoroapatite, in which part of the phosphate ions are by fluoride and carbonate ions. This fluoroapatite is commonly refered more than 85 % of the world's raw phosphate came from sedimentary and China other prior washed [1]. The raw phosphate, produced by open mining, consists

to as francolite. In deposits USSR, contains to be 1981 Morocco

[1]. The four major raw phosphate producers in 1981, were the USA, the several removed first minerals next to the apatite mineral. Only the apatite to the phosphoric acid production. The raw phosphate is water to remove the water soluble minerals.

mineral is needed for the production of phosphoric acid. The other minerals have normally Thereafter ore from with

several flotation steps are applied to remove the larger part of the raw the phosphate siliceous is and often called beneficiation. The removal of in

other minerals and to obtain the phosphate ore. This process to obtain phosphate particular small removal inorganic carbonate gangue is necessary to avoid serious

problems during the phosphoric acid production. The siliceous gangue consists of particles, which is a can cause problems during filtration. Carbonate gangue prior to the digestion of the phosphate rock by an prerequisite

acid. Otherwise the development of carbon dioxide in combination with

the release of organic material from the rock gives rise to excessive foaming.

The Lawver igneous for by some the Houot determined

current techniques for beneficiation of phosphate rock are reviewed by e.a. [21]. The procedure by deposits selected for a specific phosphate rock is its carbonate content as well as by its origin. Sedimentary and are treated differently. One of the most important processes of phosphate rock, which is applied on all rocks, is

beneficiation

flotation. An overview of the most frequently used flotation techniques is given [16]. Flotation is used mainly to remove the siliceous gangue, but in also the carbonate gangue can be removed by this technique as by Dufour phosphate consist [13] for Florida phosphate rock and by Vaman RaO [39] for ores obtained after beneficiation of sedimentary phosphate of francolite by averaging the composition of 110 cases

described The rocks, for

Mussorie phosphate rock. mainly of francolite. McClellan and Lehr [23] derived a formula composition

the mean

commercially available sedimentary phosphate ores:

Ca

iO-aVVVPV6-x(C03)xF2+0.<,X

with x = 0 - 1.5 and a = 0.6 * x. The 2H sedimentary The location vary from from phosphate ores described by Gremillion e.a [1t] conformed very closely to this mean francolite composition. chemical composition of phosphate ores varies widely with their mining [11]. McClellan 1.32 in pure while and Lehr [23] found the weight ratio of Ca0/P 2 0 5 to fluoroapatlte, to about 1.62 in highly substituted
on tne

francolite, reactivity

according to Caro e.a. [7] the weight ratio of F/P-O- varies

0.09 to 0.15 respectively. The influence of the weight ratio FVP2°5

of the ore with acid is unclear. The reactivity of the ore with acid

was found to be higher at increasing C0./P„0 c weight ratio in the phosphate ore. 2 2 5 This observation was confirmed by Chien [10,11], who came to the same conclusion from a thermodynamic approach.
i

The crystallographic by Beevers lattice series to have of

structure a

of

fluoroapatlte structure

has been described in

detail crystal

and Mclntyre [2]. Montel e.a. [2*4] report the fluoroapatlte hexagonal with two series of parallel has a diameter of about 2 A, while the

channels. other channel lattice all ions

One series of narrow channels consists wide containing therefore seem the fluoride

channels with a diameter of about 3.5 A, each ions centered on its axis. The fluoroapatite

has a very open structure. According to Kreidler [20] almost

to fit to some extent in the apatite lattice, due to its open

structure.

9

Not

only

the

fluoroapatite

lattice

itself

has an open structure on an

atomic scale, but also the fluoroapatite as a mineral has an open structure on a microscopic scale. Caro e.a. [6] investigated the pore structure of phosphate

ore with mercury porosimetry and nitrogen desorption. By comparing the pore size distributions fractions, throughout specific um, and of large found particle the fine size pore fractions structure with small particle size

they

to be uniformly distributed

the material, irrespective of particle size. Hill e.a. [15] measured surface areas and found, for particle size fractions smaller than 150 2 to be varying between about 1 m /g for Virginia phosphate ore

these areas 2 37 m /g for Tunisian phosphate ore. This relatively large surface areas are to pore space within the particles. These particles are often viewed

attributed

as aggregates of fine crystals. The average dimension of these elementary grains is deduced from the broadening of X-ray diffraction bands and compared with a from surface area measurements of several suitably fine

figure samples

calculated (10

ym). The results obtained by both methods are within one order of

magnitude. The elementary grain size for Moroccan and Tunesian phosphate ore was found to be about 1000 100 500 A, while for Virginian phosphate ore, it was

approximately

- 3000 A. The average dimension of the elementary grains is

one of the most important factors determining the reactivity of the ore [15].
S I C » • COM • H U T * PHOSPHORUS

Q
ncm

•vntnm

SUM ACE

VBCOSITT COITML ABUTS

Figure 1: Uses of phosphoric a c i d produced by dry and wet p r o c e s s e s [ 3 2 ] .
10

1.3 Phosphoric acid production processes 1.3.1. Introduction of process routes Phosphoric acid can be produced from phosphate ore via two major process routes: the so-called wet processes, using strong mineral acids for digestion of the ore and the dry processes, producing elemental phosphorus as an intermediate by burning of the ore in an electric furnace or in a rotary kiln [3] An outline of the field of applications of phosphoric acid produced by dry processes as well as by wet processes is given in figure 1 [32]. Since phosphoric acid produced through dry routes contains less impurities its application lies mainly in the "high added value" areas such as detergents and food additives, while phosphoric acid from wet processes is mainly further processed into fertilisers. 1.3.2. The dry processes In the dry processes, the phosphate ore is reduced, by addition of silica and carbon, to phosphorus and slag at about 1500 °C in a furnace: Ca 1Q (PO l) ) 6 F 2 + 20 Si0 2 + 28 C —> 20 CaSiO + 28 CO + 3 Pj,
+

2 ?2

AH = 27.9 MJ/kg of ?k produced [22] The heat, AH needed for this reaction is substantial and could until 1985 only be achieved by internal resistence heating of the molten charge in an electric furnace. In 1985, however, a direct fired rotary kiln was found to be able to supply the heat [22]. A flowsheet of the KPA process, based on this way of supplying the necessary heat is shown in figure 2. After the combustion of the evaporating phosphorus, the obtained phosphorus pentoxide is absorbed in water or in moderately concentrated phosphoric acid, to obtain concentrated phosphoric acid (> 60 w$ P-0,-). The direct production of clean and concentrated phosphoric acid is possible with the dry processes, because most impurities from the ore, remain in the slag [3]. Although the heat of combustion of the phosphorus and the carbon monoxide is recovered in the KPA process, these processes are still too expensive for use in the fertiliser industry, because of their high energy consumption. Moreover, 11

fine ore particles cannot be used directly in these processes, since they hamper the interstitial gas flow through the ore bed. The where the product product of the dry processes can, however, be used in applications,

from the wet processes is not sufficiently pure. This does,

sometimes, require additional removal of arsenic and fluoride.

vent
gas scrubbing phosphate ore wafer fuel — 1 rotary kiln reactor acid absorption
i,

f
coke

t
balling preheating

^
silica

raw feed preparation

1
i

A
i
i

i
— —I

'
heat recovery acid cleaning

Figure 2: Flowsheet of the KPA process [22].

---1
air

*
j

spent solids »-

70 w % P 2 0 5

1.3.3. The wet processes

1.3.3.1. General procedure

Phosphoric mineral Sulphuric calcium acids, acid from

acid can be released from phosphate ore by the action of strong such as nitric acid, hydrochloric acid and sulphuric acid.

is the only acid, which forms an insoluble precipitate with the the phosphate ore, thus allowing the phosphoric acid to be

separated directly by filtration. The chlorides and nitrates of calcium are both soluble, or In so special techniques, like solvent extraction [28], ion exchange [19] crystallisation [1,36] are required to recover the phosphoric acid. of this phosphoric acid is being commercially produced using nitric

cooling spite

acid as well as hydrochloric acid. The economical feasibility of these processes is mainly determined by the availability and price of the mineral acid and by

local production facilities and by the desired products.

12

1.3.3.2. Acidulation with hydrochloric acid The acidulation of phosphate ore in hydrochloric acid can be represented by the following reaction [28]: Ca ln (P0„),F o
10

4 O £

+

20 HC1

— >

6 H_PO..
j

1

+

10 CaCl.

2

+

2 HF

dissolution liquor

aqueous acids to distillation water

to

stripped liquor "l»ent recovery ' J

recyc le wash phosphate ore gas m dissolution liquor to s olvent extr action to » aste

recycle •^extraction)—■»] pufification]

reflux

i

dissolution

i r

solids separation

solids washing

J1"""J-L —) washing]

—| stripping}-

extracted aqueous liquid circulating solvent

- solvent streams - aqueous streams

Figure 3= Flowsheet of the ore digestion section [28]. The hydrogen from chloride can be

Figure 4: Flowsheet of the solvent extraction section [28]. supplied, either as a gas entering an aqueous

suspension separated In shown section. solvent

of phosphate ore or as hydrochloric acid. The phosphoric acid can be the calcium chloride solution by solvent extraction with C,. and

C_ alcohols or with a mixture of these solvents. figure 3 a flowsheet of the ore digestion section of the IMI process is and in figure 4 the corresponding flowsheet of the solvent extraction The phosphoric acid and the quantity of hydrochloric acid dissolved in is distilled off and subsequently the phosphoric acid and hydrochloric

the solvent are recovered from the solvent by washing with water. Thereafter the acid are separated by evaporation. An additional advantage of this method is the reduced impurity level of the obtained concentrated phosphoric acid (> 50 w$ P_O c ), because the impurities are less easily soluble in the solvent than in phosphoric acid. A disadvantage, however, is the severe corrosion.

13

1.3.3.3. Acidulation with nitric acid

There are three main processes in which nitric acid is used for acidulation of phosphate ore: the Odda process, the DSM sulphate-recycle process [5,36] and

the Superfos process [19]. In °C. the Odda process, the phosphate ore is digested in 60 w% HNO. at 50-70 a and large part of of the the calcium nitrate is removed by cooling crystals. The calcium nitrate crystal

Thereafter,

crystallisation

separation

slurry is further processed to obtain a fertiliser, while the filtrate is partly recycled. This is shown in figure 5. phosphate HNO,
dissolution

-L^-N°x.F
-■-inerts |

I

crystallisation

— HN03

filter

...

1 '

Ca(N03)2AH20 Ito conversion)

neutralisation

— NH3 r»H20
■L—NH2NO3 (from conversion) |

evaporation granulation

Figure 5: Flowsheet of the Odda process [5].

In °C,

the

DSM

process, the phosphate ore is digested with nitric acid at 65 the solution, sulphate filtered after containing insoluble phosphate ore particles,

whereafter with

reacts gypsum filtrate ammonium ammonium

ammonium and

at 55 °C. The calcium ions are precipitated as off. Subsequently by the moisture content of the

crystals is

reduced

neutralisation

steam evaporation to obtain an

phosphate fertiliser. The gypsum cake is fed, together with a 52-53 w$ carbonate and solution into a crystalliser, in which calcium carbonate is ammonium sulphate is recovered for recycling. A flowsheet of

precipitated

this process is shown in figure 6. The third process is the so-called Superfos process, in which the phosphate ore is digested with nitric acid. The so obtained calcium nitrate and phosphoric acid containing solution is fed into an ion exchange section, where the calcium

11

ions are exchanged against potassium ions. The ion exchange r e s i n , loaded with calcium, is regenerated with a potassium chloride solution, giving an CaCl effluent stream. The product, consisting of a K N O and H PO^ solution i s used as an intermediate in the manufacturing of f e r t i l i s e r s . In a process modification, where not all the calcium ions are removed, these residual calcium ions are precipitated with the major part of the phosphate as CaHPO.. A feed grade quality i s claimed, which i s only possible if the impurities were removed before or in the ion exchange section. This process is i l l u s t r a t e d in figure 7.
Phosphate

OPEJ I " ™ *
I | V. \ ,. dissolution h * N0X.F [_~ i n e r t s

JGypsum precipitation}—— INHJ3SQ1, (From conversion)

granulation

Figure 6: Flowsheet of the DSM process [5].

potassium chloride water phosphate ore nitric acid


phosphoric acid

'

L_
I

1 ion exchanqe ] CaCl2 ammonia

_ _ K

1

pre-neutrs 1

ammonia

separation

| to NPK plant

r
| concentration! | crystallisation f-«—

1 L l_.

"I *
^neutralisation! | separation |

1
| granulation ] chlorid >-freefi PK |

drying

| dicalcium phosphate

Figure 7: Flowsheet of the Superfos ion exchange NPK process with CaHPO. coproduction [19].

15

1.3-3.1). Acidulation with sulphuric acid Although term wet During with applied. the production of phosphoric acid from phosphate ore by acidulation acid, huge amounts of calcium sulphate are precipitated as a sulphuric of all acidulation processes are refered to as wet processes, the

process

is mainly reserved for processes in which sulphuric acid is

byproduct. Depending on the temperature as well as on the phosphate and sulphate content the solution, either calcium sulphate dihydrate (DH), hemihydrate (HH) or anhydrite (AH) is formed, as shown in figure 8 [1,35]. The which The can solid lines in figure 8 represent quasi equilibrium curves, indicating will initially precipitate under the given conditions. The broken

phase

line in figure 8, is the border of the regions, where either AH or DH is stable. HH phase only exists as a metastable phase. The influence of sulphuric acid be taken into account by assuming one mole of sulphuric acid to be

equivalent with about 1.5 mole of phosphoric acid [32].

100 temp°[ 80

AM precipitation

HH precipitation

60- -

DH precipitation

40' 20

C A H stable stable"^N

/DH

20

30

40

50

w%P205

^

Figure 8: Phase diagram of calcium sulphate in phosphoric acid. Commercial a processes have been developed, producing either DH, HH or AH as

byproduct. An overview of these processes is given in table 2 [31], where the

process is named after its byproduct.
16

process | temperature

| concentration | company/name

|
D H 70 -85

w

* P 2°5
28 - 32 Prayon, Jacobs Dorco, SIAPE Kellog-Lopker, Norsk Hydro, IITPIC, Rhone Poulenc

H H

90 - 100

35 - 50

Norsk Hydro, Jacobs Dorco, Occidental

DH/HH double

stage 1 : 65 - 70 stage 2 : 95 - 100 35 - 38

Prayon

filter
HH/DH stage 1 : 90 - 100 stage 2 : 55 - 65 30 -■32 Nippon Kokan, Nissan Mitsubishi

single filter
HH/DH double filter AH |

90-100

30 - 50

Singmaster and Breyer, Norsk Hydro, Nissan, Nippon Kokan

100 -240

|

40-50

| (Nordengren)

Table 2: Wet phosphoric a c i d p r o c e s s e s . The advantages and d i s a d v a n t a g e s of the various processes are summarized in detail and P-0,.) filter the by Becker [ 1 ] . The main disadvantage of the DH, the s i n g l e f i l t e r HH/DH DH/HH processes, acid, i s the production of r e l a t i v e l y d i l u t e (about 30 wj has to be concentrated for use in fertiliser which

phosphoric

a p p l i c a t i o n s . Due t o the energy consuming c o n c e n t r a t i o n s t e p , t h e H H and the two HH/DH p r o c e s s e s , a l l o w i n g d i r e c t production of 40 w$ P 0 a r e r a p i d l y gaining field. or even higher c o n c e n t r a t e d acid from the f i l t e r ,

17

AH problems

processes

are not operational at this moment [1], due to the serious

observed in small scale commercial batch plants [25], such as enhanced

corrosion at the required high temperature as well as a prolonged residence time following from the low growth rate of AH. Each product efficiency. processes process has its own requirements regarding raw materials, utilities, quality and last but not least, overall phosphate and byproduct

An important disadvantage of the HH processes for instance, is the is the production incorporation. to Becker [1], the ultimate process route in phosphoric acid of a relatively clean byproduct especially with

relatively low (< 95$) phosphate efficiency. An advantage of the HH/DH and DH/HH regard to P 0 According

production processes is the double filter HH/DH process route, because: - concentrated phosphoric acid is directly produced from the filter - the highest overall phosphate efficiency is obtained, - the lowest sulphuric acid consumption is needed, - relatively clean phosphoric acid is produced, due to the reduced solubility of impurities in the concentrated acid and - phosphogypsum with a low phosphate content is produced.

WASTE GAS

ISULPHURIC ACI0|-

N°1 H°2 DIGESTER

COOLING PUMP TANK TANK

N°1

N"2 N"3 HYDRATION TANKS

Figure 9: The Nissan C p r o c e s s .
18

In

figure

9,

one

of

the

commercially

available

double

filter HH/DH

processes is shown [1]. Additional process time, aspects, can and which have to be taken into account before a proper

selection raw material

be made are: capital cost, maintenance cost and on-line utility cost and also product as well as byproduct

quality. These aspects depend largely on the local situation.

1.1. Impurities in relation to the applications of the calcium sulphate byproduct

The [to]. In cadmium,

phosphate

ore

contains

a

lot of impurities, as is shown in table 3

all wet processes impurities, such as radium and heavy metal ions, like originally present in the phosphate ore, are distibuted between the

phosphoric acid and the byproduct. Several methods have been developed to remove impurities from the phosphoric acid, such as flotation [33], ion exchange [9,37] and solvent extraction [29]. One of the recently published solvent extraction

processes

is the BESA-2 process [30], which claims to produce a phosphoric acid

quality comparable with the acid produced by the dry process for almost half the price of the dry process acid. One production of is the the most important environmental problems in phosphoric acid

cadmium

content

of the phosphoric acid and of the calcium

sulphate byproduct. Cadmium concentrations as low as 1 mg/1 in water have led toa painful bone disease, known as Itai-Itai [1].

40 K 238(J
232 226

6 40

pCi/g pCi/g

Cd Zn
Cu Pb As Ni Hg

18 ppm 250 ppm 10 ppm 30 ppm 20 ppm 50 ppm <0.1 ppm

Th Ra

1.2 pCi/g 38 to pCi/g pCi/g

Ra-equi valence

Table 3: Indicative concentrations of heavy metal ions and radio-active elements in phosphate ores from sedimentary deposits.

19

In the last years, there is a growing concern, particularly in Europe, that this kg toxic P?0(in metal the plans in the is ion could enter the food chain in increasing amounts. Some product, as a preventive the measure [17,38]. The countries intend to adopt a cadmium limitation of no more than 90 mg cadmium per fertiliser legislation byproduct also Netherlands the levels restricting levels of heavy metal ions in

phosphate fertilisers as well as in other products used in agriculture, and also hydrated calcium sulphate. The disposal of this by its radium content. In phosphoric acid byproduct buiding processes in is no is limited by its cadmium content, while its application as an indoor material hampered operating good nowadays the calcium sulphate byproduct is either disposed Another possibility is to use the so-called

water or stacked on land [3]. In urban countries, however, the land stacking alternative.

phosphogypsum [40]. Applications already operational or still under investigation are [8,40]: - in the building industry for the production of gypsum board, blocks etc. - as a settling retarder for cement - in super sulphated cement - as a filling material for paper, plastics, paint, etc. - for conversion into sulphuric acid and cement additives - for conversion into sulphur - for conversion into ammonium sulphate - for agricultural use - as a substitute for sand in road works - in glass production - as new building materials - in the production of gypsum ammonium nitrate as a substite for calcium ammonium nitrate In problem, content product most applications, the cadmium content of the phosphogypsum remains a because leaching of heavy metal ions cannot be totally prevented [18]. is also a major problem, because the radio-active radon gas, a decay

If the phosphogypsum is used for manufacturing of building materials, the radium of radium, can build up in the atmosphere. Methods to reduce the radium

content of the phosphogypsum, however, have already been developed [26,34,40].

20

1.5. Aim of this study In the foregoing paragraphs the importance of the impurity content of both acid and its byproduct, phosphogypsum, has been elucidated. From the

phosphoric

viewpoint of environmental pollution action is required. The process aim of this study is the development of a new commercially competitive for the production of concentrated phosphoric acid, where the following

requirements must be fulfilled: - a low cadmium content and a low fluoride content of the phosphoric acid and - a low cadmium content and a low phosphate content of the calcium sulphate byproduct as well as a low radium content to make the phosphogypsum suitable for building purposes. 1.6. Literature 1. 2. Becker, P., Phosphates and Phosphoric Acid, Fertiliser Science and Technology Series, Vol. 3, New York, Marcel Dekker Inc. (1983). Beevers, C.A. and Mclntyre, P.B., Min. Mag. 27 (1947) 254. British Sulphur Corporation Limited, London, 4th. Ed. (1984). 4. Burova, M.S. and Kazak, V.G., Khim. Prom., 1 (1985) 29. production," 192th A.C.S. national meeting, september 7-12 (1986) Anaheim, U.S.A. 6. Caro, J.H. and Freeman, H.P., J. Agr. Food Chem., 9, 3 (1961) 182. 7. Caro, J.H. and Hill, W.L., J. Agr. Food Chem., 4 (1956) 684. 8. Chang, W.F., Ed. "Condensed Papers of the Second International Symposium on Phosphogypsum, December 1986, University of Miami, Florida, USA. 9. Chemische Fabrik Budenheim, DE 3218599A1 (1-2-1983), DE 3327394A1 (14-2-1985). 10. Chien, S.H., Soil Science 123, 2 (1977) 117. 11. Chien, S.H. and Black, C.A., Soil Science Soc. Am. J., 40 1976) 234. 12. Deer, W.A., Howie, R.A. and Zussman, J., Rock Forming Minerals, 5 (1962) 324. 5. Calis, G.H.M., "The role of impurities in nitrophosphate fertilizer 3. British Sulphur Corporation, Phosphoric Acid, Outline of the industry,

21

13. Dufour, P., Predali, J.J. and Ranchin, G., US. patent 4.436.616., mar. 13, 1984. 14. Gremillion, L.R. and McClellan, G.H., Trans. Soc. Mining Engineers of AIME, 270 (1981) 1975. 15. Hill, W.L., Caro, J.H. and Wieczorek, G.A., J. Agr. Food Chem., 2, 25 (1954) 1273. 16. Houot, R., Int. J. of Min. Processing, 9 (1982) 35317. Hunter, D., "Low-Cadmium H-PO. for fertiliser use," Chemical Week, 136, 8 (1985) 25. 18. Jansen, M., Waller, A., Verbiest, J., Van Landschoot, R.C. and Van Rosmalen, G.M., Industrial Crystallisation
v

8 4 , The Hague, pg 171.

Ed. Jancic and De Jong, Elsevier, Amsterdam (1984). 19. Knudsen, K.C., Proc. of the Fertiliser Society of London* 3 oktober 1985. 20. Kreidler, E.R., "Stoichiometry and Crystal Chemistry of Apatite," PhD Thesis, Department of Ceramic Science, Pennsylvania State University, Michigan, USA (1967). 21. Lawver, J.E., McClintock, W.0. and Snow, R.E., Minerals Sci. Engng., 10, 4 (1978) 278. 22. Leder, F., Park, W.C., Chang, P.W., Ellis, J.D., Megy, J.A., Hard, R.A., Kyle, H.E., Mu, J. and Shaw, B.W., Ind. Eng. Chem. Process Des. Dev., 24 (1985) 688. 23. McClellan, G.H. and Lehr, J.R., Am. Mineralogist, 54 (1969) 1374. 24. Montel, G., Bonel, G., Trombe, J.C., Heughebaert, J.C. and Rey, C , er Proc. 1 Congr. Int. des Composes Phosphores, Rabat, 17-21 oct., (1977). 25. Nordengren, S., Francia, I. and Nordengren, R., Proc. of the Fertiliser Society of London, nr. 33 (1955). 26. Olin Corporation, US patent 4,146,568, Mar. 27, (1979). 27. Philipson, T., Lantbrukshogskolans Annaler, 29 (1963) 267.' 28. Phosphoric Acid Manufacturing using Hydrochloric Acid, Phosphorus and Potassium, 125 (1983) 29. 29. Purifying wet-process Phosphoric Acid, Phosphorus and Potassium, 139 (1985) 34. 30. Rubin, A.G., "The BESA-2 Process," Phosphorus and Potassium, 137 (1985) 28..

22

31. Scott, W.C., Patterson, G.C. and Hodge, C.A., Fert Solutions, 18 (1974) 62. 32. Slack, A.V., "Phosphoric Acid", Fertiliser Science and Technology Series, Vol. 1, Marcel Dekker, New York, (1968). 33. Societe Uranium Pechiney, NL patent 8103788 (26-06-1985). 34. Stamicarbon B.V., NL patent 8006946 (16-06-1982). 35. Taperova, A.A. and Shulgina, M.N., J. Appl. Chem. USSR, 23 (1950) 27. 36. The nitro-phosphates Alternative, Fertiliser International, 209 (1985) 8. 37. Tjioe, T.T., PhD Thesis, To be published, Technical University of Delft. 38. UKF/DSM, Private Communication with D.C. Oosterwijk. (1986). 39. Vaman RaO, D., Narayanan, M.K., Nayak, U.B-., Anantnapadmanashan, K. and Somasundaraan, P., Int. J. of Mineral Processing, 11 (1985) 57. 40. Weterings, K., "The Utilisation of Phosphogypsum," Proc. of the Fertiliser Society of London, nr. 208 (1982).

23

2. SCOPE OF THIS INVESTIGATION

Especially heavy between metals on

in

Europe

their

is One

a growing concern about the influence of of the results of extensive discussions

human

health.

the members of the European Community is to prohibit the use of cadmium

containing materials and to forbid the disposal of cadmium in the environment. Some containing companies, byproducts however, which have a in license the for disposal of their cadmium future. Due to the new

expires their

near

environmental terms. So

restrictions have to

licences for

will not be renewed under the same

they

look

solutions of their problems. One of these

companies is DSM which license for disposal of phosphogypsum into the river ends in 1988. The use of the phosphogypsum is also limited by its impurity content.

Moreover, the total quantity of phosphogypsum produced in the Netherlands by far exceeds its potential use in known applications. Studies to look initiated and sponsered by the Government, were therefore started

for new applications of phosphogypsum and for new processes to produce

clean phosphogypsum, suitable for application. Additionally, the cadmium content of the fertilisers, made from phosphoric acid should be reduced as well to prevent

build up of cadmium in the soil and thus an increase in cadmium in the food

chain. This production study is part of the development of a new process route for the

of clean phosphoric acid and clean gypsum. There are three basically

different routes. First reduced by of all the amount of cadmium introduced into the process can be

either using phosphate ore with a low cadmium content, of which the is limited, however, or by removal of cadmium from the phosphate

availability ore

prior to its use. This last possibility is attainable by either calcination

of the ore or by selective digestion of the carbonate fraction of carbonate rich phosphate ores with a mineral acid with a relatively high halogenide content.

Although the carbonate fraction of these ores is known to contain an appreciable quantity factor so of two the total amount of cadmium present in the ore, a reduction with a of the total cadmium content of the ore is the best result obtained

far. The calcination procedure consumes much energy and moreover, the CdO is into the atmosphere, because it is difficult to recover the cadmium

released

completely from the off gasses.

24

The the free level

second

method acid ion

is

to

prevent by

the

incorporation solvent

of cadmium in the flotation,

phosphogypsum by addition of complexing agents for cadmium and to remove it from phosphoric or the cadmium with of afterwards, exchange. in the either extraction, flocculation If the cadmium content of the ore is high, the

level

solution can only be reduced to an acceptable low for the cadmium is therefore, a good solution for integral and This thus method by which the cadmium is reducing its

addition of relatively large amounts of complexing agents. The agents is

addition The removed ways.

complexing

phosphate ores with a relatively low cadmium content. third from alternative the in the process stream simultaneously

incorporation precipitation removed is based (chapter small To cadmium because step and

phosphogypsum.

alternative can be obtained in two

The first one is the removal of cadmium, ions from the solution before the of gypsum. Therefore a predigestion step is necessary to obtain a

clear calcium-di-hydrogen-phosphate solution, from which the cadmium ions can be by either ion exchange, extraction or another technique. The second way on the of relatively high cadmium uptake of calcium sulphate anhydrite calcium sulphate anhydrite, precipitated from the recycled 5 ) . The cadmium is removed from the solution by its incorporation in a

amount

phosphoric acid by addition of calcium ions. produce content this the concentrated phosphoric acid and phosphogypsum both with a low the alternative with the predigestion step has been chosen, route also has the possibility to optimize the digestion

process

crystallisation step independently from each other, and moreover

complexing

agents can be applied for a further reduction of the cadmium content

of the phosphogypsum. This technology composed been contents of thesis a covers series in the important parts of the development of a "clean

phosphoric

acid" course

(CTPA) process along a predigestion route. It is of the investigation. A small overlap in the

of self consistent articles, some of which have already

published

of the various chapters as well as some inconsistency in the notations

were therefore unavoidable. The various articles have been arranged according to the sequence in process steps, when possible.

25

Chapter (CTPA) separate regarded

3 gives as

a brief overview of the Clean Technology Phosphoric Acid developed at the Technical University of Delft. Also the of the investigation. It links the separate

process, as an

process steps are indicated and briefly discussed. This chapter can be extended summary

process steps together. One chapter The of 4. the Here new and essential steps of the CTPA process is treated in

the digestion of phosphate ore in phosphoric acid is treated.

digestion The

conditions were systematically varied by changing the phosphoric

acid concentration, temperature and particle size of the Zin phosphate ore. subject of chapter 5 concerns the second new and important step of the the crystallisation of calcium sulphate hemihydrate from a clear crystallisation phosphoric The conditions were varied over a wide range by acid concentration, the sulphuric acid concentration, cadmium the as well as the phosphate incorporation in the experiments, performed with the The the CTPA process,

solution. changing the the

stirrer speed, the solid over liquid weight ratio and the residence time in crystalliser. Chapter 6

precipitated calcium sulphate hemihydrate (HH) were measured. describes filtration phosphoric 5. as The filtration acid-HH slurries obtained from the experiments described in chapter of the calcium sulphate hemihydrate (HH) cake obtained by

permeability

of the phosphoric acid-HH slurry from the crystalliser is determined

a function of process parameters like the sulphate content and the residence Chapter 7 deals with the fluoride distribution between the phosphoric acid phase. Because of environmental restrictions the fluoride removal in a controlled way. The fluoride distribution coefficient is a function of temperature, phosphoric acid concentration, sulphuric an equation, which can be used to predict the fluoride place

time of the solution in the crystalliser. and must the take as gas

studied made to

acid concentration and fluoride content of the solution. Moreover, an attempt is develop distribution coefficients as a function of the process parameters. Most 8 to plant, focussed developed of the results obtained in the foregoing chapters are used in chapter according to the CTPA process. Most attention a priori was

estimate the mass and heat balances of a 1000 tons P„0 C per day producing operating dy on energy and phosphate efficiencies. The flowsheeting program TISFLO, DSM is used for the calculation of the composition of all process

streams and of the overall mass and heat balances.

26

To phosphate

study

the

influence

of

impurities,

a bench-scale plant of the more

relevant parts of the CTPA process was build. The influence of impurities on the and cadmium incorporation in the HH as well as on the permeability of the HH cake obtained by filtration of the HH slurry was studied. The obtained with the according produce results from to a the results obtained obtained CTPA in this a study should be combined with the results reasonably give sized pilot plant; operating

simultaneous

study of the cadmium removal techniques [1] and a clear view of the possibility to

from

process, to

"clean" phosphoric acid and "clean phosphogypsum" with the CTPA process

in an economically feasible way. [1] Tjioe, T.T., PhD Thesis, To be published, Technical University of Delft

27

3. OVERVIEW OF THE CTPA PROCESS

3.1. Summary

Phosphoric 'wet process',

acid for use in fertiliser applications is mainly produced by a i.e. by digestion of phosphate ore with sulphuric acid. In such

wet processes, however, impurities like cadmium and radium, originating from the phosphate ore are distributed between the phosphoric acid and the byproduct, a

calcium sulphate modification. The use or disposal of the byproduct and probably the use of the phosphoric acid in future as well is limited by its impurity

content. The aim of the currently acid developed process is the direct production of a low cadmium content as well as the

concentrated

phosphoric

with

production of a major amount of calcium sulphate as hemihydrate (HH), with a low phosphate, cadmium and radium content, in a commercially feasible way. For this purpose the phosphate ore is first completely digested in recycled phosphoric of the acid, containing about 40 w? P?0,- a n d 1«8 w? H?S0j,. After separation ore residue together with a minor amount of calcium sulphate

insoluble

hemihydrate, precipitated in the digester, a clear calcium-di-hydrogen-phosphate 2+ (CDHP) solution is obtained. From this solution the Cd -ions can be removed by e.g. ion exchange. sulphuric Thereafter the calcium ions are removed by adding

concentrated In this way the

acid to the CDHP solution in the crystalliser at 90 °C.

a clean calcium sulphate hemihydrate can be obtained. In order to individual process steps, each step had to be investigated

optimize

separately. By performing HH crystallisation experiments, a linear relationship was

found between the molar phosphate over sulphate ratio in the crystals and in the solution. sulphate the The phosphate content of the crystals decreases with increasing

concentration content was also

in the crystalliser. It was found that above 3 w$ H SO. of the HH was as lower than 0.1 vi% P2°c:Tne

phosphate

cadmium

incorporation appears w* H 2 S O r Filtration of the ore, to

measured

function of the operating conditions and

increase significantly with raising sulphate concentrations above 2

studies are

showed, that the HH crystals obtained during digestion to filter, while the HH crystals developed in the well. A maximum filtration rate was reached, if a

difficult quite

crystalliser,

filter

sulphate content of about 1.8 wï H SO. was maintained in the crystalliser.

28

A an

study of the fluoride emissions in the process led to the development of for the fluoride distribution coefficient as a function of the

expression

operating conditions. Preliminary which part of results the from a is continuously studied, were operated bench-scale plant, in in agreement with the results

process

obtained from the separate studies. A . preliminary experimental less process flowsheet and mass balance, in combination with our show that concentrated phosphoric acid (40 wJ'P-Cv) with

results,

than 5 ppm Cd as well as clean calcium sulphate hemihydrate with less than

1 ppm Cd and less than 0.3 w% P ? 0_ can be produced.

3.2. Introduction

Phosphoric phosphoric acid

acid

is

mainly used for the manufacturing of fertilisers. The is almost directly linked to the world phosphate

production

fertiliser consumption, which is expected to rise from 30,7 million tons P-CL in 1982 to about 11,7 million tons P„0,. in 1990. This represents an increase of the wet phosphoric acid production from 19,7 million tons P-CL in 1982 to 27,8

million tons P.0,. in 1990 [19]. Phosphoric mineral Sulphuric calcium directly acids acid acid can be released from phosphate ore by the action of strong such is as nitric acid, sulphuric acid and hydrochloric acid.

the only acid which forms an insoluble precipitate with the

of the phosphate ore, thus allowing the phosphoric acid to be separated by filtration. The chlorides and nitrates of calcium are both soluble,

so special techniques, like solvent extraction [18] ion exchange [14] or cooling crystallisation [2], [31] of well mainly this, as phosphoric hydrochloric determined by acid acid. the are required to recover the phosphoric acid. In spite is being commercially produced using nitric acid as The economical feasibility of these processes is and price of the mineral acid and the

availability

local production facilities. Although the these acidulation methods are all referred to as "wet processes",

term "wet process" is mainly reserved for processes in which sulphuric acid

is applied. During the production of phosphoric acid from phosphate ore by wet

processes, e.g. by applying sulphuric acid, huge amounts of calcium sulphate are precipitated phosphate and as a byproduct. content Depending of the on the temperature as well as on the solution, either calcium sulphate

sulphate

29

dihydrate

(DH), hemihydrate (HH) or anhydrite (AH) will be formed, as is shown

in figure 1 [1, 29].

100temp°C 80-

AH precipitation

HH precipitation 60DH precipitation

40' 20

- - C A H stable
, / D H stable""*N

20

30

40

50

w%P205

^

Figure 1: Phase diagram of calcium sulphate in phosphoric acid. The indicate HH solid lines in figure 1 represent quasi-equilibrium curves, which

which phase will initially precipitate under the given conditions. The

broken line in figure 1 bounds the regions, where either DH or AH is stable. The phase only exists as a metastable phase. The influence of the sulphuric acid can be taken into account wet as processes a are by assuming that 1 mole of sulphuric acid is developed producing either DH, HH or AH or Becker [1] summarizes the advantages and content

equivalent to about 1.5 mole of phosphoric acid. Commercial even combinations The processes phosphoric applications. filter filter, moment plants HH/DH are main is byproduct. of of the a to

disadvantages of such processes. disadvantage the production which to the has DH, the single filter HH/DH and the DH/HH relatively be diluted for step, (about use 30 in w$ P„0_) 2 D fertiliser from the

acid, Due

concentrated concentration

expensive field.

the HH and the two

processes, allowing direct production of 40 - 50 w$ P 0 rapidly to gaining

AH processes are not operational at this

[1], due

serious problems observed in small scale commercial batch

[17], such as the severe corrosion at the required high temperature and

the low growth rate of AH.

30

In all wet processes, impurities, such as radium ions and heavy metal ions, like cadmium, originally present in the phosphate ore, are distributed between

the phosphoric acid (up to 80$ of the Cd) and the byproduct, 'phosphogypsum'. Cadmium Concentrations is responsible for a painful bone disease known as Itai-Itai. [1], Cadmium

as low as 1 mg/1 in water have led to that illness

is one of the most worrisome environmental problems, and in the last years there is growing in concern, e.g. the particularly wet Some in Europe, that this toxic metal, which is

present

phosphoric acid, could enter into the food chain in countries intend to adopt a cadmium limitation of no

increasing more than

amounts. 90 The

mg per kg P 2 0_ in the fertiliser product as a preventive measure Netherlands plans legislation as restricting in other the levels of heavy products, used in

[12,33]. metals in

phosphate and also

fertilisers the

well • as

agriculture water. These

levels in phosphogypsum, which is disposed into the may well be taken up by the European Economic

restrictions

Community in the near future. The which byproduct, calcium sulphate, also tends to incorporate phosphate ions, the a overall phosphate efficiency of the process. The use of this building material is hindered by its radium and phosphate

lowers as

byproduct content,

while the development of new applications for phosphogypsum is limited

by the uptake of heavy metal ions, since leaching of heavy metal ions can not be totally clean an prevented phosphoric [13]. The direct production of concentrated and relatively

acid is so far only possible by applying the furnace process,

alternative to acidulation processes. In the furnace process the phosphate ore is reduced, by addition of silica

and carbon, to phosphorus and slag at about 1500 °C:

2 Ca 1Q (P0 1) ) 6 F 2 + 20 Si0 2 + 28 C

- — > 20 CaSiO

+ 28 CO + 3 P^ + 2 F 2

(1)

AH = 27.9 MJ/kg of P^ produced [16].

The years in to an ago

heat

needed

for this reaction is substantial, and could, until a few

only be achieved by internal resistance heating of the molten charge

electric furnace. In 1985, however, a direct fired rotary kiln was used the into heat water [16]. After or moderately acid combustion of the phosphorus, the P 0, is 2 5 phosphoric The direct acid, to obtain production of

supply

absorbed

concentrated w$ P„0,-).

concentrated concentrated because most

phosphoric and clean

(>60

phosphoric from the

acid is possible with the furnace process, ore remain in the slag [19]. This process,

impurities

31

however, energy the phosphoric byproduct In acid wet

is

too

expensive for use in the fertiliser industry, due to the high there are other possibilities to remove Cd from wet like for instance flotation [28], solvent extraction [21] or the use

cost. Moreover, acid, remains order for Clean

Budenheim process [3]. In all these processes, however, the disposal of the a problem, mainly due to its cadmium content, while

of the byproduct as e.g. building material, is hampered by its radium content. to produce not only relatively clean and concentrated phosphoric applications, at a feasible price, but also pure HH, the Phosphoric Acid (CTPA) process is currently being fertiliser Technology

developed. 3.3. Objective of the study The acid with aim a of the CTPA process is the production of concentrated low cadmium and fluoride phosphoric

content as well as the production of

calcium sulphate hemihydrate with a low cadmium, radium and phosphate content in a commercially feasible way. 3.4. Description of the CTPA process 3.4.1. Introduction to the process To meet the foregoing requirements, the Cd
2+

2+

-ions have to

be removed from
2+ 2+ '

a large process stream. An alternative would be to prevent incorporation of Cd -ions ions of by Cd a in the HH or to leach the Cd -ions from the HH, in which cases the Cd

-•

only have to be removed from the much smaller product acid stream. Removal from the phosphate ore by e.g. calcination, is far too expensive to be a alternative. Selective leaching of cadmium from ground phosphate ore mineral acid to with a high chloride concentration is another [4]. Due the high chloride content, however, severe corrosion to of produce HH with less than 0.5 ppm Cd, nor the diluted

reasonable possibility

will probably occur. So far no methods are known to prevent the Cd uptake during crystallisation methods reached. For HH, which to sufficiently, the Cd removal leach from the byproduct until an acceptable low level is Cd from the large process stream, before

Therefore,

major amount of the calcium sulphate is crystallised, is a necessity. this purpose the digestion of phosphate ore and the crystallisation of normally occur more or less simultaneously, have to be divided into

two separate stages (see figure 2 ) .

32

This each the

also

makes

it

possible to control each stage apart and to optimize of phosphate ore, occurs in a recycle stream of conditions in the

stage on its own, instead of the combination of the two. The first step of process, the digestion acid. ions in an amount Since the recycled acid stream, however, unavoidably contains dictated by the operating

phosphoric sulphate

crystalliser, some of the HH, up to a maximum of 25 w$, will precipitate during digestion of the ore. After filtration of the insoluble ore residue, together with the'relatively HH precipitated, a clear calcium-di-hydrogen-phosphate (CDHP) 2+ solution is obtained, from which the Cd -ions can be removed by ion exchange or extraction. digestion raise (> 98 w$ Thereafter the HH is crystallised. The HH precipitated during of the phosphate phosphate ore has to be recrystallised into DH in order to efficiency of the process to an acceptable level acid (> 40 w$ P„0_ ) is still produced,
c. D

small

amount

of

the overall

P„0 C recovery). Although recrystallisation of this part of the HH is concentrated phosphoric step

necessary, because

the recrystallisation

is fully

integrated in the process. The

scheme of the process is given in figure 2.

\
digestior Cd removal HH crystallisation

HH

recrystallisation H H — — OH H 2 SO fc

DH

1

t
recycle acid product

Figure 2: Process scheme. The sections, [32]. cadmium followed most important steps of the CTPA process will be discussed in the next except for the Cd of inorganic removal step, which will be presented elsewhere agent, like bromide or iodide ions, the Cd removal by ion exchange is the addition of a complexing of the Cd-halogenide complex by anion exchange with

The principle specific by

the removal

commercially available basic ion exchange resins. 3.4.2. The digestion stage The phosphate main phosphate ores ores used today of are sedimentary fluoroapatite phosphates or part of the

franeolltes.

These

mainly

consist

with

ions replaced by fluoride and carbonate ions. By beneficiation of the

33

ore, still

large

amounts

of waste

material are removed. The treated ore, however,

contains residual calcite and dolomite, which cause severe foaming during Fluoroapatite is dissolved in pure phosphoric acid according to the

the digestion [1]. following reaction: Ca 1 Q (P0 4 ) 6 F 2 + 1 1 4 HgPO,, — > 10 Ca(H 2 P0 4 ) 2 + 2 HF fluoroapatite after which CDHP the calcium-di-hydrogen-phosphate, further referred to as CDHP, (2)

dissolves in the phosphoric acid stream. 6 5 4 3 2 1 ^\_ 0 30 35 40 45 w%P205 ^ Figure 3: Solubility of CaO in phosphoric acid. The depends amount of CDHP which 100 °C w%CaO

can be dissolved in phosphoric acid strongly

on the temperature and the phosphate content of the solution, as shown acid to be used for the production of mono- and di-ammoniumcontain by 40 w? P„0 C
2 D

in figure 3 [7]. Phosphoric phosphate digestion into DH. must stage In at least is [11]. The temperature in the boundary, because the

restricted

the

HH-AH phase

precipitated digestion

calcium

sulphate has to be HH, which can be easily r e c r y s t a l l i s e d

order to minimize the recycle acid stream, necessary for complete

of the phosphate ore, conditions with the highest CaO solubility have 3t

to

be

chosen. a of of

The

optimum of

conditions for digestion of the phosphate ore are acid and sulphuric acid is used for the

therefore about 40 w? P-O- and approximately 90 °C. When digestion digestion At ore tends to mixture the phosphoric two ore, processes will occur more or less simultaneously: in the digestion stage above 2.5wJ H SO., the HH

the phosphate ore and precipitation of calcium sulphate (HH) [1]. concentrations not only upon the present HH crystals, but also upon the

sulphate

precipitate

particles. Such coating of the ore reduces the digestion rate and is called

blinding [5]. Since the highest possible digestion rate should be obtained, the sulphate in the digestion stage must be carefully selected in order to

concentration a low

avoid blinding. In a continuous process, blinding can only be avoided by keeping sulphate concentration in the digester, which implies maintaining a high concentration. proceeding in very pure Under such conditions, the continuously added sulphate precipitate upon the hemihydrate crystals and the digestion can be treated if in pure phosphoric acid. The digestion experiments were thus phosphoric acid [25]. At 90 °C, however, the digestion calcium ions as

performed proceeds The In order dolomite

fast and is accompanied by severe foaming. Most experiments were

thus performed at lower temperatures, with pretreated ore. phosphate ore used was a mixture of Khouribga/Zin in a 40/60 \>% ratio. to with reduce the foaming, the ore was pretreated to remove calcite and a 0.5 N tri-ammonium-citrate solution at pH = 8.1 for a few days

[22]. The remaining fluoroapatite was washed with water and dried at 60 °C for a few days. Thereafter, the ore was divided in twelve fractions by sieving through "Twente" sieves. The ore particle sizes range from 150 to 2000 ym. The 1.5 liter reaction 1 kg were vessel was thermostated. About 50 grams of ore were suspended in about from the of the reactor by vacuum withdrawal, filtered over a G^ glass of acid. To monitor the digestion process with time, periodically samples taken From digestion the

filter, coated with perlite, and analysed for the CaO content. results obtained, it can be deduced that in a first approach the phosphate ore in phosphoric acid depends on the concentration of acid as well as on the temperature and the particle size of the of rate the ore and the step higher in the temperature, the higher the

phosphoric size the an

phosphate ore. In figures 4 and 5 it is shown that, as expected, the smaller the particle If reaction, digestion rate of the calcium present in the ore. determining the digestion process were a chemical increase of the digestion rate with increasing acid concentration

is expected, due to the increase of the hydrogen ion concentration. If, however,

35

diffusion expected,

is the rate due to

determining

step, a decrease of the digestion rate is of the viscosity with increasing acid

the increase

concentration.
conversion conversion

emp.PC) 0.00129-0,00151 0,000655-0.000780 0.000462 0,000181-0,000256 50 70 50 60 70

particle size (ml 0,00185 0.00185 0,00078 0,00078 0,00078

time (mini

10

time (min) -

Figure 4: Influence of the particle size on the digestion rate of the phosphate ore at 50 °C in 40 u% P o 0 r .
2 D

Figure 5: Influence of the temperature at different particle sizes on the digestion rate of the ore in 40 w% P„0,_. 2 5

In

figure

6 the influence of the concentration of phosphoric acid on the the digestion rate decreases,

digestion rate shows that from 35 up to 45 w? P_0
2 O

while for 30 up to 35 w$ PT) the digestion rate seems to increase. This changes diffusion can be explained by assuming that at 50 °C the rate determining step from chemical reaction at low phosphoric acid concentrations to for higher phosphoric acid concentrations. At 90 °C diffusion will be

the rate determing step also for 30-35 wj P-O... This study has been continued in 2 5 order showed to determine the rate controlling mechanism results at different operating conditions [23, chapter 4 ] . Preliminary from our bench-scale plant

that a residence time of about 1 hour is enough, for ore particles up to

2000 vim, to reach more than 99 % conversion.

36

t
conversion 1-

temperature = 50°C particle size = 0.000655m w% P ; 30 35 40

I

f

i
u

5

10

time (min)

•-

Figure 6: Influence of the phosphoric acid concentration on the digestion rate of phosphate ore at 50 °C. 3.4.3. The crystallisation stages In in as ore, the CTPA process several crystallisation stages exist. The first occurs approximately 1.8 w$ H_SO ü , which almost completely precipitates

the digestion stage. The recycled acid, used for digestion of the phosphate contains HH. From previous batch experiments [13] the phosphate incorporation in this plant also a phosphate incorporation of approximately 3 w? P_0C was found HH. Because about 25 wj of the total calcium present in the phosphate precipitated during digestion, the overall phosphate efficiency of the would be unacceptably low. Therefore, this HH must be recrystallised to [10] that due to recrystallisation of HH into DH, a reduction in the is

HH is expected to be high (above 2 w$ P„0_). In our continuously operated benchscale in ore this

process known

reduce the phosphate incorporated in the calcium sulphate crystal lattice. It is phosphate incorporation of about 90 % can be achieved. Batch recrystallisation experiments of HH into DH showed that a phosphate '-35^
i3 a in D H

incorporation of 0.3 w$ P2°5 however, is needed for

reasonable estimate of the value to

be obtained in a production plant. A residence time of approximately 5 hrs [10], complete conversion of HH into DH. In order to reduce 37

this

residence The most of acid. the

time, a

more

detailed investigation of the recrystallisation

process is required and will be reported in the near future [35]. important crystallisation step in the CTPA process is the direct clean This optimal HH from a clean and clear CDHP solution and concentrated operating conditions. The influence of the w$
P 2 0

production sulphuric determine

crystallisation was extensively investigated in order to R'
the

w$ H9SOj. and the residence time in the crystalliser on the phosphate and cadmium incorporation studied. The filterability. The and given to the the after 80 continuous crystallisation crystalliser experiments were performed with chemically pure CDHP in the HH as well as on the size and shape of the HH crystals was size and shape of the HH crystals have been correlated with their

sulphuric elsewhere

acid solutions of varying concentrations in a separate, 1 liter, at 90 °C. A more detailed description of this study is [27]. Experiments were performed with residence times of 20 up Each experiment lasted for 8 to 10 residence times. After each samples were taken and analysed for the cadmium as well as for residence time. The samples taken to be representative for the content of the HH crystals. The cadmium and phosphate content of remained constant after the 6 residence time were considered

minutes. time,

residence

phosphate crystals the 8

"steady state" of this system. In (less still needles is were phosphoric than higher were 0.7 w% acid containing 40 u% P_Oc and a low sulphate concentration H ? S0n) aggregates of HH crystals were obtained. At raising concentrations (above 2 w$ H-SOj.) mostly single needles

sulphate concentrations single needles were formed in addition to aggregates. At sulphate were grown which were longer (up to 2 mm) and relatively thinner. Also many tiny observed. The influence of the HH crystals on their filterability in section 3.1.3 (see also figure 10, 11 and 12). By performing due to the higher supersaturation caused by the lower in more concentrated phosphoric acid (47 w$ PpOc) mainly aggregates possibly quantified obtained,

experiments

solubility of HH, which stimulates primary nucleation. The phosphate incorporation in the HH was found to be a competition between the phosphate and the sulphate ions in the solution. In figure 7 the molar phosphate No over sulphate ratio in the HH crystals is given versus the same ratio significant influence of stirring rate and residence time on the

in the solution. phosphate uptake was found. Small variations in supersaturation therefore do not appear to have any influence on the uptake. In batch experiments, however, where

38

larger

variations

in the supersaturation were used the phosphate incorporation

appeared to increase with enhanced supersaturation [13]. The relationship between the molar ratios presented by: in figure 7 for

sulphate concentrations between 0.1 and 2.5 w$ is given

[ HPO^ 2 "] —
2

[ H3P04 ] ( crystals ) = 1.4 * 10~ 4 * [ H2S04 ] ( solution) (3)

[ SO,, " ]

From equation (3) it can be calculated that at sulphate concentrations above 1.8 w% in phosphoric acid containing HO w$ P-0_ a phosphate incorporation in the HH of less than 0.3 w$ P-0C is obtained. This incorporation is acceptable process and is in agreement with the preliminary results obtained from

crystals for our

our bench-scale plant.

i


0.04 (HPO^] | 0.03—
so2-

| install 4 '
residence w%P 2 0 5

0.02250 rpm 7°

time 20 min. 40 min. 60 min. 80 min.

40

47


O


D

0.01-

0

fo °
/■^ 1570 rpm

0 100 200 300

[H3P0 J
-(solution) (H2SO4] ^ Figure 7: Phosphate incorporation expressed as the molar phosphate over sulphate ratio in the crystals versus the same ratio in the solution. 2+

The Ca 2+

incorporation

of

cadmium in the HH, expressed as the molar Cd

over

ratio

sulphate

content

in the HH crystals is plotted in figure 8 as a function of both the 2+ 2+ of the solution and the molar Cd over Ca ratio in the

3 9

solution. At higher,

In this figure, only results are given for experiments in phosphoric higher possibly phosphate due to concentrations the cadmium uptake was found to be

acid containing 40 w$ P„Cv. the reduced solubility of HH. The curve presented in

figure 8 shows that, up to about 2.5 w$ H ^ O ^ , the cadmium incorporation remains almost constant for experiments with a residence time of 10 minutes. An increase in uptake occurs with increasing sulphate concentrations for experiments with a residence time of 20 minutes. No explanation for this difference can be given.

I,

3
r 'sidence fime
105xl"l I Ca J hal) • 20 min. o 40 min.

2

1

0

Q^

» 1 i
2 1

w% H SO
3 1

500

1000

1500

5

(«I
|Ca|

2+ 2+ Figure 8: Cadmium incorporation expressed as the molar Cd over Ca ratio in the HH crystals versus the same ratio and the sulphate concentration in the solution. During and HH in continuous operation of the bench-scale plant, however, it was

observed that in the digester, at very high calcium concentrations (see table 1) thus at low sulphate concentrations (below 0.05 w$ H,SCv) the precipitated 2+ 2+ crystals contained a very small amount of Cd. The molar Cd over Ca ratio the crystals was less than 4 * 10~ . Therefore, it can not be excluded that 0.1 wj H 2 S0. the actual time and the stirring Cd uptake will decrease. Variations of the rate had no significant influence on the Cd

below uptake it

residence

either. From the results mentioned above and from the bench-scale plant, can only be reduced to less than 1 ppm by preventing the cadmium

can be deduced that the cadmium incorporation in the HH obtained in the HH

crystalliser,

HO

incorporation through the use of complexing agents or by the previous removal of the cadmium from the process stream. An large during additional quantity of result the from the bench-scale plant experiments was that a radium present in the ore was precipitated with the HH

digestion. The majority of the HH, obtained in the HH crystalliser, thus less Ra than HH obtained from commercial processes. This result is in

contained

good agreement with those described in a DSM patent [6]. 3.1.1. The filtration stages Three figure filtration stages are encountered in our CTPA process as is shown in first, located after the digestion of phosphate ore, separates from of the the CDHP HH solution. DH. The second filter is placed after filter is installed after

13. The stage

the ore residue particles together with a minor amount of HH precipitated in the digestion recrystallisation crystallisation into The third

of the major part of the HH, which should be clean enough to be

used as e.g. a building material. In sulphate be order cakes to calculate the filter area needed for each stage, the calcium

obtained in all three stages, should be characterized. This can

achieved by measuring the permeability of the formed cake, which can be used

to calculate the linear filtration velocity, U, from the equation: 1 U = — A in which * dt A V t K n h The n*h = filter area = volume of filtrate = filtration time = cake permeability = liquid viscosity = cake height K, can be obtained by dV K*AP (4)

[m ] [m 3 ] [s] [m 2 ] [N*m~2] [N*s*m~2] [m] substituting the specific cake

AP = pressure drop over the cake

permeability,

resistance, o, the solid density, p

and the cake porosity, e into the equation:

11

where

a = specific cake resistance e p = cake porosity = solids density

[m*kg
-•3

] ]

[kg*m

The cake porosity follows from a mass balance over the filter cake: G * s = (1-e) * a * h » p s in which G« ■ mass of slurry f i l t e r e d s = weight fraction solids in the slurry The specific cake resistance can be calculated from the slope, B, of the At/AV versus V curve, obtained from f i l t r a t i o n experiments at constant pressure by the equation [34]:
B * 2 * A * AP

(6) [kg]

a
c * n

(7)

i n which

c
m

= (s * p . ) / ( A * (1 - m * s ) e * Px
= 1 +

[kg»nf 5 ]

(1-e)

* p

p. = liquid density To obtain uniform have crystals been and reproducable

[kg*m

-3 ]

results, all crystallisation crystalliser, with an

experiments First precipitated (mean

performed

in a continous

unclassifying slurry withdrawal. the filtration during of the small HH particles (mean diameter = 100 ym), mixed with the very tiny ore residue particles digestion,

diameter

= 5 pm) was studied. This filtration is obviously difficult,

because of the small particles involved. Only by using a pressure filter we were -1 3 able to calculate with equation (H) an approximate permeability, K, of 1*10 to 1*10
-ill

m for the HH/ore residue cake. This is very low, especially since a of the huge process stream is necessary. In practice, a

p

large

throughput

42

sedimentary liquid. The packed during such DH acid a

system

is therefore

recommended

to separate the solids from the

Washing CDHP

of the cake solution which

is not needed, because the crystals have to be

recrystallized. must be almost free of solids to avoid blockage of the might be used for removal of cadmium by anion exchange. columns,

The filtration of the DH obtained after recrystallisation of the HH precipitated digestion, is assumed to be equal to the filtration of DH obtained after of HH produced in common HH/DH processes. The permeability of recrystallisation

DH cake was calculated with equation (4) and with data given by Becker -12 2 [1], to be about 1*10 m . This permeability was also found by filtration of a slurry from a commercial HH/DH process. Because in practice the quantity of 30 m for a 1000 tons P_0_ per day plant) will never be an to be filtered here is relatively small, the industrial filter area needed

(about - 20

operational l i m i t a t i o n .

701012xKlm2) residence time

—•- 20 min --o-- 40min
60 min

50-

30-

10-

-*•

w%H2S0<,

Figure 9: Influence of the residence time and the sulphate concentration on the permeability of the H H cake obtained in the c r y s t a l l i s e r at 40 w% P o 0 lr . The third filtration stage, of the majority of the HH, was studied more

intensively

[ 2 1 ] , p a r t i c u l a r l y because the capacity of this f i l t e r was expected

to be an important item in the capital cost of the plant.

43

In figure 9 the influence of the sulphuric acid content in the crystalliser on the permeability of the HH cake is shown. A maximum permeability is observed 1.5 and 2 u% H SO. as was also found by Dahlgren [5] for a single stage

between

HH process. This result can be explained by the shape and size of the crystals. At low sulphate concentrations both very small crystals are formed, while at high (up to 2 mm) and small crystals were

sulphate

concentrations

large

observed. These different crystals are shown in figure 10, 11 and 12.

Figure 10: HH crystals obtained at 90 °C in 40 u% ?20

and 0.5 w j H 2 S0

The

influence

of the residence time on the permeability of the HH cake is

also demonstrated in figure 9. Above about 1.5 u% H_S0j. an increase in residence time be HH seems caused needles in to lead to a reduction in the permeability of the HH cake. This can by the formation of small crystals due to the breakage of the longer obtained at longer residence times. By maintaining about 1.8 w?

H SO. of the

HH cake is about 65*10

the crystalliser and a residence time of 20 minutes, the permeability -12 2 m . From preliminary results, obtained in our plant, this permeability is expected to be in practice one fifth of obtained, due to the presence of impurities. The filter area needed 2 calculated to be approximately 75 m for a 1000 tons P 0~ per day This value is satisfactory small. More information about this

bench-scale the can value then

be

producing

plant.

subject will be gathered in the near future [23].

44

Figure 11 : HH crystals obtained at 90 °C in 40 w% P_0,- and 2.4 w$ H„S0„. do i n

Figure 12: HH crystals obtained at 90 °C in 40 w$ P.O.. and 3.2 wj H„S0, . 2 5 2 4

45

3.4.5. The fluoride removal

Fluoroapatite phosphoric acid,

contains the

approximately

1 w$ F [1]. During its digestion by

fluoride

is released as hydrogen fluoride. The hydrogen

fluoride reacts with the silica present in the ore or added as a clay, to form a fluorosilicic precipitates remaining turn acid with solution in phosphoric acid. Some of the fluorosilicic acid sodium or potassium ions as Na SiF,, K SiF,, or NaKSiF,. The acid an the partly decomposes in SiF ü and HF, which on their

fluorosilicic evade between In the in

partly

unknown ratio. The residual fluoride in solution is phosphoric acid and the byproduct during its 2,

distributed precipitation.

byproduct, fluoride is assumed to be present as A1F_ 5 2-

which can substitute for SOj. not only makes this acid

[26]. The presence of fluoride in phosphoric acid more corrosive, but also makes it unsuitable for

fertiliser

applications, of

if the concentration is too high. It also causes post like chuckrovite. The fluoride content of the

precipitation byproduct in the

compounds

may also hamper the use of the "phosphogypsum". Discharge of fluoride air is limited in the Netherlands to about 2 ppm for environmental

reasons [1, 33]. So the fluoride discharge the has to be carefully controlled. In commercial mainly evades during digestion and

phosphoric

acid

plants, while

fluoride

crystallisation, stream. Half of

the residual fluoride is stripped from the product acid

the fluoride present in phosphate ore, however, is removed as

solid material, either incorporated in the byproduct or as a sodium or potassium fluorosilicate digestion fluoride air are and precipitate. To calculate the amount of fluoride released during crystallisation and to design the fluoride stripping unit,

distribution needed. Due

coefficients between the phosphoric acid and the ambient to lack were of available data for the our system, fluoride acid and the air as a

distribution function the acid of and

coefficients the

measured

between

operating conditions like: w? P„0 r , w$ H„SO„ and w% H„SiF, in

the temperature. Also the influence of impurities was taken into

account [26]. Experiments three bottles were performed in which a N ? gas stream was first led through phosphoric acid of the desired concentration and

containing without gas

temperature, saturated phosphoric saturate N.

fluoride, was

to saturate the N~ with water. Thereafter, the led through with four bottles containing the same added as H„SiF,, in order to to measure the fluoride

stream but gas

acid, the N„

this with

time

fluoride To be

fluoride.

able

concentration

in the gas, it was led through two absorption bottles filled with

16

water

for

a

given

time. The absorbed fluoride was determined with a fluoride after addition of a buffer solution to keep the ionic

specific

electrode,

strength constant. A theoretical model used to correlate the measured distribution

coefficients is based on a simplified model of the H..PO.-H SiFg-H 0 system [26]. In this model the following reactions are assumed to take place:

SiFg 2 " + 2 H +

<—>

SiF 4 (l) + 2 HF(1)

(8)

SiF^l)

<---> SiF^Cg)

(9)

2 HF(1)

<—>

2 HF(g)

(10)

The fluoride distribution coefficient H, can now be defined as:

total F concentration in the gas phase H total F concentration in the liquid phase (11)

If it is further assumed that the concentration of SiF^ and HF in the liquid are negligible compared to the concentration of SiF, o , equation (11) can be

rewritten as: ( 4 * [SiF^] + [HF] ) gas phase H 6 * [SiF 6
2_

— ]

(12)

Because measured

the with

silica

concentration in the gas phase at 90 °C is too small to be

any accuracy, the separate SiF ü and HF concentrations in the gas

phase are unknown. These concentrations are, however, related to the SiF ü and HF activities in the solution by Henry's law. If the gases are assumed to behave

ideal, these relationships are given by:

[HF] (gas phase) h(HF) a(HF) (13)

and:

47

[SiFjj] (gas phase) hCSiF^) = - - - - a(SiF4) in which a(HF) h(HF) = activity of HF = Henry coefficient of HF (14)

a(SiF.) = activity of SiFy h(SiF.) = Henry coefficient of SiFn If furthermore, a constant ratio q = a(HF)/a(SiF^) is assumed and the equilibrium constant, K, of equation (8), is defined as: a(HF)2 * atSiF^) K = a(SiF62") where * a(H )
+ 2

(15)

(16)

a(H ) = activity of H 22a(SiFg ) = activity of SiFg

equation (12) can be rewritten as: 2 3 1 h(SiF„) [SiFg "] h(HF) * (K * q * a(SiF 2 ") * a(H + ) 2 ) 1 " 3 3
6 2

a(SiF,2") * K * a(H + ) 2
6 2

1 V? q

+ - * — 6 2[SiF^ ]

(17)

Since K, q, h(HF) and h(SiF.) are constants, only the activity coefficients and the hydrogen ion molality are needed to calculate the fluoride distribution 2the SiF, concentration follows from the total amount of added as H.SiF,. The ion specific interaction model of Pitzer [20] can calculated from Elmore's model of phosphoric acid [8], In Pitzer*s as molalities instead of concentrations are used.

coefficient, because fluoride be can well be as

used to calculate the activity coefficients, while the hydrogen ion molality in Elmore's model

18

Therefore, the fluoride distribution coefficient, H is redefined as: total F concentration in the gas phase H = — (18)

H SiF, molality in the liquid phase Equation (17) now becomes: K * a(H + ) 2 H = 1 * h(SiF„) * ( —)°-33 * Y(siF,2") + 6 2 2-2 d q^ * atSiF^ ) K * q * a(H + ) 2 + h(HF) * (— 2-2 )
0 , 3 3

* Y(SiF 2 ~)
6

(19)

in which Y(SiFg ") = the activity coefficient of SiFg Taking the logaritm of equation (19) and rearranging the terms leads to: in H = C. + |* ln(m(H+)) + §* ln(Y(H+)) - ;* m(SiF,2") + \* ln(Y(SiF,2")) 1 3 3 3 . o 3 o where C.
+

(20)

= a constant = molality

Y(H ) = activity coefficient of H + m

Also the temperature influence on the fluoride distribution coefficient can be taken into account by applying a Clausius Clapeyron equation for the relationship contribution is calculated between with the temperature and the gas pressure. Moreover, if the assuming the sulphuric acid to be

of the sulphuric acid to the hydrogen ion molality in the solution Pitzer's model, and

completely dissociated, equation (20) becomes: In H = C, + | * ln(m(H+)) - | » ln(m(SiF62")) + C 2 * ind^PO^) + C 3 * m(H2SiF6) + + C 4 * m(H2S0^) + C5/T (21)

49

The values of the constants, derived from our experimental data, were: C
\

- 32,n

C„ = 0.156
d

C. = 1.0
i

C„ = 0.157
n

C
D

= -9550

The above equation was found to describe the experimental results in the following area: 30 < w? P 2 0 5 < 50 70 < temperature °C < 95 0 < wj H SO,, < 6 w$ H 2 SiF 6 < 4 and a molar F/Si ratio less than 10. The influence of impurities on the distribution coefficient has hardly been studied. Acid from a commercial wet process, however, was used to check equation (21) in for for an impure system. The measured fluoride distribution coefficients were "merchant grade" acid, where the molar F over Si ratio was much higher than fairly good agreement with the values, calculated with equation (21), except

10. In this case, equation (21) cannot be used, because the fluoride is not only present as fluorosilicic acid. It is present also as hydrogen fluoride and monofluoro-phosphoric acid. The existance of mono-fluoro-phosphoric acid was already suggested by Kopylov e.a. [15]. With process can PTFE be and hydrogen equation stage used to (21) produce can be the the amount of fluoride which will release in each

can be estimated. The fluoride recuperated as fluorosilicic acid hydrogen fluoride as well as pyrogenic SiO_ [93. The used in the production of engineering plastics like Si0 ? can be used for the production of ceramic

fluoride

PVDF, while

materials [30]. 3.5. Simplified process flowsheet and mass balance Most reagents. bench-scale This is of In the order plant foregoing to check experiments were performed with chemically pure

the influence of impurities on these results, a only by continuously operating under steady state of HH as well as their respective

has been built, covering the essential parts of the process. because the impurity levels are completely built up. The digestion of the crystallisation

necessary, ore and are

conditions, the phosphate filtrations,

investigated by performing continuous runs in the bench-scale

50

plant.

Not all steps are investigated, owing to the complexity of the necessary results those obtained achieved with with this equipment, showed no essential pure reagents, only the

equipment and the difficulty in controlling the process on a bench-scale. Preliminary differences investigation presented. with only chemically flowsheet

filtration of HH was five times worse. Because all process steps are still under a simplified process and mass balance can be A heat balance is being studied. Basic information about the process

conditions is given in table 1, while the composition of the phosphate ore used, is given in table 2. digestion | recrystallisation | crystallisation | w % P205 wj HgSO,, w$ CaO wj s o l i d s temperature 40.6 28 5.0 40 1.7 10 90 | |

5 4 90

23 60

|
| |

Table 1: Process conditions.

w$ P 2 0 5 w j CaO
w% SOjj

31.55 50.80 2.40 4.24 1.0

w$ F w$ H20

Table 2: Composition of the phosphate ore. The day plant streams process simplified process flowsheet and mass balance for a 1000 tons P-0,. per operating 24 hours in tons to per day, is given in figure 13, where the mass be about 99 %, if the filtration losses are are given per hour. The overall phosphate efficiency of the

can be estimated residence

neglected. Accurate residence times can not yet be given. For the digestion the time, however, will be about 1 hour, for the crystallisation about 30

51

minutes, tanks number

and

for for

the

recrystallisation

approximately 5 hours. The number of

needed of

digestion of phosphate ore will be two or three, just as the required for the recrystallisation of HH into DH. For the

tanks

crystallisation of HH one tank will be sufficient. The HH as well as the DH filter can be vacuum filters. After the digestion, the solids and the CDHP solution may be separated by sedimentation.
Hl

°JW
,)9

,
108 "11
vapour Yi 1113

, ,
36

^
113

H 2 S0 4

ore 132

vapour 4

digestion * - '■ 1052

• *
60

Cd removal
vapour 5 _ _

<— HH crystallisation

137 203 33
" " 46 DH 23 water

1354
138 HH 69 water

recrystallisation
.i ,,

104
recycle acid 1052 product acid 1156

104

Figure 1 3 : Simplified process flowsheet and mass b a l a n c e .
3.6. Conclusions

A well as

new

process for the production of clean phosphoric acid (10 w$ P„0,-) as 2 5 clean calcium sulphate hemihydrate is currently being developed. This

process has the following features: * The rate limiting step in the digestion of phosphate ore by phosphoric acid at 50 °C changes from chemical reaction at low v% P„0 C (about 30 wj) to diffusion beyond 35 wj P ^ . 30 vi$ P 2 0 5 . * Due to the extremely low sulphate concentration in the digester, unground phosphate ore can be used in this process, because blinding will not occur. At 90 °C diffusion will be the rate limiting step also for

52

* The phosphate incorporation in HH can be expressed as a linear relationship between the molar phosphate over sulphate ratio in the solution and in the crystals between 40 - 48 w$ P^Cv at 90 °C. * The phosphate content of the HH crystals decreases with increasing sulphate concentration in the crystalliser. It was found that above 3 w$ H.S0 L in 40 - 48 w$ PpCv» the phosphate content of the HH was lower then 0.1 w$ P 0 . * The Cd incorporation increases with increasing sulphate concentration in the crystalliser for residence times of 20 minutes. * No influence of small variations in stirring rate and residence time on the cadmium and phosphate uptake has been observed. * In the Cd removal step, the Cd concentration has to be lowered until about 3 ppm in solution, to obtain HH with less then 1 ppm Cd incorporated, unless complexing agents for Cd are used. * Due to the precipitation of a quantity of radium in the digestion stage, the HH obtained from the crystalliser contains less radium than HH from commercial processes. * Separation of the solids after the digestion stage is difficult due to the presence of fine ore residue particles. * A maximum filtration rate has been observed with HH crystals obtained from phosphoric acid containing 40 w$ P.0_ and about 1.8 w% H„S0„. * The filtration rate of the HH crystals decreases with increasing residence time, above 20 minutes, in the crystalliser. * It is recommended that, in the crystallisation stage, the sulphate concentration should not exceed 2 w? H.SO,,, because of the steep increase in Cd incorporation and the relatively slow decrease in phosphate incorporation with further raising sulphate concentrations. Moreover, the filtration rate is decreasing with increasing sulphate concentrations above 2 w$ H.SO.. * An equation has been derived for the calculation of the fluoride distribution coefficient as a function of the operating conditions. 3.7. Literature 1. 2. Becker, P., (1983), Phosphate and Phosphoric Acid, Fertiliser Science and Technology Series, Vol. 3, New York, Marcel Dekker, Inc. Burova, M.S. and Kazak, V.G.,0985), Crystallization of calcium nitrate from nitric-phosphoric acid solutions in the presence of an inert coolant. Khim. Prom. 1 (1985) 29.

53

3. I. 5.

Chemische Fabrik Budenheim, DE 3218599 A1 1-2-1983, DE 3327391 A1 11-2-1985. Chemische Fabrik Budenheim, DE 3332698 21-3-1985. Dahlgren, S.E. and Hakansson, R., (1966), Manufacture of 10-45 per cent P-Cv
d D

phosphoric acid by the semihydrate process. Acta Polytech. Scand. Chem. Met. Ser. 52 (1966) 3. 6. 7. 8. DSM NL-Patent NOS 8006916 20-12-80. Elmore, K.L. and Farr, T.D., (1910), Ind. Eng. Chem. 32, 1 (1910) 580. Elmore, K.L., Hatfield, J.D., Dunn, R.L. and Jones, A.D. (1965), Dissociation of phosphoric acid solutions at 25 °C, J. Phys. Chem. 69 (1965) 3520. 9. Flemmert, G.L. (1977), Hydrogen fluoride and pyrogenic silica from fluosilicic acid. The Fertiliser Society of London, proceedings No 163. 10. Frochen, J., Laine, J., Allyot, H. and Gosse, G. (1972), Concentrated phosphoric acid manufacturing process by double crystallization. Bulletin d'informations HEURTEY No 57 (1972). II. Hignett, T.P. and Mudahar, M.S. (1985), Energy consumption in the world fertilizer sector. Fertilizer Technology 1, 1 (1985) 39. 12. Hunter, D. (1985), Low-Cadmium H.-PO^ for fertilizer use. Chemical Week 136, 8 (1985) 25. 13. Jansen, M., Waller, A., Verbiest, J., Van Landschoot, R.C. and Van Rosmalen G.M. (1981), Industrial Crystallization '81 The Hague, Jancic and De Jong, ed., pg 171. 11. Knudsen, K.C., (1985), The Fertiliser Society of London, Proceedings of 3 oct. 1985. 15. Kopylov, V.A., Senotova, G.I. and Pozin M.E. (1975), Equilibrium partial vapor pressure of HF, SIFj. and H„0 over solutions of the system H.PO.,-H_SiF,-H_0, Zh. Prikl. Khim. 18, 11 (1975) 2155.
3
H

d

0

d

16. Leder, F., Park, W.C., Chang, P.W., Ellis, J.D., Megy, J.A., Hard, R.A., Kyle, H.E., Mu, J. and Shaw, B.W. (1985), New process for technical-grade phosphoric acid, Ind. Eng. Chem. Process. Des. Dev. 21 (1985) 688. 17. Nordengren, S., Francia, I. and Nordengren R. (1955), The firs.t installation of a phosphoric acid plant according to the anhydrate method at Verticelli, Italy. The Fertiliser Society of London, Proceedings No 33. 18. Phosphoric acid manufactoring using hydrochloric acid. Phosphorus and Potassium 125 (1983) 29. 19. Phosphoric Acid, Outline of the industry. British Sulphur Corporation Limited, London, 1981.

51

20. Pitzer, K.S. (1973), Thermodynamics of electrolytes. 1: Theoretical basis and ground equations, J. Phys. Chem. 77 (1973) 268. 21. Purifying wet-process phosphoric acid. Phosphorus and Potassium 139 (1985) 34. 22. Silverman, S.R., Fuyat, F.R. and Weiser, J.D. (1952), Am. Mineralogist 37 (1952) 211. 23. Sluis, S. van der, (1987), PhD thesis. To be published. Technical University of Delft. 24. Sluis, S. van der, Leenhouts, W., Wesselingh, J.A. and Rosmalen, G.M. van, (1987), Filtration and washing of calcium sulphate-phosphoric acid slurries. To be published. 25. Sluis, S. van der, Murach, Z., Wesselingh, J.A. and Rosmalen, G.M van (1986), The predigestion stage of a new phosphoric acid process, Procedings of World Congrss 111 of Chemical Engineering, Tokyo, Japan, Vol. 4, (1986) 96. 26. Sluis, S. van der, Schrijver, J.H.M., Baak, F.P.C, and Rosmalen, G.M. van, Fluoride distribution coefficients in wet phosphoric acid processes, to be published. 27. Sluis, S. van der, Witkamp, G.J. and Rosmalen, G.M. van (1986), The crystallization of calsiumsulfate in concentrated phosphoric acid. J. Cryst. Growth, 79, (1986) 620. 28. Societe Uranium Pechiney. patent NL 8403788, 16-06-1985. 29. Taperova A.A. and Shulgina, M.N. J. Appl. Chem., (USSR), 23, (1950), 27. 30. Technisch Keramiek, Technieuws W-84-09, okt. 1984. Ministerie van Economische zaken, Direktie R. en 0., 's Gravenhage. 31. The nitro-phosphates alternative. Fertilizer international 209, (1985) 8. 32. Tjioe, T.T., Weij, P. and Rosmalen, G.M. van (1986), "Removal of cadmium by anion exchange in a wet phosphoric acid process", Proceedings of World Congress 111 of Chemical Engineering, Tokyo, Japan, Vol. 2, (1986) 925. 33. UKF, private communications (1986). 34. Willis, M.S., Tosun. I. and Collins, R.M. (1985), Filtration mechanisms. Chem. Eng. Res. Des., 63, (1985), 175. 35. Witkamp, G.J., Schuit, S.P.J. and Rosmalen, G.M. van (1986), Recrystallization of calcium sulfate modifications in phosphoric acid, Condensed papers of the Second International Symposium on Phosphogypsum, University of Miami, W.F. Chang ed., Miami, Florida, USA, (1986) 106.

55

1. THE DIGESTION OF PHOSPHATE ORE IN PHOSPHORIC ACID 1.1 . Summary Phosphoric the in 2000 important phosphoric acid acid is used for fertiliser applications. To minimize

environmental pollution by heavy metals, a new process is being designed. One of steps in this process is the complete digestion of phosphate ore acid. were The rates determined. acid of 60 and of digestion of from of fluoroapatite particles in was varied from 150 to
anci t h e

phosphoric temperature controlled digestion rate model

The particle

size

ym, the phosphoric between by process transport

concentration ions to

30 to 50 w$ P 2 0 c

90 °C. The rate calcium

digestion was found to be

the solution. A model for the

was developed, based on the diffusion of calcium ions as the

limiting on

step. The masstransfer coefficients, calculated by applying this

the experimental data, are slightly increasing with temperature and -5 -1 have values of 5 to 10 * 10 i « 3 1.2. Introduction Phosphoric yields acid is a major as a component of many fertilisers. It is mainly and hydrated calcium sulphate as a

produced by digestion of phosphate ore (fluoroapatite) with sulphuric acid. This phosphoric acid product byproduct. The ore also contains traces of heavy metal ions, of which cadmium A new "clean technology" phosphoric acid (CTPA) process is

and radium are the most worrisome. They can cause serious environmental problems (Becker,1983). This therefore being developed to reduce these problems (Van der Sluis e.a.,1986). process aims at producing a 10 w$ P ? 0_ solution, with less than 5 ppm to the conventional acid processes, the ore is not digested in a cadmium and hydrated calcium sulphate with less than 1 ppm cadmium. Contrary mixture phosphoric simultaneous obtained, 1986). After removal of the cadmium ions, the precipitation of the calcium ions is performed by adding sulphuric acid. of sulphuric acid. and recycled phosphoric acid, but only in recycled of all calcium sulphate. After separation of the

This allows almost complete digestion of the ore, without the

precipitation which

insoluble ore residue and a minor amount of calcium sulphate a clear solution is from the cadmium can be removed by ion exchange (Tjioe e.a.,

56

Large phosphoric Several

equipment acid

is

required,

due

to

the

very large recycle stream of

needed for complete digestion. For its design reliable data on have been devoted to this subject, which are

the digestion rates are a necessity. publications contradictory. unfortunately proposed: - diffusion of calcium ions away from the particle. (Serdyuk e.a., 1982 and Hufmann e.a., 1957) - diffusion of hydrogen ions towards the particle. (Bloise e.a., 198H) - the chemical reaction of the acid with the ore particle. (Ivanov e.a., 1977) This inconsistency explains, why the subject was reinvestigated under the conditions expected in the CTPA process. t.3. The digestion stage of the CTPA process The phosphate phosphate If phosphate ores used in wet processes today are mainly sedimentary Three different rate determining steps have been

phosphates or francolites. These ores consist of fluoroapatite, with part of the ions replaced by fluoride and carbonate ions. By beneficiation of the rock, large amounts of waste material are removed. The phosphate ore, phosphate ore is digested by phosphoric acid, the following reactions

however, still contains residual waste components. can take place (Elmore and Farr, 1940): U H-POjj

Ca 1Q (P0 lt ) 6 F 2

+

>

10 CaHPO^

+ 2 HF

(1)

Ca

iO(P04)6F2 The

+

14 H

3 P °t

>

10 C a ( H 2

P0

H)2

+ 2 HF

<2>

amount of calcium ions, which can be dissolved strongly depends on the as well also as on the phosphoric acid concentration of the solution. determine, which type of calcium phosphate is formed as

temperature These

parameters The

shown in figure 1 (Elmore and Farr, 1940). phosphoric stream acid used for the digestion is recycled product acid. This recycle unavoidably contains sulphate ions in an amount dictated by the

operating conditions in the crystalliser. So part of the calcium sulphate, up to a maximum of 25 w%, will precipitate during digestion.

57

When of the

a mixture

of

phosphoric

acid

and

sulphuric acid is used for the

digestion of the ore, two processes occur more or less simultaneously: digestion ore and precipitation of calcium sulphate hemihydrate. At high sulphate the calcium sulphate tends to precipitate not only upon the crystals, but also upon the ore particles. Such a coating is often concentrations hemihydrate

called blinding (Becker, 1983).
6_i

w%CaO

54321100°C

^V

30

35

40

45

w%P 2 0 5

Figure 1: Solubility of CaO in phosphoric acid Since obtained, carefully keep Sluis the a the high digestion acid rate, as well as complete digestion should be in the digestion stage has to be

sulphuric

concentration

selected to avoid blinding. In a continuous process blinding can only sulphuric 1986). crystals acid concentration sufficiently low (< 2 w$ H-SO^MVan der Under such conditions, sulphate ions precipitate upon the and the digestion process can be treated as if proceeding

be avoided by maintaining a high calcium concentration in the digestion stage to e.a.,

hemihydrate In most the used (mono solid as a the of calcium-(mono hardens digestion

in pure phosphoric acid. of the work on the digestion process, as presented in literature, is a coprecipitate of hydrated calcium sulphate and solid since this product is often directly or di)-hydrogen-phosphate, product

fertiliser. The complexity of this combined precipitation, however, unraveling of the mechanisms of the individual steps. The calciumthe phosphate ore in a large amount of phosphoric acid, at low

or di)-hydrogen-phosphate can, however, also be produced as a solution by

58

sulphate calcium (Hufmann 1982). 24-47 even w$

concentration. diffusion e.a., both, 1957)

In this case the rate determining step was found to be in diluted in 47 phosphoric acid (< 5 w$ P.0C) at 25 °C and wj P ^ , between 15 and 85 °C (Serdyuk e.a,

It was, however, also reported to be a fourth order chemical reaction in P-O^, between 80 and 120 °C (Ivanov e.a., 1977). The confusion became
£ D
. . .

larger, when in 1984 a mathematical model was presented, in which the rate step ions of to the the digestion particle be step at 70 °C was assumed to be diffusion of surface drawn (Bloise e.a., 1984). No unambiquous about the rate determining step of the

limiting hydrogen conclusion

could

therefore

digestion process.

1 = thermostated reactor, 2 = polypropene baffles, 3 = six-bladed polyvinylidene fluoride starrer, 4 = thermometer, 5 = polypropene lid with silicon-rubber seals, 6 = syringe, 7 = reflux cooler. The sampling hole is not shown.

Figure 2: Experimental reactor used for digestion of phosphate ore in phosphoric acid. 4.4. Experimental The fractions obtained ore stirred phosphate (150 ore used was Zin ore from Israel. Four different size

- 212 ym, 425 - 500 ym, 1000 - 1180 ym and 1700 - 2000 ym) were

by sieving through "Twente" sieves. To remove agglommerates of smaller twice with about 2 kg of distilled water and sieved again. Then the

particles from these fractions, 500 grams of each size fraction were gently

59

fractions acid (85

were dried at 60 °C for at least 21 hours. Chemically pure phosphoric wj H^POj.) and distilled water were used to prepare the solutions

containing 30,40 and 50 w$ P0CL (i.e. 11, 55 and 69 wj H.PO,,). d 3 3 1 Figure 2 shows the reactor used, a double walled glass vessel with baffles. The temperature was kept at a constant value of 60, 75 or 90 °C by a thermostat. To prevent evaporation of water during the experiment, the vessel was

equiped with a polypropene lid with a reflux cooler. A 50 ml plastic syringe was used to feed by the the ore suspension turbine in water to the reactor. The power input, 3 stirrer, was maintained at about 5 kW/m

provided (1000

six-bladed

rpm). This

power input is sufficient to keep even the largest particles

suspended. An grams This of amount water of and was 20 or 10 grams of an ore fraction was suspended in 8 or 16 1 to 3 grams of antifoaming agent in the plastic syringe. added to 500 or 1000 grams of phosphoric acid of the

suspension

selected

concentration and temperature. In this way an instantaneous suspending

of the ore particles in solution was obtained. The digestion process was followed by taking 3 ml samples from the reactor

with a "Finn"-pipette. Sampling intervals varied between 15 seconds at the start to and 15 minutes towards the end of the experiment. The samples were immediately

quickly

filtered over Teflon filters, provided with "Millipore AP 2002500"

filter cloth. The filtrate was accurately weighted. The and/or a CaO content of the filtrate was analysed by ICP (Klok e.a., 1985)

potentiometric

titration

(Jordan and Monn, 1967; Pribil and Vesely,

1966; Szekeres e.a., 1965). 1.5. Results

The of the

results are shown in the figures 3, 1 and 5 for various concentrations phosphoric acid (30, 10 and 50 wj P 2 °5^*
the

temperature (6o, 75 and

90 °C) and the mean particle sizes (181, 163, 1090 and 1850 ym). Since the Zin phosphate ore used is a mineral, it is not homogeneous. As a

consequence the CaO content of each particle size fraction is different as shown in table 1. The estimate final the CaO CaO concentration reached in the solution is therefore used to content of the ore particle size fraction, used in that

particular experiment.

60

Figure 3: Digestion curves for phosphate ore in phosphoric acid containing 30 w$ P»0_ at three temperatures; mean ore particle diameter: 2 5 a = 181 ym, b = 463 ym, c = 1090 ym and d = 1850 ym.

Figure 4: Digestion curves for phosphate ore in phosphoric acid containing 40 w$ P.0_ at three temperatures; mean ore particle diameter: a = 181 ym, b = 463 ym, c = 1090 ym and d = 1850 ym.

Figure 5: Digestion curves for phosphate ore in phosphoric acid containing 50 w$ Pj^c; a ^ three temperatures; mean ore particle diameter: a = 181 ym, b = 463 ym, c = 1090 ym and d - 1850 ym.

61

I mean particle size (urn) 181 463 1090 1850 | | | | I

Analysis of w? CaO (ICP) 1 55.3 53.0 50.8 52.2 50.6 51.3 2 52.9 3 53-0

Table 1: CaO content of Zin phosphate ore. 4.6. Discussion 4,6.1. Influence of the phosphoric acid concentration The the particle phosphate shows, P Cv. effect size, that the of ore the the phosphoric acid concentration on the digestion rate of was studied of at constant values of: the stirrer speed, the and the the figures weight ratio of phosphoric acid and 3a, 4a and 5a up to 3d, 4d and 5d temperature

phosphate

ore. Comparison

time needed for complete digestion increases from 30 to 50 w? table 2.

This is probably due to the raise in viscosity with increasing phosphoric

acid concentration as shown in Temperature °C 60 75 90 | I | | |
do

Phosphoric acid concentration 30 wjt P o 0 c 1.69 1.37 1.14 40 w* P,0C
do

50 wj P o 0 c
d O

^^

2.88 2.30 1.88

5.47 4.21 3.31

Table 2: Viscosity data (n * 1O 3 Ns*m The diffusion particles, Moreover, viscosity rate. is a is The is of strong

) for phosphoric acid (Slack, 1968)

an important parameter, because of its influence on the decreasing most digestion rate with increasing acid clearly ions revealed by the curves for the largest is commonly considered to proceed very

concentration, which diffusion

argument against a hydrogen ion diffusion limitation. hydrogen

62

fast.

Either

the

diffusion of calcium ions or the chemical reaction therefore

seem more likely to be the rate controlling step in the digestion process. 4.6.2. Influence of the temperature The and cases, is, effect the time The of the temperature can also be observed from the figures 3, 4 to reach complete digestion decreases with increasing between the digestion rates for 60, 75 and 90 °C By using only the slope at t = 0 of the digestion 3» '4 and 5, an almost constant energy of

5, and in particular from the curves for the largest particle sizes. In all needed differences small. the in

temperature. curves value

however, rather presented

figures

activation of the digestion process, Ea, has been calculated for each curve. Its was about 15 kJ per mol, independent of particle size and phosphoric acid This rough value of Ea, indicates that the digestion rate is not a chemical reaction, which normally is more sensitive to the by concentration. controlled temperature.

4.6.3. Conclusion From of the results obtained, it is reasonable to assume, that the diffusion

calcium ions from the surface of the reacting ore particles into the bulk of In the the following sections a kinetic model of the digestion process, based will be derived and the experimental data will be used to masstransfer coefficients and thus to verify the validity of the

the solution is the rate determinig step of the digestion process. on this assumption,

calculate model.

4.7. A kinetic model of the digestion process In this section a model wil be developed for the digestion process of ore

particles of one size, which is based on the following assumptions: - the transport of acid to the surface of the particles proceeds fast. - at the surface, the acid rapidly reacts, until the saturation concentration of Ca(HoP0„)„ is reached.

63

- the transport of this calcium phosphate into the solution is rate limiting. The masstransfer coefficient, k for its transport has a constant value. - the particles of one size fraction are spherical and have the same initial radius, RQ. They do not desintergrate during digestion. - the solution is well mixed. The rate at which calcium ions (taken as CaO) diffuse from a single particle into the solution is then given by: f * ~ = k * A * (c - c j dt s t Since the particles (1)

are spherical, their mass, M and external surface area, A

are given by: M = p * 5 *
A
I T

* R3

(2)

-n *

T T * R2

(3)

This leads to:

f

* »s * o1=k * (cs - V

<">

It is convenient to simplify this equation by introducing the ratio's:

R

- g-,

o - --

and

t =

T r 5

-g--S-;-j.

This yields:

— ; - 1 - o dt A second relation is obtained from the total CaO balance: M 0 = Mfc + L * cfc

(5)

(6)

64

After

complete

digestion

the final

CaO concentration in the solution, c is

obtained: MQ = L * cf Eq. (6) and (7) are easily combined to give: M
M

(7)

c
C

0

f

or in a dimenslonless form:

R*3 - 1 - Si
c f with p = — c s

(9)

So o = p « ( 1 - R 3) Together eq. (5) and (10) yield:

(10)

----;= = dt* a +p* R with a =

(11)

( 1 - p). Integration of the left hand side of eg. (11) (Weast, 1976)

leads to:

F(R*> ■ 3-5" * [\ * I" (^~-5-2-«) ♦ /3 * arctan (-2--X---"-))

(12)

with Y = (a/p) 1/3 . In a digestion experiment the following parameters are known beforehand, R and e„. s The are those determined by Elmore e.a. » (Elmore e.a., 19^0). If c , . and c. are measured, R can be calculated from eq. r * * (9) and so the corresponding value of F(R ). According to eq. (11) a plot of * F(R ) against time should give a straight line with a slope: c 3 values used in this paper

65

k *c

f"-R--;-- P ;
The masstransfer coefficient, k is then determined by the value of this slope. The density density of pure fluoroapatite is 320O kg/m 3 (Weast, 1976). The real of the Zin ore was estimated with a pyknometer to be about 2700 kg/m 3 .

This value was used in the calculations. 4.8. Determination of the masstransfer coefficient The line figure function F(R ) given by eq. (12) was plotted against time for all

experiments regression 6.

presented in the figures 3, 4 and 5. For each experiment a straight coefficient From larger than 0.99. Examples of these fits are given in

was obtained, which could be fitted by the method of least squares with a the slope of the straight lines, the masstransfer coefficients

were calculated. These values are presented in table 3. FIR')
60 °Crc= 0,994 75°Crc= 0,999 90 °C re =0,991 • X D 30w%P 2 O 5 40w%P 2 05 50w%P2O5

«-

100 lime Is)

Figure 6: F(R ) as a function of time in 40 w$ P„0_ a t t h r e e temperatures for a mean ore p a r t i c l e diameter of 463 \m-

1 Figure 7: In k as a function of T and the phosphoric acid
concentration for a mean particle diameter of 463 ym.

66

For a given temperature, the masstransfer coefficients depend only slightly on the particle for size. the of Their values are close to those predicted by existing coefficients of particles in mixed vessels correlations The digestion phosphoric increase masstransfer the

(Calderbank, 1961). influence proceeds acid in phosphoric acid concentration can best be observed A slight decrease of the k values with increasing is in observed. table This decrease is caused by the 2 and also follows from the existing from the results obtained for the largest particle size fractions, because their slowest. given concentrations

viscosity,

correlations. concentration of phosphoric acid and temperature 30 wj P 2 0 5 mean diameter of the ore particle size fraction

r n 181 u

463 pm

1090 u r n

1850 ym

60 75 90
40 w* P 2 0 5

4 6 7

4 6 8

5 7 9

7 9 11

60 75 90
50 w* P 2 0 5

5 6 8

5 6 7

5 6 8

6 8 9

60 75 90

4 6 7

4 5 6

4 6 7

4 7 8

Table 3: Calculated k values (« 10 m * s ). The a small can temperature increase on be the of also the has k a slight influence on the k values. Due to the values with temperature. The influence of the . In figure 7

decrease of the viscosity and the increase of the diffusion coefficient there is temperature which digestion process can be related to an activation energy,

obtained

from an Arrhenius plot of In k versus T

67

this is illustrated for one particle size fraction (463 um) and three phosphoric acid concentrations (30, 40 and 50 u% P 2 0 5 ) . The energy of activation appeared to be independent of the particle size fraction and nearly independent of the phosphoric acid concentration. Its value lies between 13 and 23 kj/mol, an order of magnitude expected for a diffusion controlled process. t.9. Conclusive remarks Although Huffman e.a. (Huffman e.a., 1957) also found that calcium ion diffusion was the rate limiting step of the digestion process, their model did not take into account the considerable change in surface area of the ore with time. Their equation describing the digestion process in diluted phosphoric acid is therefore too simple and cannot be used to calculate the masstransfer coefficients. The model presented by Serdyuk e.a. (Serdyuk e.a., 1982) was an empirical model, in which a coefficient of digestion was introduced and an undefined constant. Their model is thus only applicable within the limits of their experiments and cannot be used to calculate masstransfer coefficients, because the relationship between the rate of digestion and the masstransfer coefficient is not well defined. The model used here does not suffer from these disadvantages. ore From the foregoing, it can be concluded that the digestion of Zin phosphate in chemically pure phosphoric acid (30 - 50 w$ P»0_) between 60 and 90 °C
d. o

can be described by a model in which calcium ion diffusion is the rate limiting step. 1.10. Nomenclature A c. external surface area of the phosphate ore CaO concentration in the bulk of the solution after complete digestion of the ore saturation concentration of CaO in phosphoric acid CaO concentration in the bulk of the solution at time t weight fraction of CaO in the phosphate ore mass of phosphoric acid masstransfer coefficient mass of the phosphate ore at time t radius of an ore particle (mean) at time t 68 m 2 -3 c
3

kg * m kg * m

-■*

-3 kg * m kg m * s kg m

c f L k M R

t p

time density of the Zin phosphate ore

s kg *

1.11. Literature 1. Becker, P., Phosphate and Phosphoric Acid, Fertiliser Science and Technology Series, Vol. 3., Marcel Dekker Inc., New York (1983). 2. Bloise, R., Shakourzadeh, K. and Baratin, F., Industrie Minerale Techniques, 9 (1984) 721. 3. Calderbank, P.H. and Moo-Young, M.B., Chem. Eng. Sci., 16 (1961) 39. 4. 5. 6. 7. Elmore, K.L. and Farr, T.D., Ind. Eng. Chem., 32, 4 (1940) 580. Huffman, E.O., Cate, W.E., Deming, M.E. and Elmore, K.L., J. Agr. Food Chem., 5, 4 (1957) 266. Ivanov, E.V., Zinyuk, R.Yu. and Pozin, M.E., Zh. Prikl. Khim., 50, 6 (1977) 1193. Jordan, D.E. and Monn, D.E., Anal. Chim. Acta., 37 (1967) 42. Proc. XXIV Colloq. Spectrosc. Intern. (1985) 98. 9. Pribil, R. and Vesely, V., Talanta, 13 (1966) 233Zh. Prikl. Khim., 55, 10 (1982) 2190. 11. Slack, A.V., Ed., Phosphoric Acid, Fertiliser Science and Technology Series, Vol. 1., Marcel Dekker Inc., New York (1968). 12. Sluis, S. van der, Meszaros, Y., Wesselingh, J.A. and Rosmalen, G.M. van, Proc. of the Fertiliser Society of London, nr. 249 (1986). 13. Szekeres, V.L., Kardos, E. and Szekeres, G.L., J. fur Praktische Chemie, 4, 28 (1965) 113. 14. Tjioe, T.T., Weij, P. and Rosmalen, G.M. van, Proc. of World Congress 111 of Chemical Engineering, Tokyo, Japan, Vol. 2 (1986) 925. 15. Weast, R.C., Ed., Handbook of Chemistry and Physics, 57 CRC Press Inc., Cleveland, Ohio (1976) A-116.B-241. ed, 10. Serdyuk, V.V., Tereshchenko, L.Ya., Panov, V.P. and Chekreneva, G.M., 8. Klok, A., Tiggelman, J.J., Weij, P., Dalen, J.P.J. van and Galan, L. de,

69

5. CRYSTALLISATION OF CALCIUM SULPHATE HEMIHYDRATE 5.1. Summary In a continuous crystallisation procedure calcium sulphate hemihydrate (HH) crystals in were formed by feeding a calcium-di-hydrogen-phosphate (CDHP) solution concentrated phosphoric acid (5.6 and 6.6 mole H.P0 u per kg), simultaneously occurred The unclassified. Residence times of 20 to 80 minutes were

with a sulphuric acid solution, into a 1 liter crystalliser at 92 °C. The slurry removal maintained. over solid over liquid weight ratio depended on the calcium content ratio in of the solution was varied between about 0.05 and 8. A

of the CDHP solution. By slight adjustment of the feed streams the molar calcium sulphate cadmium concentration 30 ppm was maintained in the crystallising solution.

The shape of the HH crystals varied with increasing sulphate concentrations from mainly aggregates to mainly needles. During the The is of crystallisation conditions. over of The the HH crystals, cadmium as well as phosphate uptake in the decreases crystals with is increasing found to be

ions are incorporated into the lattice. The degree of uptake strongly depends on operating molar also 20 phosphate ratio sulphate concentrations in the crystalliser, while the cadmium uptake increases. phosphate sulphate proportional to the same ratio in the solution. A comparable linear relationship observed for the molar cadmium over calcium ratios at a residence time minutes. At high sulphate concentrations, long residence times and high 95 °C) the stable anhydrite modification (AH) tends to (about

temperatures

develop next to the metastable HH phase. The cadmium uptake in AH is at least 10 times higher than in HH, while the phosphate uptake is not influenced by a small amount of AH in the crystals. The cadmium incorporation in the HH lattice can be reduced by adding halogenides to the solution.

5.2. Introduction During amounts only of the tends the the to production of phosphoric acid for fertiliser applications huge incorporate phosphate ions, but also cadmium ions, originating

of calcium sulphate are precipitated as a byproduct. This byproduct not

from the phosphate ore [1,11]. Uptake of phosphate lowers the overall efficiency process [i|], while the incorporation of cadmium hampers the disposal of due to environmental restrictions. In order to obtain hydrated byproduct

70

calcium In is

sulphate this

with

a low cadmium and phosphate content from concentrated

phosphoric acid, a new process is being developed. process [t] a clear calcium-di-hydrogen-phosphate (CDHP) solution by digestion acid, enabling of the phosphate ore (fluoroapatite) in recycled 2+ the removal of Cd ions by e.g. ion exchange [17]. obtained

phosphoric the and

Thereafter the major amount of calcium sulphate hemihydrate is precipitated from CDHP solution by adding sulphuric acid. The incorporation of phosphate ions of the remaining The amount cadmium ions during ions this crystallisation has to be of foreign incorporated largely depends on the

minimized. operating determined impurities uptake

conditions, given by the H.PCv and H-SO. content of the solution, the and the supersaturation, which is, in our experiments, on its turn originating ions from the ore or purposely added components affect the sulphate. Components which are able to by the residence time and the solid over liquid weight ratio. Also by calcium

temperature,

of foreign

coordinate the cadmium ions in solution, like e.g. halogenides [8,9], reduce the cadmium uptake.

1 1 5 10 ^ mole h^PCykg
Figure 1: The precipitated calcium sulphate phase'as a function of the H,PCv content and temperature of the solution. Note that H H only e x i s t s as a metastable phase, and that A H i s s t a b l e in a very wide range of conditions. Our working conditions are indicated with a + sign.

71

The uptake of

nature

of the precipitated calcium sulphate phase also influences the ions. Depending on the temperature and the H^PCK and H SO,

foreign

content of the solution either calcium sulphate dihydrate (DH), hemihydrate (HH) or anhydrite (AH) will be formed [16], as shown in figure 1. The solid lines in figure 1 represent equilibrium curves, but since some of the modifications are metastable under the given conditions, these lines merely which phase will initially precipitate. The broken line in figure 1 the regions where either DH or AH is stable. The HH phase only exists indicate separates as with figure

a metastable phase. The influence of H_SOü on the position of the curves in 1 can be taken into account by assuming 1 mole of H?SOj, to be equivalent about 1.5 mole of H-POn [1]. The working conditions in our process, where

HH is produced, are indicated in figure 1. The phosphate conditions with the aim of the present study is to investigate the incorporation of both

and cadmium ions in HH in dependance on the above mentioned operating during continuous crystallisation. In addition a start has been made investigation of the influence of halogenides on the incorporation of

cadmium ions. 5.3. Experimental In all experiments chemically pure H PCv, H-SCL, 3CdSCL.8H_0 and ammonium were is used. The CDHP solution was prepared by dissolving CaCO.. in a restricted 5.6 3*10 mole by its solubility and was about 1 mole/kg in a (55 w$ H_PCL) and approximately 0.6

halogenides CDHP

concentrated phosphoric acid solution at about 92 °C. The calcium content of the solution in solution mole/kg solutions containing contained H.PCv/kg

a solution

containing 6.6 mole H.PCv/kg (65 w% H-PCL). The CDHP -4 2+ mole Cd /kg, which is the same as in the acid was added in the experiments where a solution

crystalliser. Concentrated containing sulphuric 5.6 mole H-POjVkg was feeded into the crystalliser, while a solution

containing 1.7 mole HpSCv/kg and 5.4 mole H,P0^/kg was added in experiments with 6.6 mole H_P0j. per kg solution in the crystalliser. In (PVDF) figure of turbine 2 the experimental set-up is given. The 1 liter double-walled was provided with a six bladed polyvinylidene fluoride crystalliser glass

stirrer. The CDHP and the sulphuric acid inlet tubes as well as

the drain tube served as baffles. The power input, generated by the stirrer, was calculated from the stirrer speed, the slurry density, and the geometry of both (stirrerspeed 640 vessel and stirrer [1], and was normally approximately 1 kW/m

72

rpm). 92 °C

The supply vessels as well as the crystalliser were thermostated at about except for the concentrated H2S0n
su

PP!y vessel, which was kept at room

temperature. Peristaltic pumps were used, equipped with marprene or viton tubes.

Figure 2: Scheme of the crystallisation apparatus. At the start of each experiment the crystalliser was filled with a solution composed amount of performed by in accordance with the selected experimental conditions and an adapted HH by from a former experiment. The continuous crystallisation was simultaneous addition of the CDHP solution and the sulphuric acid unclassified, of the removal of slurry from the crystalliser. The

solution to the crystalliser. The slurry volume in the reactor was kept constant continuous, time each residence In to used To be slurry, a defined as the reactor volume divided by the

slurry volume stream, was varied in the experiments from 20 to 80 minutes. experiment steady state was obtained after 8 to 10 residence times. For experiments were no HH was initially added, a longer runtime appeared necessary containing vary to obtain a steady state. In experiments where solutions were 5.6 mole H P0./kg solution, the solid over liquid weight ratio

was about 0.11, while in case of 6.6 mole H POjj/kg solution this ratio was 0.05. the H SO^ content of the solution from 0.02 to 0.35 mole/kg at a given corresponding with molar calcium over sulphate ratios about 0.1 and 8, only small changes in the CDHP and H 2 S0 1) feed streams H-POjj between concentration,

73

were

needed.

The

influence

of such small variations on the solid over liquid

ratio was negligible. Also the residence time had hardly any effect on it. After each residence time unclassified samples were taken from the

crystalliser with a sample tube. This tube was connected with a G.-glass filter, placed a reception tube under vacuum. The liquid was diluted with water and 2+ analysed for its phosphate and sulphate content by X-ray fluorescence, its Ca 2+ content by complexometric titration and its Cd content by inductively coupled plasma about at 60 spectroscopy (ICP) [7]. The crystals were washed two times with water of °C, saturated with gypsum and then three times with acetone and dried 2The HPCv content of the crystals was determined by colorimetry, 2+ the Cd content was measured by ICP. X-ray diffraction was used to °C. 90 on

while

identify the phase of the crystals.

Figure 3a: HH crystals obtained at 92 °C in 5.6 mole H.POj,/ kg and 0.05 mole f^SO^/kg.

5.4. Results and discussion

5.4.1. The hemihydrate crystals

When a solution

hexagonal calcium sulphate hemihydrate crystals are precipitated from containing 5.6 or 6.6 mole H,P0j,/kg, where the calcium ions are in

74

excess

of

the sulphate ions, aggregates are formed. Each aggregate consists of

numerous needles originating from one point and outstretched like the radii of a sphere (see figure 3a) • At as higher increasing [H S O J sulphate concentration in the solution, further referred to separate needles are grown, which are longer and [H„SO.], separate needles start to be formed beside the aggregates. At still mostly thinner. In addition some bundles of two or more needles are formed,

relatively

which are often oriented in twin positions (see figure 3b).

Figure 3b: HH crystals obtained at 92 °C in 5.6 mole H,P0,,/kg and 0.24 mole H S0^ /kg. At In smaller hampered [H S O J 6.6 than mole in those beyond about 0.25 mole/kg many tiny needles are formed, beside H P0n/kg solutions obtained to diffusion aggregate in the formation still occurs at much higher

needles with a length up to 2000 ym (see figure 3c). [H-SO.] than containing 5.6 mole H.PO./kg. Also the needles are 5.6 mole H_P0u/kg. This might be caused by a tops of the needles, due to the higher

volume

viscosity of the solution containing 6.6 mole H,P0j./kg. In many of the long needles, hollow cores were observed in the direction of the c-axis (see figure 3d).

75

Figure 3c: HH crystals obtained at 92 °C in 5.6 mole H-POj/kg and 0.32 mole H S0^ /kg.

Figure 3d: SEM view of hollow cores in HH crystals.

76

Examination some in fixed the crystals operating that

of is a

the

obtained

c r y s t a l s by X-ray d i f f r a c t i o n r e v e a l e d t h a t

of t h e batches of c r y s t a l s contained a n h y d r i t e . The d e t e c t i o n l i m i t for A H approximately 0.5 - 1 w%. The amount of A H varied even a t In and spite of a a of this i r r e p r o d u c e b i l i t y , i t can be residence time, dosage of combination acid of prolonged conditions.

concluded concentrated The high

sulphuric

high [H„S0,J in t h e s o l u t i o n promotes the A H is enhanced, when the o p e r a t i n g

formation of AH. conversion and/or sulphuric rate H H into c o n d i t i o n s are approaching t h e HH-AH e q u i l i b r i u m l i n e given in f i g u r e 1, i . e . at [HpSOn] [H P O J and a t temperatures close t o 95 °C. The dosage of acid might l o c a l l y induce A H n u c l e i . Once A H nuclei a r e concentrated

p r e s e n t , t h e r e s i d e n c e time becomes very important. 5 . 1 . 2 . I n c o r p o r a t i o n of phosphate ions The Elmore likely a by affinity predominant [3], ions in the phosphoric a c i d s o l u t i o n a r e , according t o

the H , H_P_0Q and HS0„ i o n s . In the c r y s t a l s , however, more 5 2 8 ^ 22 2HPO,. ions r e p l a c e SO,, i o n s . The HPO,. ion can e a s i l y s u b s t i t u t e for ion, s i n c e t h e s e two ions are almost s i m i l a r in s i z e and share the towards calcium i o n s . The s i m i l a r i t y of these anions i s a l s o r e f l e c t e d

sulphate

the e x i s t e n c e of two comparable s a l t s : CaHP0 ü .2H.0 and CaS0ü.2H 0 , which are First crystallisation H.-PO^/kg, with and 0.35 of 0 . 1 1 . the molar experiments were performed in a s o l u t i o n containing residence times of 20 and 40 minutes, and [H SO,,]

both s p a r i n g l y s o l u b l e i n water and have the same molar volume [ 1 9 ] . 5.6 mole

between 0.02 weight r a t i o expressed as

mole/kg. These c o n d i t i o n s yielded a s o l i d over l i q u i d 2In f i g u r e 4 the HPO,, i n c o r p o r a t i o n in the c r y s t a l s ,
?2-

[HPO,.

]

over [SO,,

] r a t i o in the c r y s t a l s i s given

versus t h e molar [ H - P 0 J over [H S O j r a t i o in the s o l u t i o n . The phosphate uptake decreases with r a i s i n g [HpSO,] and a l i n e a r dependence between solution by the the drawn molar line phosphate in over s u l p h a t e r a t i o s in t h e c r y s t a l s and in the appears t o e x i s t . The r e l a t i o n s h i p between the molar r a t i o s presented f i g u r e 1 for 0.02 < [H S O J < 0.35 mole/kg i s given by

equation ( 1 ) : [HPO, 2 "] - — (crystal) = 1 . 4 * 1 0 * CSO^ ] [H,P0J --*---(solution) [H SO ] (1)

77

where 1.U*1o"

denotes the partition coefficient, D(HPO a

).

100

200

300

Figure 4: The phosphate incorporation, expressed as the molar phosphate over sulphate ratio in the crystals, as a function of the same ratio in the solution for various residence times. The slope of the curve, 2-4 D(HPCL )» i s approximately 1. 4 * 1 0 . This available growth higher linearity adsorption upon rate points sites more the at a competition between the two anions for the

at the crystal surface. An influence of the linear uptake can therefore be expected, since at a ions will be entrapped by the propagating phosphate

rate growth

phosphate

steps. This growth rate is determined by the actual supersaturation. Measurement of the supersaturation is impossible because the differences between the calcium and as sulphate are the amount for area to of concentrations in the solution and their respective saturation values too small to be determined. Therefore, the production rate, defined of HH obtained per kg suspension per second, has been used as a the linear the at growth rate, under the assumption that the specific higher supersaturation, it will never obscure the crystals remains constant. Although the specific surface

yardstick surface area tends

increase

higher supersaturation inherent to the higher production rate. In case of unclassified slurry withdrawal the production rate is directly the solid over liquid weight ratio and the residence time. In

correlated

with

78

all

experiments by not of of HH

the the the in

solid calcium

over liquid weight ratio is about constant, and is content acid calcium of the CDHP solution and by the sulphate solution. This is only true because the ions is extremely low, due to the slight

determined amount of

concentration solubility will of

sulphuric

precipitated

phosphoric acid (about 0.07 mole per kg) [1]. At shorter

residence times, the production rate is higher and therefore the supersaturation be higher, and an enhanced phosphate incorporation is expected. Comparison the results obtained for various residence times, as given in figure 4, does

not show this tendency, so the differences in supersaturation are apparently too small to cause a visible effect in uptake. Additional kW/m film or layer Besides 11 experiments kW/m were performed, with a power input of either 0.04 (stirrer speed 250 and 1570 rpm respectively). No effect of is hardly effected by the change in power input or that

these variations on the phosphate uptake was noticed. This shows that either the thickness the volume diffusion is not a predominant growth barrier in our experiments. experiments in 5.6 mole H.PCL/kg also experiments in 6.6 mole hLPOj/kg were performed to examine the effect of the H-.P0. content. For 5.6 mole H^PO,, /kg it was found that for changing [H?S0j.] in the solution, the phosphate 22uptake in the crystals, given by the molar [HPO^ by is the same varying solution however, ] over [SO. ] ratio, is ruled ratio in the bulk of the solution. If this rule remains valid for for different H..P0,. concentrations. Experiments performed in a

phosphate concentrations in solution, no shift of the curve in figure H containing 6.6 mole H PO./kg yielded values, lying on thesame line as is quite different. A lower solid over liquid weight ratio and a lower

expected

obtained for solutions containing 5.6 mole H-PO^/kg. The crystallising solution, solubility of calcium sulphate prevail, while due to the higher viscosity of the solution the diffusion coefficient is also lower. No estimation can therefore be made 5.6 mole 4, of the differences in supersaturation for experiments performed in either or 6.6 mole H-PO^/kg. Since, however, all results obtained in 6.6 or in 5.6 H.POjVkg for various residence times contribute to the same line in figure small changes acid in supersaturation, due to variations in residence time and apparently do not influence the uptake concentration,

phosphoric Results where the influence of

significantly. formerly obtained from batch experiments [6] in 6.6 mole H,P0j/kg, production rate was varied over a much wider range, showed that the larger increases in feed rates and thus in supersaturation can no

longer be neglected. Therefore, if much higher feed rates were applied, a higher uptake can be expected in our experiments.

79

In increase

some of of

of our experiments AH was formed. In the experiments where the AH the the a crystals remained below approximately 10 w } , no significant phosphate few uptake was observed. A visible higher uptake was performed where under further similar

percentage

noticed only for AH percentages above 15 w$. Finally conditions experiments Cl , Br or were I either was added. Addition of halogenides did not

influence the phosphate uptake. 5.4.3. Incorporation of cadmium ions 2+ 2+ 2+ ionic radii of Ca and Cd are almost equal( r(Ca ) = 1.12 A 1.07 A [5], both with an 8-fold coordination [2,12]), the Cd 2 + the Ca
2+

and ions

Since the r(Cd 2 + ) = can The

replace

ions in the crystals, without causing much lattice of these ions, on the contrary, are quite

strain.

chemical

properties

different. solutions

Cadmium sulphate as well as its hydrates are very soluble in aqueous 2+ 2[11], so the interaction between the Cd ions and the SOj. ions at 2+ 2ions and the S0 Ü also counts for a solution containing 5.6 mole H-POn/kg at 92 °C,

the crystal surface must be much weaker than between the Ca ions. This

where the molar solubility of cadmium sulphate has been measured to be about 0.7 mole per kg solution, which is ten times higher than the molar solubility of HH. For the experiments concentration expressed as in 5.6 mole H P0./kg with sulphuric acid concentrations ranging cadmium uptake, from 0.02 to 0.35 mole/kg and residence times of 20 and 40 minutes, the in the HH crystals was measured. In figure 5 the cadmium the molar cadmium over calcium ratio in the crystals, is

presented as a function of the sulphate concentration in the solution. The [HpSOj,] in the solution can be converted to a molar cadmium over 2+ calcium ratio, because the product of [Ca ] and [H_S0.] is about constant, and -3 2 2 2+ equal to 5*10 3*10 ratio the mole/ phosphate the For mole /kg in 5.6 mole H,P0,./kg, while [Cd ] in the solution was kg in all experiments. In figure 5 the molar cadmium over calcium uptake, cadmium a competition between cadmium and calcium ions for the

in the solution is also given on the horizontal axis. If, in analogy with adsorption sites at the interface takes place, a linear relationship over calcium ratio in the crystals and in the solution is performed with a residence time of 20 minutes this time could not be performed at excessive AH

available between expected.

experiments with

linearity indeed exists for sulphate concentrations of 0.1 up to 0.35 mole/kg. Experiments sulphate formation. 40 minutes beyond residence about 0.25 concentrations mole/kg, without

80

The partition coefficient for cadmium, expressed as: ( [Cd 2 + ] / [Ca 2 + ] ) ( crystal ) D (Cd 2+ ) ( [Cd 2 + ] / [Ca 2 + ] ) ( solution ) equals 1*10
J

(2)

for H H . residence time • 20 min O M)min Q12%AH

3.10 [Cd] — - (crystal) ICa] 2.10~5H

5

O 11%AH

1.10"5H

.0-'
0 . 1 0.5-10" 0 . 2 1.10"

O

3 ° , IH2^%)

^ [Ca] Figure 5: The Cd incorporation expressed as the molar Cd + over Ca ratio in the crystals as a function of the same ratio and of the sulphate concentration in the solution. The star indicates the reduced level of incorporation that could be obtained by addition of halogenldes to the solution (see text), e.g. 0.7*10 -2 mole I per kg solution. For sulphate contents below 0.15 mole/kg the cadmium uptake is higher for 40 than for 20 minutes residence time. For the moment no explanation for this phenomenon can be given. An indication, that at sulphate concentrations below 0.05 mole/kg the cadmium incorporation is lower than predicted by our experiments with 40 minutes residence time, is given by the results of continuous operation of the phosphoric acid process on a bench-scale. During this operation a small amount of HH is precipitated during the digestion of the ore. The solution contains in that case about 0.005 mole H SO./kg, and in the crystals only a very small amount of cadmium, corresponding to a molar cadmium 81

1.5-10"' (solution)-

over can

calcium hardly and

ratio

below H * 10 from a

is found. This difference in cadmium uptake difference in residence time (120 versus 10

be resulting not excluded in

minutes) therefore uptake also

in solid over liquid ratio (0.01 versus 0.11 or 0.05) only. It is that for [H-SO^] below 0.05 mole/kg the actual cadmium

will decrease. The tendency of increasing uptake with raising [H_S0^] is found batch experiments [17], although in that case the extent of the in power uptake input from 0.01 to 11 kW/m did not have a visible

incorporation was higher [12], A effect on the sulphate variation on cadmium the cadmium uptake. In figure 5 the strong influence of AH formation is elucidated. The cadmium uptake in the AH at various could a be estimated relationship from experiments, where AH was

concentrations data make

formed, after correction for the amount of cadmium incorporated in the HH. These preliminary calcium the linear between the molar cadmium over

ratio D

in AH

coefficient cations assumed partition

and the solution likely. The corresponding partition -2 is about 1*10 . This linearity points at a competition between for the phosphate and sulphate ions. Comparison of the

for the available adsorption sites at the interface, which is also

to occur

for cadmium ions in the HH phase, which for a residence -3 time of 20 minutes equals 1*10 , with the partition coefficient for phosphate -it 2+ uptake, which equals 1.1*10 in HH, demonstrates that substitution of the Ca 2+ 2ions by Cd ions occurs about 7 times more frequently than replacement of SOj, 2ions by HPOj. ions. 2+ 2Regarding the weak affinity of the Cd ions towards the S 0 U ions at the 22+ interface and the much stronger affinity of HPO^ ions towards the Ca ions at 2+ the interface, this high Cd uptake is rather surprising. The preliminary 2+ -2 partition coefficient for Cd in AH, D = 1*10 , is even substantly higher than 2+ 2D(Cd )HH and D(HP0Ü )HH. A possible reason for this enhanced uptake follows 2+ from the lower solubility (about two times) of AH, [Ca ] * [H.SOj is about -3 2 2 2*10 mole /kg in 5.6 mole H P0L/kg, which causes the supersaturation for AH S * 2* to be much higher than for HH, resulting in a higher Cd uptake in AH due to a kinetic overgrowth effect. Also thermodynamic effects have to be considered as a possible HH. These reason for the enhanced cadmium uptake in AH compared to the uptake in thermodynamic effects on the partition coefficient can be taken into

coefficient

account by writing D, according to Mclntire [13], and assuming the activity 2+ 2+ coefficients of Cd and Ca to be about equal, as:
K(CaSCv)

■>«"2+> = K(cds5;)* * (

f.All/RTx

iu/RT)

(3)

82

Here solution solubility

the is 2+

difference assumed to

in be

chemical taken

potential between Cd

2+

and Ca

2+

in the

into account mainly by the quotient of the

products K, while An represents the difference in chemical potential 2+ and Ca in the crystal lattice. 2+ If Ay were similar for Cd uptake in AH and in HH, the partition 2+ coefficient for Cd in HH is expected to be twice the value in AH, due to the 2+ lower solubility of AH. The observed D value for Cd in AH is at least ten between Cd times Ay higher be than its value in HH. Therefore, if we assume eq.(3) to be valid, 2+ 2+ the same, and replacement of Ca by Cd possibly requires less

cannot

energy in AH than in HH. This assumption is not unlikely because CdSO. and CaSCv are almost identical salts, while this is not true for their hydrates. Partition the coefficients of were also determined by Kushnir, who investigated

incorporation

many foreign ions in DH, HH and AH, precipitated from or

recrystallised in seawater [10,11]. A striking difference between our results 2+ 2+ 2+* for Cd uptake and Kushnir's results for Mg uptake is, that D(Mg )AH is two 2+ 2+ times smaller than D(Mg )HH, while we found D(Cd )AH to be more than ten times 2+, 2+ larger than D(Cd )HH. The partition coefficient for Mg in AH from seawater is 2+ smaller than for Cd in AH from phosphoric acid, although the solubilities of CdSCv and MgSCv in aqueous solutions are comparable. The apparantly existing 2 + 2 + differences in Ay values of Mg and Cd in CaSCv are probably caused by the 2+ 2+ 2+ larger differences, e.g. in ionic radii, between Mg and Ca compared to Cd 2+ 2+ 2+ and Ca , leading to a larger lattice mismatch for Mg . The Mg ions probably 2+ fit equally bad in the HH as in the AH lattice, while Cd ions fit better in 2+ 2+ the AH than in the HH lattice and apparently better than Mg ions. Our Cd

incorporation experiments. Finally added. 2.7*1 o" solution the The a

results

will be verified in the near future by recrystallisation

few experiments were performed where either Cl results 1.3*10~ 1 4
2

, Br

or I

was

preliminary Cl" ,

presented mole

in

figure 5 demonstrate that when

mole

Br" or 0.7*10 -2 mole i" is added to 1 kg 2+ 2+ , a reduction in Cd incorporation in

containing of

3*10

mole of Cd HQ% is

crystals

about

achieved. These results are in agreement with complexation by halogenides in aqueous

literature

data

concerning

cadmium

solutions [6,7]. In these data a decrease in complexing activity is mentioned in the order I~ > Br" > Cl~.

83

5.5. Conclusions - The habit of the H H crystals changes with raising [H SO.] from mainly aggregates to mainly needles.
2- The HPCv incorporation decreases with raising [H~SOv] and is directly proportional to the phosphate over sulphate ratio in the bulk of the solution. 2+ - The Cd incorporation increases with raising [H.SCv] and is directly proportional to the molar cadmium over calcium ratio in the solution for residence times of 20 minutes and between about 0.15 and 0.35 mole H„S0. per kg solution. - High HpSOj, concentrations, high temperatures and long residence times stimulate the formation of AH. 2+ - Under identical operating conditions, the Cd uptake in AH is at least 10 times higher than in HH. 2+ - Halogenides reduce the Cd uptake. 5.6. Literature [I] Becker, P., "Phosphates and Phosphoric Acid," Fertiliser Science and Technology Series, Vol. 3, Marcel Dekker N.Y. (1983). [2] Bushuer, N.N., Russian Journal of Inorganic Chemistry, 27, (1982) 341. [3] Elmore, K.L., Hatfield, J.D., Dunn R.L. and Jones, A.D., J. Phys. Chem. 69 (1965) 3520. [4] Gorecki, H., Indian Journal of Technology, 23 (1985) 51. [5] Huheey, J.E., "Inorganic Chemistry," Harper and Row (1975), p. 74. [6] Jansen, M., Waller, A., Verbiest, J., Landschoot, van R.C. and Rosmalen, G.M. van, Industrial Cryst. (1984), 171, ed. Jancic and De Jong, Elsevier Amsterdam. [7] Klok, A., Tiggelman, J.J., Weij, P., Dalen, J.P.J. van and Galan, L. de, Proc. XXIV Colloq. Spectrosc. Intern. (1985) 98. [8] Kolthoff, I.M. and Elving, P.J., "Treatise on analytical chemistry," Vol. 3, Part 2, Interscience N.Y. (1961). [9] Kostelnik, R.J. and Bothner-By, A.A., J. Magn. Resonance 14 (1974) 141. [10] Kushnir, J., Geochimica et Cosmochimica Acta, 44, (1980) 1471. [II] Kushnir, J., Geochimica et Cosmochimica Acta, 46, (1982) 433. [12] Lager, G.A., Armbruster, Th., Rotella, R.J., Jorgensen J.D. and Hinks, D.G. Amer. Mineralogist, 69, (1984) 910. [13] Mclntire, W.L., Geochimica et Cosmochimica Acta, 27. (1963) 1209. 84

[1H] Slack, V.A., "Phosphoric Acid," Fertiliser Science and Technology Series, Vol. 1, Marcel Dekker N.Y. (1968). [15] Sluis, van der S., Murach, Z., Wesselingh J.A. and Rosmalen, G.M. van, "The predigestion stage of a new phosphoric acid process," Proc. of World Congress III of Chemical Engineering, Vol J J (1986) 96. [16] Taperova, A.A. and Shulgina, M.N., J. Applied Chem. (USSR) 23 (1950) 27. [17] TJioe, T.T., Weij, P. and Rosmalen, G.M. van, "Removal of cadmium by anion exchange in a wet-phosphoric acid process," Proc. of World Congress III of Chemical Engineering, Vol. 2 (1986) 925. [18] Tjioe, T.T., Woude, van der H., Verbiest, J., Durville P.F.M. and Rosmalen, G.M. van, Proceedings of the international conference "Heavy metals in the environment," Vol. 1, 292, Athens 1985, Editor Lekkas, T.D. [19] Weast, R.C., "Handbook of Chemistry and Physics," 59th edition, CRC press, Florida, (1978).

85

6. FILTRATION OF CALCIUM SULPHATE HEMIHYDRATE 6.1. Introduction The The which is separation of calcium sulphate from its slurry in phosphoric acid is

always done by filtration. main objective of the filtration is to obtain a clear phosphoric acid, not diluted is with also wash suitable water, for by a means of simple and economical which thorough cake washing, to prevent

equipment, The US per cake of day

discharge of phosphoric acid with the calcium sulphate cake. washing a plant of acid is of the cake is extremely important, because about one million produced in a 1000 tons P 0 discharged with the cake. The amount of water available for sulphate It also formed depends as on well the as on the concentration of moisture content of the cake dollars washing year are lost, if 0.5 % of the P 0

strongly depends on the acid strength to be produced, on the type calcium used.

hydrate

sulphuric always

discharged from the filter. Phosphoric acid processes operating nowadays, nearly use a three washing steps. This is certainly necessary for the processes, high acid strength is produced, because the quantity of wash water in which

available is then very small. The the wash water must be supplied, when the liquid level reaches the surface compartment, of are the most lowering the efficiency of the washing sometimes even important parameters in the filtration and washing

of the cake, because otherwise the cake tends to detach itself from the walls of filter Some procedure shape, from about 98 to 80 % [4], [2]: the physical properties of the liquid, the particle size,

size

distribution and packing characteristics and the solids content of

the slurry to be filtered. The description of the filtration and washing of the calcium sulphate cakes is relatively easy, because the resistance of the filter cloth and support medium can usually be neglected and because the calcium sulphate cakes are found to be incompressible [4]. The To than obtain the total area needed for filtration and washing is found to be about four a clear phosphoric acid, most of the time a so-called prefiltration which are to be removed and the filter will work times the area needed for filtration only, if three wash steps are used [1]. section is incorporated. In general the pores of the filter cloth will be larger particles, efficiently only after an initial deposit has been trapped in the medium [1,2].

86

This of

first part of the product acid is normally recycled to the digestion stage the plant. In some cases anionic polyelectrlytes are used as flocculants to filters are always selected from experience with the same type of

improve the filtration characteristics [1]. Although ore plant size which in the same process or from pilot plant studies [1], laboratory studies of data and is are shape hardly of first always preferred, is the large influence of impurities on the in laboratory studies. Scaling can be caused by the [1] or alkaline fluoro compounds, and is frequently used in 1930, was a horizontal belt filter.

the filtration can give an estimation of the filter area needed. The reason, why of the crystals obtained as well as the occurrence of scaling, observed

formation The The [1]; they important

chukhrovite continuous

encountered in phosphoric acid plants [1]. filter Around 19t5 horizontal table and tilting pan filters came into use [4]. types of filters used at this moment are quite well described by Slack have not changed for greatly a over the last are the twenty years. The most capacity, the total parameters selecting filter

investment, maintanance cost and susceptibility to corrosion, which is severe in phosphoric acid media. The type of filter cloth used varies widely and depends on the acid strength to be produced, the temperature, the type of phosphate ore used and the required clarity of the phosphoric acid. Some of the materials used are : saran, polyethylene polypropylene, terylene and dacron. The aim of this study is to determine the influence of the sulphate concentration and the residence time in the crystalllser on the filterabllity of the HH-phosphoric acid slurry, expressed as the permeability of the HH cake. 6.2. Theory of filtration The through resistance In filter two the principle the cake against of and the filtration the flow to filter is is the shown in due figure 1. The filtrate flows to a pressure gradient. The

medium,

combined resistance of the cake and the

filter medium. experiments be described, the pressure drop over the cake and medium is held constant. The cake formed is assumed to be incompressible resistances in series. The filtrate flow rate per unit filter

[4] and homogeneous. Furthermore, the cake and filter medium are assumed to form independent area is then given by:

87

AP "*~(Rc~

Rm)

(1)

where Re and Rm are the cake and filter medium resistances respectively, AP the pressure drop over the cake and filter medium and n the viscosity of the filtrate. This can also be written as: (Re + Rm) * 1 * 5Y A dt

n

(2)

1 = slurry 2 = filter cake 3 = filter cloth 1 = support medium 5 = filtrate

Figure 1: Filtration principle

The cake resistance can be expressed as a relationship between the specific cake resistance, a and the mass of solids deposited per unit filter area, w as:

Re

* w = a * p s * (1 - e ) *

(3)

This proportionality between the cake resistance and the cake height can also be written as: Rc= -

(4)

where K is the cake permeability. If slip between the particles and the fluid in the feed is neglected, the superficial velocities of the solid and the liquid are equal and the following relationship yields:

88

s 2— = (1 - ef) The volume V
3

u

l f -i >u = i *u (5) ef s ef 1 of solids deposited can be calculated from the following expression: (6)

U

= A * y u * dt
O S

and as:

the cake height, h can be obtained from eq. (6) and the cake porosity, e,

h

■ r b * oK "dt - u-h) * ~--iy~ *o* ui •dt
(1 - e )

(7)

This can be written as:

h

- s--.-(rh) * i-

(8)

in which V = volume of filtrate. After substitution of eq. (8) in eq. (1) , the result can be inserted in eq. (2) to give: (1 - E ) * V ( „___ff..-.I— ^e„ * (1 - e) * A * K , 1 * 3V = AP A dt n

+ R mm; )

"

(9)

^'

which can be written as:

-Jj - o, * c 2 * V
«».,*. in which 1 * Rm = -=-»-j „ and c (1 " e ) « n .

(10)

c

ef * (1 - e) * A * K * AP So a plot of -- versus V should give a straight line. The slope of this line then yields, together with the values of e and e f , the cake permeability, K.

89

6.3. Experimental 6.3.1. Equipment The equipment used for the filtration experiments is shown in figure 3. The top be part of the filter consists of a double walled pipe of 0.4 m height, with a measured fitting with a measuring-tape on the outside. The lower part of the filter for easy cleaning. The connection between the two parts, as well diameter of 0.031 m. This tube is thermostated. The liquid level in the tube can is shown in more detail in figure 4. It can be detached from the upper part by a screw as the connections between the glass and the metal are sealed with viton rings

to prevent leakages. The liquid flowing through the filter medium passes a glass valve (inner diameter 0.01 m) and is collected in a round flask of 0.5 litre.

Figure 3= Filtration apparatus.

Figure 4: Lower part of the filter with filter medium.

One outlet of this flask is connected to a vacuum pump and a manometer. The other acts outlet as a is buffer also to connected to the manometer and a 50 litre vessel, which maintain a constant vacuum. The volume of filtrate was

registered by the lowering of the slurry level in the glass tube. After each cm, the time was noted down. The filter medium was filter cloth made of terylene 2342 and glued between two PVDF rings.

90

6.3.2. Chemicals The chemically described immediately recrystallised been obtained. phosphoric pure in chapter after into DH acid-calcium were These 5. their sulphate hemihydrate slurries, produced from obtained from the crystallisation experiments slurries were used for filtration experiments because otherwise the HH might be

reagents,

formation,

before the filtration and erroneous results would have

6.3-3« Procedure About phosphoric thermostated minutes. about will the a In 300 acid at the grams slurry 90 of is the freshly formed calcium sulphate hemihydrate-

weighted and suspended in the' glass tube, which is the pressure below the filter medium is reduced to

°C. The slurry is homogenised by gently stirring for a few

meantime

25 kPa. So a mean pressure drop over the cake and filter medium of 29 kPa result start of of during the filtration. The stirrer is quickly removed, just before the filtration The experiment. At time t = 0 the glass valve is opened and the level of the slurry in the glass tube is monitored as time. experiment is stopped, when the slurry level almost cake water level. After measuring the cake height, the filter is opened saturated with gypsum, and thereafter three times with

completely function the with reaches washed

and air is blown through the tube to remove the cake. The solids are three times acetone. The weight of the solids is determined after overnight drying.

6.4. Results and discussion The checked crystals times five was in are reproducebility by in performing of the results obtained with our equipment was first

filtration experiments after each residence time of the

the crystalliser. From the results obtained in the crystallisation required, before the crystalliser attains a steady state. It is also times under the same conditions. The crystallisation experiment at 90 °C in 40 w$ P n
dO

experiments as well as from literature, it is known that at least five residence believed, that the crystal size, shape and size distribution hardly change after residence performed and 1.8 wj H»S0„. The mean residence time
d.
H

the crystalliser was 40 minutes. After 2, 3, 5, 6, 7 and 8 residence times a

dt/dV versus V curve was made; these are shown in figure 5.

91

Figure obtained

5 shows, that after 5 residence times the slope of the dt/dV versus constant and the results obtained with our equipment are

V curve does not change anymore. This means that the permeability of the HH cake is indeed reproduceble. Important process parameters are the sulphate concentration in the solution and the residence A content maximum of time of the crystals in the crystalliser. The influence of of the HH cake is observed between a sulphate both parameters on the permeability is shown in figure 6. permeability 1.5 and 2.0 w$ H SO. in the crystalliser. This was also found by

Dahlgren [3] in a single stage HH process, without a separate digestion stage.

"-i-x10"5s/m3

110

number of residence times
o = 2, • = 3 , D = 5 1 ■ = 6.7,8

50 -*- Vx10 6 m 3

100

Figure 5: Influence of the number of residence times of the crystals in the crystalliser on the dt/dV versus V curve. The influence of of the sulphate content in the crystalliser on the

permeability At formed larger The 1.5

the HH cake

can be explained

by the size, shape and size

distribution of the crystals. low sulphate concentrations small crystals and clusters of crystals are as shown in figure 7. At higher sulphate concentrations the crystals are and more uniform, as shown in figure 8, while at very high sulphate

concentrations both large and small crystals are obtained, as shown in figure 9. influence of the residence time is also illustrated in figure 6. Above w$ HpSO,, in the solution in the crystalliser, an increase in residence time

92

from 20 to 60 minutes seems to lead to a reduction in the permeability of the HH cake. This of might the be caused HH by the formation of small crystals, due to the obtained at longer residence times and breakage sulphate maximum longer needless,

concentrations

above about 1.5 w$ H-SOn. The permeability reaches its

solution in the crystalliser. The maximum value is about 65 * 10

value with a residence time of 20 minutes and about 1 .8 w$ H?S0,. in the -12 2 m .

70residence time —•- 20 min --o-- 40min 60 min

50-

30-

10I 3 w%H2S04 Figure 6: Influence of the residence time and the sulphate content of the solution in the crystalliser on the permeability of the HH cake obtained at 90 °C in 40 w$ P 0_ with a stirrer speed of 650 rpm.
<i 5

x. = 11 w% AH, x 2 = 1560 rpm, x, Furthermore, permeability smaller crystal The of the the

280 rpm.

influence of a small amount of AH in the crystals on the crystal cake was checked. The AH crystals are normally

than HH crystals and have a different size, shape and size distribution cake is large indeed. The permeability obtained was about 50 % of the

[1,4], The influence of only 11 w$ AH in the crystals on the permeability of the normal value, as illustrated in figure 6 by point x . influence of halogenides, added to reduce the cadmium incorporation in the crystals (see chapter 5 ) , is not shown in figure 6. No significant change of the permeability of the HH cake, however, was noticed.

93

Figure 7: HH crystals obtained at 90 °C in MO w$ P ^

and 0.5 w% H^O^.

Figure 8: HH crystals obtained at 90 °C in 10 w* P20

and 2.4 w$ H^O^.

94

A of 6).

process parameter, which did influence the permeability was the stirring

speed in the crystalliser. Under otherwise similar conditions the stirring speed about 650 rpm was increased in one experiment to about 1560 rpm (point x_ in Lowering of the to stirring speed seems to increase the permeability of the keep the crystals in suspension and to mix the CDHP and figure 6) and in another experiment lowered to about 280 rpm (point x_ in figure cake. This might be caused by less breakage of the HH needles. Good stirring is, however, sulphuric must high be required acid solution thoroughly and quickly. The mixing of these solutions These small crystals will inevitably lower the

fast enough to prevent the formation of small crystals, due to locally

supersaturations.

permeability of the HH cake.

Figure 9: HH crystals obtained at 90 °C in HO w$ P Cv and 3.2 w$ H-SO^. The reality, HH results obtained here are for HH from chemically pure reagents. In

impurities will influence the size, shape and size distribution of the

crystals. This influence has been checked in the bench-scale plant and will Last but not least a comparison was made between the results predicted by and the results obtained with a commercial filter. The linear

be presented in chapter 9. our P p 0_ equipment

filtration

velocity of the commercial filter can be obtained from the amount of meter filter area per day, which is given as 7 tons 50 % of the acid is recycled and 50 % is actually 95

produced per square 2 P20,-/m per day. Because

produced,

filtered is thus 14 tons P„0,_/m /day. The data 2 5 for the density and concentration of the commercial acid given in table 1 have -4 been used to calculate a linear filtration velocity of about 5 * 1 0 m/s. The slurry of the commercial plant was also used in our equipment, in which -12 2 of this DH cake of 1 * 10 m was obtained (the slurry was at 60 and °C). The the linear of filtration velocity calculated from this

the

amount

of

acid

a

permeability

filtered

permeability given in

values

table in our

1, is also equal to about 5 * 10 laboratory

the cake height, viscosity and pressure drop -4 m/s. So simular results are

obtained material.

equipment and on a commercial filter for the same

acid concentration viscosity density cake height pressure drop over cake permeability (chapt er 9)

26
1.5 * 10~ 1250 5 * 10~ 2
3

v% P 2 0 Ns/m kg/m3

m
kPa
2 m

50
-1 2 1 * 10

Table 1: Data for a commercial filter.

The filterability of the HH-phosphoric acid slurry obtained from chemically pure HH reagents cakes are is good, because the values obtained for the permeability of the substantially higher than those obtained for the DH cake from a

commercial plant.

96

6.5. Nomenclature A h K Re Rm t u. u V V„ w a AP e e n p filter area cake height permeability cake resistance filter medium resistance time liquid velocity particle velocity filtrate volume volume of solids mass of solids deposited per unit area specific cake resistance pressure drop cake porosity volume fraction of liquid in feed viscosity solids density N * s * m -3 kg kg * m m * kg Pa m m s 1 m * s -1 s m m m

6.6. Literature 1. Becker, P., Phosphates and Phosphoric Acid, Fertiliser Science and Technology Series, Vol. 3-, 369-^OiJ, Marcel Dekker Inc., New York (1983). 2. Coulson, J.M., Richardson, J.F., Backhurst, J.R. and Harker, J.H., Chemical Engineering, Vol. 2, 3rd ed, pg. 126, 321, Pergamon Press Inc. New York (1978). 3. Dahlgren, S.E. and Hakanson, R., Acta Polytech. Scand. Chem. Met. Ser., 52 (1966) 3. 4. Slack, A.V., Ed., Phosphoric Acid, Fertiliser Science and Technology Series, Marcel Dekker Inc., New York (1968), Vol. 1, pg. 107.

97

7. FLUORIDE DISTRIBUTION COEFFICIENTS (G/L) IN WET PHOSPHORIC ACID PROCESSES 7.1. Summary Phosphoric 2-4 acid for use in fertiliser applications is mainly produced by

digestion of phosphate ore with sulphuric acid. The phosphate ore contains about w$ F. During the digestion of the ore, the fluoride is released as hydrogen which with reacts alkaline with silica in to the fluorosilicic acid. Part of it ions early stages of the phosphoric acid fluoride, precipitates partly

production process and part of it decomposes in SiFj. and HF, which on their turn evade into the air. The residual fluoride in the solution is distributed between the phosphoric acid and the byproduct, a calcium sulphate modification. The phosphoric Removal limited of disposal acid the So of and this the byproduct as well as the application of both the

byproduct can be hampered by their fluoride content.

fluoride from the phosphoric acid is therefore a necessity and accurate fluoride distribution coefficients between the

has to be carefully controlled, because the fluoride concentration in the air is too. phosphoric acid and the ambient air have to be known. These nitrogen absorption distilled A Elmore's Pitzer, fluoride gas stream distribution coefficients were measured by saturation of a passing through several absorption bottles in series. The

bottles were filled with fluorosilicic acid dissolved in mixtures of water, chemically pure phosphoric acid and chemically pure sulphuric model, based phosphoric on the description of the acid mixture with and the ion specific interaction model of

acid at various temperatures. theoretical model of of acid

is used to describe the results. An expression is derived, which allows the fluoride distribution coefficients between the acid and the

calculation

ambient air at temperatures between 70 and 95 °C, for solutions containing 30-50 w$ PJD,., up to 6 w? H„S0„, maximal 4 w$ H„SiF, and a molar F/Si ratio of six. Comparison of the fluoride distribution coefficients predicted by the

derived expression with those measured for commercially "wet process" phosphoric acid with molar F/Si ratios below 10, showed no significant difference. 7.2. Introduction The acid production of phosphoric acid is almost directly related to the world

phosphate fertiliser consumption, which still tends to increase [28]. Phosphoric for use in fertiliser applications is mainly produced by wet processes. In

98

these

processes acid

the

phosphate

ore

is digested by a mixture of sulphuric and

phosphoric as a

and huge amounts of hydrated calcium sulphate are precipitated The phosphate ore is mainly fluoroapatite (Ca (P0jJ,F ) with

byproduct.

some additional compounds such as calcite, quarts, clay etc. During The hydrogen to form digestion of the ore the fluoride is released as hydrogen fluoride. fluoride reacts with the silica, present in the ore or added as a fluorosilicic acid. Some of the fluorosilicic acid precipitates

clay, during

the production process with sodium or potassium ions as Na SiF>, K SiF,, or as more complex compounds [14]. The remaining fluorosilicic acid in acid partly decomposes and evades as SiF,. and HF. The residual is distributed between the phosphoric acid and the

NaKSiF, o the

phosphoric in

fluoride

solution

byproduct during its precipitation [2,28]. In this byproduct the fluoride is 22assumed to be present as A1F,. ions, which can substitute for the SO,. ions in b 4 the calcium sulphate lattice [19]. The building content natural fluoride material is higher is content or of the byproduct hampers its application as e.g.

as a settling retarder in cement [42], when the fluoride

than about 0.15 wj F [15]. The disposal of the byproduct in restricted by an environmental limitation of 6 ppm F in

water

seawater [2], The the fluoride remaining in the phosphoric acid is eventually deposited on

meadows

through the application of phosphate fertilisers. This can give an content of the grass, which can cause fluorosis of e.g. cows

enlarged [1.35]. An

fluoride

accepted

limit

for

the

fluoride content of phosphoric acid, used in

fertiliser

applications, is about 1 wj F [40]. If the phosphoric acid were used

in cattle feed production, this limit is even lower (0.2 w$ F) [35]. The evaded fluoride has to be recovered, because the fluoride concentration in air is limited to about 2 ppm for environmental reasons [2,40]. The fluoride, acid evaded solution as SiF^ and HF, can be absorbed in water to give a [2,28]. These H SiF, solutions are applied for

fluorosilicic

fluoriding potable water in the U.S.A. and for sterilisation of wood [28]. In addition, processes to produce SiO. and HF from these solutions [12] are gaining material field. The Si0 o
£

produced

from

H„SiF, solutions is a suitable basic
2 b

for the production of ceramics [12,40]. This market for application of

Si0 2 is growing, due to the increasing interest in ceramic materials [24], Hydrogen carbons fluoride is is also mainly used for for the the production of chloro-fluoroproduction of highly resistant

[28], but

applied

99

engineering plastics like PTFE and PVDF, which use is increasing [6] and for the production of cryolite (Na^AlF,) for use in the aluminum industry [28]. The welcome fluorosilicic fluoride acid from phosphoric the acid ore production processes is a used nowadays for the

source,

because

fluoride

production of hydrogen fluoride, fluorite (CaF„) is getting scarse [28]. For all reasons mentioned above the fluoride content of phosphoric acid has to be reduced fluoride and from almost all fluoride has to be recovered. Possible ways to acid are extraction [10,14], precipitation

remove

phosphoric

[6,7,16,25], stripping and flashing [20,23,31]. If extraction from huge the methods are used, a second liquid phase is generated, which phosphoric has to acid be phase purified, can cause problems. Moreover, a

separation relatively

stream

so the extraction equipment is

expected to be large. Another way to remove fluoride from the phosphoric acid is precipitation by addition of alkaline cations. The disadvantages of this method are the increased scaling in the with process respect equipment caused by the permanent state of

supersaturation

to the alkaline silicates in the phosphoric acid

solution and the difficulties connected with the fluoride and SiO„ recovery from the mixture of solids. So only to An stripping remove advantage and flashing from seem the to be commercially feasible unit acid and to recover the possibility to obtain the

operations fluoride.

fluoride of

phosphoric is the

these

methods

fluoride in a directly salable form. In during order to calculate or flashing the amount of fluoride evaded into the gas phase various process conditions, the fluoride

stripping

under

distribution coefficients between the phosphoric acid solution and the gas phase are indispensable data. In the next section a survey of previous measurements of these coefficients will be given and the objective of this study will be

defined.

7.3. Literature survey

The phosphoric acid, calcium

fluoride

distribution

coefficients between the the gas phase and the

acid, which contains several additional compounds, such as sulphuric acid, fluorosilicic data for acid, an iron, magnesium, aluminum and design of the fluoride

hydrofluoric ions, are

essential

accurate

stripping unit of a phosphoric acid plant.

100

Most [36] vapour HF

of

the

research

on fluoride distribution coefficients presented in

literature is done on H„SiFg-H 0 systems. Illarionov [18], Baur [1] and Shrambam studied the H„SiF,-H„0 system. At low H„SiF,-concentrations they found the
2 o
d.
d

o

pressure SiF.

of HF to be higher than the vapour pressure of SiF.. The molar ratio in the gas phase lessened with increasing H ? SiF,

over

concentration. According to Lehr [22] the hydrolysis of SiF,, is reduced and thus its evasion stimulated, due to the decrease in the water content of the solution with increasing H„SiF, concentration. Teslenko e.a. [39] even suggested that the fluoride is mainly present as SiF.(H-O),, in strongly acidic media. Borisov and Mel'nikova [3] and Kopylov e.a [20] performed measurements with the out chemically by passing They with of the pure H.PO.-H SiF,-H„0 system. These investigations were carried an report inert that gas the stream through the acid until saturation was predominance of SiF. over HF in the gas phase the molar HF over SiF. ratio in the gas

reached. increases increase 60 and

increasing

phosphoric acid concentration in the system, but an raises

temperature

phase. They measured the fluoride evasion, however, only at temperatures between 90 °C in phosphoric acid solutions with P_CL percentages between 10 and
2 D

55 w%, in which range they could only detect SiF. evasion. In the "wet F/Si due gas a later article, however, Kopylov e.a. [21] were able to detect HF in phase as well, in the same concentration range during concentration of phosphoric acid (W.P.A.). They measured an increase of the molar the liquid phase from 6 to approximately 100. So the vapour in

process" ratio to

pressure

of SiF. above phosphoric acid must be higher than of HF [21], probably the stronger interaction of HF with phosphoric acid. This results in an

increasing HF concentration in the liquid phase during concentration of W.P.A. Also Senetova e.a. [33,3*0 and Spijker [38] studied the evasion of fluoride into the of but gas phase also of during not evaded concentration of W.P.A.. Spijker investigated the during as concentration of the H P0.-H2SiF,-H?0 evasion system, the fluoride only

during concentration of the H PO.-HF-HpO system. He presents fluoride a function of the P o 0 c content of the
2 D

percentage

phosphoric acid during concentration. From these experiments a sharp raise in the amount of evaded fluoride was noticed above approximately 10 wj P_0 C , if the 2 5 fluoride is initially present as H SiF,. This must be assigned to the reduced hydrolysis of SiF^ by water at the decreasing water content of the W.P.A. during concentration, and not the resulting in an enhanced SiF. evasion. Only the fluoride content silicon content in the gas phase was measured, so the molar F/Si

ratio remained unknown.

101

The

amount of

of

evaded

fluoride partly 10 due

will to

thus the

decrease near the end of the lower Henry coefficient of HF

concentration H.PO.F, above

W.P.A.,

compared to SiF^ and partly due to the formation of mono-fluoro-phosphoric acid, approximately w$ P..CL. The amount of mono-f luoro-phosphoric acid increases with an increasing molar F/Si ratio in the solution [21]. Senetova e.a. [33] also measured the influence of the addition of sulphuric acid and Si0 ? to the W.P.A. on the evasion of fluoride during concentration of e.a. [27] of measured the the influence of Mg ions on the fluoride W.P.A.. Both variables are found to enhance the fluoride evasion. Odintsova evasion. partial To a An vapour remove increase Mg concentration in the solution diminishes the

pressure almost

of fluoride owing to the precipitation of MgF ? , which all fluoride from phosphoric acid and to obtain the

even predominates the formation of MgSiF,-. highest fluoride distribution coefficients it is therefore necessary to maintain molar F/Si ratio of approximately 6 in the solution by continuous addition of Furthermore recovery found to of be the less a lot the corrosion of the equipment used for the removal and silicon as for instance a clay. fluoride as well as for the production of phosphoric acid is

if the fluoride is present as fluorosilicic acid instead of of results between and general trends are presented, fluoride

hydrogen fluoride [13,26]. Although distribution acid solutions coefficients the liquid and the gas phase for phosphoric

between 70 and 90 °C containing 140-55 wj Pp0 5 , 0-5 w$ H SO, and

0-4 wj F and a molar F/Si ratio of approximately six are lacking. The objective of this study is therefore to determine fluoride distribution coefficients influence fluoride between phosphoric acid solutions and the gas phase, while maintaining a molar F/Si ratio of about six in the phosphoric acid solution. The of the phosphoric acid concentration, temperature, sulphuric acid and content of the phosphoric acid on the fluoride distribution

coefficients is studied. 7.4. Model development 7.4.1. General remarks In liquid order and the to predict gas phase the as fluoride a distribution coefficient between the of the temperature and process

function

102

parameters,

such

as

the

concentration

of

H„SiF,, H„SO„ and 2 O 2 4

H PO. in the 3 1

solution, an expression has to be developed. The most the taken highly species composition and the temperature of the solution are believed to be the parameters, which determine the amount of evading fluoride. In of the composition the activities of the species have to be activity coefficients of the instead of their concentrations since we are dealing with electrolyte solutions. The essential description into in

account, such

concentrated

solutions can be calculated with the ion specific interaction

model of Pitzer [30]. 7.H.2. Pitzer Calculation of the activity coefficients [29D showed that the ion activity coefficients of an electrolyte MX can

be calculated from the following equations: I n YM = z**F + E m *(2*B M + Z*C M = ) + E m * ( 2 * 0 M + E m *ï) M M a Ma Ma c Mc a Mca a c a + I * E E m *m ,** , M + | z J * E E m *m *C 2 , a a ' a a ' M ' M ' c a c a a a' c a i n Tx = z£*F ♦ E V ( 2 * B X c + c
Z C

(1)

" Xc>

+ l

m

a

a*(2*QXa+

Z

c

V

W (2)

+ I * I E m *m *<? , + | z v | * E E m *m *C 2 , c c ' cc'X ' X' c a ca c c' c a where where: '/ _«*(___! * ,.h,T 'z 1+b*I z

the subscripts M, c and c' refer to cations and X, a and a' to anions and

F =

+

I * ln(1+b*I t >

/a

)) + E E m *m *B' c a ca ca (3) J

+ 5 * E E m *m *0' , + \ * Z E m *m *6' 2 c c' cc' 2 , a a' aa' c c' a a' Z = E m *|z. I = 2.* E m *z i'l' c c l c For 1-1 and = 2 * E m *|z I a ' a' a

(H)

1-2 electrolytes the coefficients B.„, which are functions of the MX ionic strength have the following form:

103

B

MX

" *m

+

6

MX )

* *(x>

(5)

B,

MX

=

B

MX}*«,(X)/I

(6)

g(x) = 2 * (1 - (1 + x) * e"x)/x2 g'(x) = - 2 » (1 - (1 + x + | * x 2 ) * e"X)/x2 x = 2 * /I and b = 1.2.

(7) (8) (9)

In these calculations the third virial coefficients can be neglected, since these with coefficients concentrated do not have a great influence on the activity coefficients solutions the Debye-Huckel term A can also be [30]. This implies that the C and i | i terras can be omitted. Because we are dealing electrolyte omitted. Without these terms the equations (1) and (2) can be rewritten as: In YM = E m *2*B„ + Z m *2*0M + M a Ma c Mc a c + z 2 * ( Z Z m *m *B' + \* Z Z m *m *0' , + \* Z Z m *m ,*Q' ,) M c a ca 2 c c , c c' cc* 2 & &, a a' a a " c a in Yx = I mc*2*BXc c Z m a *2*0 Xa a (10)

+

+

+ z 2 * ( Z Z m *m *B' + I* Z Z m *m ,*0' , + \* Z Z m *m »0' ,) X c a ca 2 . c c' cc' 2 , a a' aa' c a c c' a a' Due

(11)

to the high ionic strength of the solutions, g(x) in equation (7) and

g'(x) in equation (8) will tend to zero and the derivatives of the second virial coefficients can be considered to equal zero. These approximations are simplifying the equations (10) and (11) considerably: In Y = Z 2*m *BM + Z 2*m «0.. M „ a Ma c Mc a c in Yx - Z 2*mo*BXc ♦ Z 2*ma*0Xa c a These concentrated expressions (12)

(13)

for the activity coefficients of an electrolyte MX in a solution can be used for a description of the liquid

electrolyte

■\0k

phase in terms of activities of the species, if the composition of this phase in concentrations of the species is known. The In species hydrogen section ion concentration T.H.H. it will be obtained of the phosphoric acid solutions can be that only the hydrogen ion calculated by using Elmore's model [8], as will be shown in the next section. be demonstrated concentration has to be calculated, because the concentrations of the other

can directly

from the amount of H-PO., H.SCK and H SiF,

applied for preparing the solutions. 7.4.3 • Calculation of the hydrogen ion concentration in phosphoric acid In order to calculate the hydrogen ion concentration in phosphoric acid,

Elmore e.a. [8] assumed the following three equilibria to take place mainly: HgPO^ ■* H+ + H,,PO~ K1 (11))

H

6 P 2°8 3P°4
+ H P0

t 2 ~H t

H+

+

H P

5 2°8

%
K

(15)

H

H

5 P 2°8

0

(16)

where the K-values are given in molarities as: K 1 = 7.1 * 1 0 " 3 , K Q = 1.263 and K 4 = 0.3. The The existence hydrogen in concentrated phosphoric acid of the dimeric (H P O J or ion concentration at 25 °C can be calculated for a 1-1 HgPpOg was recently confirmed by Wertz and Cook [41], electrolyte with equation (25) from an article of Elmore e.a. [8] as:

1O (K

8 I-H3P°'.)

+ l08(1+K

°* a H 3 pV = iStislisfe+ 2*log ° c +
+

0.3387298 * ac + 0.030961 * ( a c ) 2 (17)

where a

= activity of the undissociated part of the phosphoric acid monomer expressed in mole per litre, c a = the total phosphate concentration expressed as H.PO^ monomer per litre and = c H + /c.

Substitution of c R + for ac in equation (17) leads to:

105

-1.0182/c +

^V^PO^

+

^^V^PO^

m

ÜÜ396557Ö-; + 2*10g °H+
+ 0.3387298 * cH+

+

+ 0.030961 * c^+

(18)

The

activity

of the undissociated

part of the phosphoric acid monomer,

a u on , can be calculated, according to Van Rysselberghe [32] with the equation: H PO 3 t d log a
H P

3 °4

= -§5i5_(_d log a„ .) B H H P0 4 2°

(19)

in which 55.5 is the number of moles H O per kg H O . The hydrogen ion molarities can be converted into hydrogen ion molalites with the following formula:

p

l

C

H PO,,

H3P01(

Elmore acid

e.a. [9] calculated the values of a„ _ as a function of the phosphoric concentration from vapour pressure data above phosphoric acid solutions at

25 °C with:

log a
H20

- log jjPQ

(21)

where P/Pn = vapour pressure of the phosphoric acid solution divided by the vapour pressure of pure water. Then -log they graphically evaluated at 25 °C from a plot of 3 4 for phosphoric acid concentrations between 7.5 and 80
M

the values of a

a„ - versus 1/IIL, on "2° 3 H molal. Equation from dependence

(17) has also been used for phosphoric acid solutions at temperatures no information is available about the temperature and the constants in equation (17). Hereby it is for phosphoric acid solutions containing 30 - 55 of the K-values

70 - 95 °C, because

assumed that the values of a„ w$

P _ 0 , _ between 70 and 95 °C are the same as those obtained at 25 °C. This is 25 not unrealistic, if the ratio P/Pn in equation (21) is assumed to be hardly temperature dependent. From the equations (18) and (20) and the values of a„ p n given by Elmore e.a. 3 H [9] the hydrogen molality can be obtained as a function of the phosphoric acid

106

concentration. molality the equation: n^+ = 0.551 * n^

Between

30

and

55

w$

P 0

a l i n e a r i n c r e a s e of the hydrogen

with the phosphoric a c i d m o l a l i t y i s found, which could be f i t t e d with

po

- 1.7179

(22)

7.H.H.

Determination of an expression for the fluoride distribution coefficients

For

the at

derivation

of

an

expression

for

the

fluoride

distribution

coefficients model of

the various phosphoric acid concentrations and temperatures, a

the H„P0„-H„SiF,-H„0 system is needed. The following simplified model 3 1 < = t > < = is taken, by lack of any other adequate model of the system: + SiF 4 (l) + 2 HF(1) (23)

SiFg" + 2 H +

SiF 4 (l)

+

SiFl4(g)

(24)

HF(1)

;

HF(g)

(25)

The

fluorosilicic

dissociated into The

acid is a strong acid and is assumed to be completely 2+ SiF, and H in pure water as well as in phosphoric acid [2]. constant, K, of the dissociation of H ? SiF, in the liquid

equilibrium

phase (equation 23) is represented by: a2
3

* HF

a

a SiF ü (26)

K =

a2+ * a

H

2SiFf 0

the volatile SiF a and HF compounds in the liquid phase 2are both assumed to be negligible compared to the activity of SiF, , at a molar F/Si ratio of six, which has to be maintained in the liquid phase if a maximal is therefore assumed only to be

The

activities

of

evasion is pursued. The fluoride 2present as SiF, in the liquid phase. In Pitzer's model as well as in

fluoride

Elmore's model molalities instead of

concentrations are used for the liquid phase. Since furthermore the gasphase can be assumed to behave as an ideal gas at about 100 kPa, the fluoride distribution coefficient can conveniently be defined as:

107

total_F_concentration in_the_gas_ghase SiF, molality in the liquid phase

Here H is defined in such a way that its value can easily be calculated from the measured total fluoride concentration in the gas phase and from the measured corresponding amount of F in solution, since the SiF. and HF concentrations in

the solution are neglected. Equation (27) can be rewritten as:
(4

H =

* C Si Fl) + eHF>g i-

(28)

The individual SiFü and HF concentrations in the gas phase are unknown, but these concentrations are related to the SiFj. and HF activities in the liquid phase by Henry's law:
C

HP(g)
(29)

h

(HF) ■ a"(i)
C

Si F l J ( g )

*(SiV - I - U )
The activities of SiF,. and HF in the liquid phase are assumed to be 2compared to the activity of SiFfi , but it will be assumed that they

negligible

always remain in the same ratio q:
a

HF(1)
(31)

q

= a--"(l)

Substitution of equation eq. (30) leads to:
HF m "2= m 2 SiF6 and:
C

(31) into eq. (26) and combination with eq. (29) and

K*q*a*+ ,
= h

(HF) (HF) *

(

}

a» 2SiF 6

2_ * YSiF SlF 6

(32)

108

C

a

S1F, - — « SiF 2 6

K*a*+ , = h,„.„ , * (2 ) / a * Y„ 2(SlI SiF V q *a*26 SiFg

(33)

Substitution of eq. (32) and eq. (33) in eq. (28) gives:

H = 1»h,

<

Sl

. * (— t t

V
K,

q *a%. p 2SiFg

2

) '3 * Y

SlF

2-

♦h

6

(HF)

* (

S-) ' 3 * Y
6

a%._2blt

SlF

2-

(34)

6

Since and

h,,.^, , h. . and q are constant only the activity coefficients (HF) (MFjJ 2the hydrogen ion molality have to be known. The SiF, concentration follows

from the total amount of F added as H?SiF, (see 7.6). Taking the logaritm of equation (32) and rearranging the terms leads to:

lnH =

V

-f"1" V
the in

+

-f"1" V " -f"ln m SiFf + -3"ln ^SiF2'
(12) and (13) for electrolyte as the activity solution are applied

(35)
coefficients of an on the

If

equations

electrolyte

a concentrated

H-PCL-HpSiFg-H-O

system, containing

most important species H , H_P_0„ and

SiF, , this delivers: 6 lnY+=2*m 2-*B+ 2'H SiFf H -SiF^ o o
ln

+ 2 * m - * B + HcPo0Q H -H c P o 0 0 5 2 8 b^o
+ 2

(36) ^ J

^SiF2" " 2 * V

* V-SiF2"

* m H 5 P 2°8 ^ 0SiF 6"- H 5 P 2°8

^
(38)

ln

V 2 0 8 " ■2 # V * V-H^o" * 2 " ™SiF2- * VA-SiF 2 In If equation (35) only the

values of t h e a c t i v i t y c o e f f i c i e n t s given by

equations (36) and (37) have t o be i n s e r t e d . a l s o s u l p h u r i c acid i s p r e s e n t i n the l i q u i d phase, i t i s assumed to be
+ -

d i s s o c i a t e d i n H and HSCL, and t h e e q u a t i o n s (36) and (37) become:
In Y + = 2*171 2- * B + 2 - + 2*m * B + - + ?*m
+

i n TH

ms.F£

BH _ s i F £

t

m

- * R +

-

fWl

H5P2o8

uH - H 5 P 2 O 8

2 m ^

V - H S O ^ (39)

109

In Y 2- = 2*m. + * B + 2- + 2*m - * e 2Y 0 SiF 6 2 % H -SiF6 H 5 P 2 0g SiF^ -H 5 P 2 O g 2*m - * 0 2HSOj, SiFg -HSO^ (MO) K u '

The data ion it

hydrogen

ion molality is difficult to calculate, since no literature

for H PO.-H SO.-H SiFfi mixtures are available. In calculating the hydrogen molality the H_SiF, is assumed to be completely dissociated and one mole of
d 0

therefore

gives two moles of hydrogen ions. One mole of H SO. is assumed to of hydrogen of ions. The hydrogen ions resulting from the of H.POj. can be calculated as indicated in the former section with the presence of H SO,, and H ? SiF, the degree of

deliver equation

one mole

dissociation

(22). Because

dissociation of H,POü will lessen. The degree of dissociation of phosphoric acid was calculated to lessen about 5-7 % for phosphoric acid solutions containing 38 wj P„0 C and up to 17 w? HoS0... This relatively small decrease is neglected,
do d "

because

such

high

H-SO. or H?SiFfi concentrations will never be present in the prevailing in the CTPA process and the following

phosphoric

acid

solutions

equation is used: m + = a *m
H

H,PO„ 3 4

- 1.7179 + 1m
'•'"*

"HSO„ d 1

+ 2 * m.

KsiF, do

(Ml)

Equation (35) can be rearranged by inserting the equations (39), (40), (41) and (12) (with a = 0.551):

m

H 5 P 2 0 - " -■»H3P0J, "

K7179

{ 2)

"

into: In H = C* , | » in V
2 x (i * ( 3
Q

- I * in m
d 0

m m

a

H3P04

H 2 * a + 2 - + - * a * B + - + - * a * 0 2-) B B H -SiF^ 3 H -H5P20g 3 °SiF^ - H ^ O g ' +

+ m * (- * B + 2-) H2SiF6 ^3 H -SiFg ;

m

U 2 ? * ( _ * g+ _ + _ * e 2- + - * n + „.„2-) H 2 S0^ ^3 H -HS0^ 3 SiFg -HS0y 3 H -SiFg 110

U P 2 1 717Q * ( - * B + - + - * 0 2-+-*B+ 2-) '•<''* ^3 D H -HSO,, 3 SiF^ -HcP„0o 3 H -SiF^ ;
1 0 D £. 0 D

(H?1 ^i>

Replacing the terms with the constant C., a, B and Q factors in equation (43) by the constants C to C^ leads to:

in H - C, ♦ f • in

V

- f • in m ^ ^

♦ O, *

m

^

+ C3 *

m ^ . ^

By this equation the dependence of the fluoride distribution coefficient, H upon known or calculable of this from species in can the phosphoric acid solutions, is given. The now with be verified by comparing the H-values

validity calculated

equation this

equation

those

calculated from measured fluoride

concentrations in the liquid and in the gas phase by using equation (27).

7.5. Experimental

7.5.1. Chemicals

Chemically acid molar acid (98 wj

pure HjSOjj),

phosphoric

acid (85 wj H.PCO, chemically pure sulphuric

technical grade fluorosilicic acid (36 w$ H 2 SiF 6 ) with a 6, and distilled water are used to prepare the selected grade fluorosilicic acid is obtained from the

F/Si

ratio The

of

mixtures.

technical

fluoride recovery unit of a single filter HH/DH (Nissan-H) process. A molar F/Si ratio of six is maintained in the liquid phase, since the fingered filters of source.

boro-silicate glass present in the solution acted as a continuous SiO In all experiments

the gas phase consists of nitrogen gas saturated with

water vapour.

7.5.2. Equipment

In

figure

1

the

apparatus is shown.

for It

the

determination

of

the

fluoride

distribution boro-silicate tube situated gas

coefficients glass in

consists of ten wash bottles made of

with an inside diameter of 3 cm each. The end of each long the liquid in order was to a fingered filter needed to generate small create a large gas-liquid interface for

nitrogen

bubbles

masstransfer.

111

Wash disposure. fluoride.

bottle The In and

1

is

needed to protect the nitrogen supply pipe against acid bottles the nitrogen gas is heated to the selected

wash bottles 2 till 4 contain the selected acid mixture without these wash saturated with water vapour. The water vapour pressure in the

temperature since the

wash bottles 5 till 8 is assumed to be the same as in the wash bottles 2 till 4, composition of the liquid phase is only slightly different. The wash bottles 5 till 8 contain the same acid mixture as the bottles 2 till 4, but this time with the selected amount of fluoride added as H„SiF,. The absorption HF and in SiF^ vapours water are in removed from the nitrogen gas stream by distilled the wash bottles 9 and 10. All bottles are

filled with about 50 ml of liquid. WASTE 6AS

WASTE 6AS

Figure 1: Apparatus for the determination of the fluoride distribution coefficients. 7.5.3. Procedure The bottle. set nitrogen gas is supplied at a temperature of about 20 °C by a nitrogen The flowrate of the nitrogen gas is measured by a dry-gas flowmeter and m V h r . At higher values the fluoride content of the

with a flow controller. The maximum flowrate of the gas at a temperature of

20 °C is found to be 2.M 10

112

nitrogen

gas stream will not be in equilibrium with the fluoride content of the

liquid phase. The real gas flowrate through the wash bottles at the selected temperatures of the experiments can be calculated with:

6

= * (20°C) * (-1-) "

* ( 12!—-) in 5 - p H20 gas stream is

(D5)

After

the

nitrogen

set, the gas is led through the wash

bottles 2 till 8 and led to the waste-pipe via three-way valve 2. After checking for leakages, the wash bottles 2 till 10 are placed in a thermostated water bath of the selected temperature. When after the content of the wash bottles has reached the required temperature 20 min., three-way valve 2 is reset and the gas is led through the bottles 9 and 10. After a fixed time of about 30 to 60 min. the gas

about

absorption is led

again

to the waste-pipe by resetting three-way valve 2. Thereafter the

complete apparatus is taken out of the thermostated bath. The contents of the absorption bottles 9 and 10 is assembled in a 250 ml

flask and diluted with distilled water to 250 ml. The 10 as fluoride well 5 as in content in the absorption liquid from the wash bottles 9 and the wash bottles 5 and 8 is measured. The contents of the

bottles fluoride amount six.

and 8 are analysed for their fluoride concentrations to check if the content of wash bottle 8 remained constant and equal to the added

of

fluoride and if the molar F/Si ratios in the bottles 5 to 8 remained of both quantities ensured saturation of the gas stream with

Constancy

fluoride under the selected conditions.

7.5.4. Analyses

The selective

fluoride content of the absorption bottles is measured with a fluoride electrode (F1052F of Radiometer). A TISAB-IV buffer [37] is used to

keep the ionic strength of the solution at a constant value. Hereto 25 ml of the absorption liquid and 25 ml of the TISAB-IV buffer are well mixed. These acid

probes are diluted with water by a factor 50-100 and analysed for their fluoride content with a calibration procedure.

113

The and 10

silicon concentration in the absorption liquid from the wash bottles 9 as well as in the wash bottles 5 and 8 is measured with the ICP-

technique. 7.6. Results and discussion In molar all experiments a molar F/Si ratio of six was found in the wash bottles ratio acid in the liquid was maintained during the experiments, due to phase of the HF formed by partial dissociation of the

5 and 8 as well as in the absorption liquid from the wash bottles 9 and 10. This F/Si reaction in the liquid

fluorosilicic the molar of

with the fingered filters of glass at the long tube ends in in the absorption liquid was found to be also six. The no signs of reaction with HF contrary to the

the wash bottles. The molar F/Si ratio in the gas phase was six or more, because F/Si the ratio bottles surface showed

fingered filters in the solution. The fluoride distribution coefficients are calculated from the total amount of fluoride present in the wash bottles 9 and 10, the known quantity of gas led of the acid in mixture in wash bottle 8 by applying equation (27). The through the absorption liquid in the given fixed period of time and the fluoride content procedure The of wide phase. given fluoride 1 the appendix (7.10) was used to convert the concentrations

given in wj P„0_, w? H_S0,, and w$ F into molalities. distribution coefficients are given in table 1 as a function shows to that the fluoride distribution coefficients vary over a the influence of both the temperature and the acid the temperature and the H_P0Ü, H.S0Ü and H.SiF, concentrations in the liquid Table range, due

concentration. The influence of the phosphoric acid concentration on the fluoride 3 distribution coefficient (expressed in mg F/ m vapour/ w$F in the solution, i.e. units normally used in the industry) is illustrated in figure 2 (curve 1). In this figure also the fluoride distribution coefficients obtained by Spijker [38] in the a simulation of an industrial evaporator (curve 3) as well as the values of distribution coefficients calculated from the results obtained by [20] are from not gas reached are saturation experiments are given (curve 2). This the maximal in an values industrial of the fluoride distibution is not evaporator. This shows that e.a. clearly fluoride

Kopylov figure

coefficients industrial calculated

surprising, because

the molar F/Si ratio in the liquid is not equal to six and designed to evaporate water from W.P.A. and not to

evaporators from the

remove fluoride from W.P.A.. The values of the fluoride distribution coefficient results of Kopylov e.a. [20] are significantly lower than 114 •

those the

obtained here. They could only detect SiF. in the gas phase and therefore F/Si ratio in they the solution probably increased with time in their with a molar F/Si ratio of six in the although started

molar

experiments, solution the

also. Another explanation can be that not all fluoride present in the fluoride in the alkaline solutions used for the absorption of the

gas phase was detected in their experiments, due to the precipitation of part of evaded The is The fluoride from the gas phase. influence of the temperature on the fluoride distribution coefficients in figure 3. This figure shows that the fluoride distribution illustrated

coefficient is proportional to the reciprokal value ofthe absolute temperature. temperature dependence of the fluoride distribution coefficient can thus be If the temperature dependence expressed by a Clausius-Clapeyron type relationship [3.18]. is accounted for by adding a C./T term to 5 equation (14), this equation can be rewritten as: in H = | * in m H + - | * In m ^ g ^ ♦ C, ♦ O, * m ^ ♦

+

C

3 * m H 2 SiF 6
C.,

+

S * "HJJSO,

+

S/T

W)

The

parameters

derived from our experiments and optimised with a computer

program are:

°1 = 32,i|' °2= °- 156 '
The above equation

C =1 -°' Cn = 3
with the

°'H57

and c =
C-values

5 "955°
was found to describe the

given

experimental results in the following area: - wï P 0 - w$ H SO in the phosphoric acid solution between 30 and 50. between 0 and 6.

- w* H2SiF, below 1. - temperatures between 70 and 95 °C. - a molar F/Si ratio of 6.

115

exp. no. '

C

Po° c 2 5 (w*)

C

H„S0„ 2 4 (w$)

C

F

T

VPO, 3 4
l

"HOSO,,

2

4

VsiR
2

H.10 6

-4

(wj)

(°C)

, mole . . mole . , mole . kg"H~5J

. mg F/m 3 vap_our ^inoïe H^SÏFg/kg H^>'

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 21 25 26 27 28 29 30 31 32 33 31 35 36

35 38 10 10 13 17 52 55 17 17 40 10 38 38 47 17 47 17 17 10 10 10 10 10 10 17 17 17 17 47 47 47 47 40 40 40

0 0 0 0 0 0 0 0 2 4 2 4 4 8 0 0 0 0 0 0 0 2 2 4 4 2 2 2 2 2 2 4 4 4 4 4

1.81 1;86 1.90 1 .92 1 .85 1.85 1.77 1.77 1.83 1.83 1.83 1.93 1.91 1.83 0.83 3.3 1.7 1.88 1.85 1.86 1.83 2.07 2.07 2.06 2.05 1 .90 2.03 2.00 3.82 4.22 4.22 2.10 2.10 4.06 1.06 1.11

91 90 90 94 90 90 90 86 90 90 94 94 90 90 90 90 90 73 83 70 81 70 80 70 80 70 80 90 70 80 90 70 80 70 80 90

9.99 11.84 13-291 13.30 15.81 20.19 28.18 35.46 21.48 22.97 13.91 11.69 13.02 11.37 19.125 21.383 23.678 20.212 20.188 13.275 13.263 11.026 11.026 14.753 14.749 21.543 21.657 21.633 23.390 23.815 23.815 23.248 23.248 15.799 15.799 15.841

0 0 0 0 0 0 0 0 0.662 1.416 0.504 1.064 0.990 2.192 0 0 0 0 0 0 0 0.508 0.508 1.069 1 .069 0.664 0.668 0.667 0.721 0.734 0.734 1.434 1 .434 1.145 1 .145 1.148

0.327 0.361 0.393 0.398 0.424 0.495 0.597 0.711 0.521 0.557 0.387 0.441 0.111 0.131 0.211 0.935 1.412 0.504 0.195 0.385 0.378 0.453 0.153 0.173 0.171 0.512 0.582 0.573 1.184 1.332 1.332 0.647 0.647 0.999 0.999 1.020

2.51 2.77 2.46 3.02 7.31 16.16 43.55 134.34 31.7 57.5 6.70 9.80 7.20 12.0 14.0 . 19.0 28.0 5.23 9.72 0.726 1.31 1.01 2.10 1.29 3.14 6.29 12.98 27.20 9.37 18.94 47.74 9.20 16.15 2.78 7.43 12.96

Table 1: Fluoride distribution coefficients as a function of various concentrations and temperatures.

116

}Q°-\

[
io5H

Temperature 90°C mg F/m 3 vapour"!

%~F

-I

10"

io3H

10' 10 20 30 -*-

—f— 40 w%P205

50

60

Figure 2: The fluoride distribution coefficient as a function of the phosphoric acid concentration.

12H

1H

• 40w%P205,Ow%H2SO(( X40w%P205.2w%H2S0i> a i t 0w%P 2 0 5 .4w% H2S0i(

10H

I Ü

I 2.8

1

2.9 - ^

!

x103

Figure 3: The fluoride distribution coefficient as a function of the temperature.
117

ggp.

T

mH

H-raeas. * 10 mg F/m^ vap_our_ , möTe~H2SiF"7kg H Ö'

J

^kg~H~0''

l

möIe~H S i F 6 / k g - H 2 Ö ;

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36

94 90 90 94 90 90 90 86 90 90 94 94 90 90 90 90 90 73 83 70 81 70 80 70 80 70 80 90 70 80 90 70 80 70 80 90

4.44 5.528 6.391 6.406 7.841 10.40 15.00 19.24 11;82 13-47 7.224 8.322 7.274 9.254 9.413 11.93 14.15 10.43 10.40 6.365 6.364 7.425 7.425 8.426 8.418 11.90 12.05 12.01 14.26 14.80 14.80 13.82 13-82 10.13 10.13 10.20

2.510 2.770 2.460 3.020 7.310 16.16 43.55 134.3 31.70 57.50 6.700 9.800 7.200 12.00 14.00 19.00 28.00 5.227 9.719 0.726 1.307 1 .015 2.103 1.291 3.137 6.293 12.98 27.20 9.367 18.94 47.74 9.198 16.15 2.778 7.425 12.96

2.246 2.521 3.396 4.522 5.650 13-06 56.53 54.1 23-34 44.92 6.834 10.60 5.504 13.67 14.32 17.53 34.40 3-596 7.784 0.734 1.744 1 .107 2.434 1 .727 3.797 5.087 11.42 23.94 8.876 23.07 48.59 10.28 22.62 2.447 5.383 11.56

-10.5 -9.0 38.1 49.8 -22.7 -19.2 29.8 14.7 -26.4 -21 .9 2.0 8.1 -23.6 13.9 2.3 -7.7 22.9 -31 . 2 -19.9 1.1 33.4 9.0 15.7 33.8 21 .0 -19.2 -12.0 -12.0 -5.2 21.8 1.8 11.8 40.0 -11.9 -27.5 -10.8

Table 2 : Experimental and c a l c u l a t e d coefficient.

values for the fluoride distribution

118

In from values values

Table

2 the values of the fluoride distribution coefficient calculated data by and indicated by H-meas. are compared with the H-cal (46). The the derived expression fits the H-meas. high sensitivity of this kind of

the

measured

predicted reasonably

equation

well.

Considering

experiments for stoppages and leakages an error of about 10-20? is unavoidable. It turned out to be important to check whether leakages occur and whether bubbles while the are formed in the liquid at the bottom of the wash fingered filters are severely attacked and large

sufficiently bottles. bubbles

small a

After are

formed. Then the fluoride content of the nitrogen gas might not be

in equilibrium with the fluoride content of the liquid phase. Stoppages are mainly caused by the unwanted formation of SiO_, when evaded

SiF. reacts with condensed water [5,38,40] according to:

3 SlFy + 2 H 2 0

+

Si0 2 + 2 H ^ i F g

(47)

5 SiF„ + 2 H„0

>

Si0 o + 2 H.SiF,.SiF„

(48)

In

addition

to the experiments with chemically pure acids, also experiments

were performed with W.P.A. obtained from a single stage HH/DH (Nissan H) process to determine the The influence measured of impurities on the fluoride distribution

coefficients.

fluoride

distribution coefficients as well as the

values predicted by eq. (16) are given in table 3.

P205

H ^
KW

Si
W ;

F
lW%M

m 3 1

m 2 1

m 2 O

mHF

F/Si
(

H-exp ,

H-cal

(wï)
W ;

(wt)

(wï)

f„ï)(- m 2i§-w_ m 2iË.w_!!!°ie_w_!nole_.mole kg H20Mkg H20Hkg H20Kkg H 2 0 , r a " °

, __mg_F/m__vapour rnole H 2 SiF 6 /kg H 2 0 )

28.0 36.t 45.2 50.6 54.2

2.0 2.5 3.0 3.4 3.7

0.236 0.249 0 . 1 24 0.013 0.017

1.29 1.24 0.72 0.49 0.44

6.824 11.209 18.864 27.170 36.333

0.353 0.558 0.907 1 .167 1 .797

0.1458 0.1945 0.1313 0.0177 0.029

0.300 0.260 0.335 0.877 0.931

8 7 9 55 38

2.297 3.285 21.515 293-592 212.705

1.705 4.442 29.180 513.635 2575.171

Table 3: F l u o r i d e d i s t r i b u t i o n c o e f f i c i e n t s for W.P.A. a t 90 °C.

119

The (16) for ratios,

values differ

of the fluoride distribution coefficient predicted by equation phosphoric acid (> 50 wj P2°c:)> having high molar F/Si largely from the experimental values. In this case the fluoride

concentrated

is not only present as H„SiF, but also as HF and therefore the equations (3) and (9) are no longer valid. For during and F/Si the prediction from of 30 the to fluoride distribution coefficient of W.P.A. concentration above 50 w$ P-,0,., when the molar F/Si ratio

changes from about 6 to approximately 60, the model presented here is too simple leads to erroneous results for phosphoric acid solutions containing a molar ratio above ten. This again stresses the importance of the addition of if a high fluoride evasion were pursued.

sufficient SiO

7.7. Conclusions - Stripping and flashing seem to be the best methodes for the removal of fluoride from phosphoric acid production processes if the fluoride has to be recovered and is used as a new fluoride source, which can substitute for fluorite. - If almost all fluoride must be removed from the phosphoric acid pure as well as W.P.A. a molar F/Si ratio of about six should be maintained in the solution to obtain the highest fluoride distribution coefficients. - From a theoretical model an equation is derived describing the fluoride distribution coefficients between phosphoric acid solutions and the gas phase as a function of various process parameters. This equation was found to describe the measured values with reasonable accuracy between 70 and 90 °C, for chemically pure as well as for commercial phosphoric acid solutions containing 30-50 w$ P 0 , up to 6 w$ H SO., .maximal 4 w% H„SiF, and a molar F/Si ratio below 10. - The model used for the derivation of an expression for the fluoride distribution coefficient is too simple to predict fluoride distribution coefficients for W.P.A. during concentration, when the molar F/Si ratio in the liquid phase changes from about 10 to approximately 60. - The simplified model cannot predict the molar F/Si ratio in the gas phase.

120

7.8. A,
9

Nomenclature Debye-Huckel coefficient

b B c C h H I K m M P T z a

thermodynamic parameter binary interaction parameter concentration ternary interaction parameter Henry coefficient fluoride distribution coefficient
ion strength equilibrium constant molality molar mass vapour pressure absolute temperature ion charge number degree of dissociation thermodynamic parameter activity coefficient density binary interaction parameter ternary interaction parameter volume flow

mol/1

mg F/m^ vap_our möl"H~SiF77kg"H~Ö
2 0 2

mole/kg HO g/mole Pa K

B
Y P

kg/mJ

e
*
V

m 3 /hr

subscripts:

a,a' c,c'

anions cations gas phase component liquid phase

g 1 1

supers cript:

t

derivative

121

7.9. Literature 1. Baur, E., Zeitschrift fur Phys. Chera., 48 (1984) 483. 2. Becker, P., Phosphates and Phosphoric Acid, Fertiliser Science and Technology Series, Vol. 3 (1983), Marcel Dekker Inc., New York. 3. Borisov, V.M. and Mel'nikova, S.V., Zh. Prikl. Khira., 57, 3 (1984) 705. 4. 6. 7. 8. 9. Buskus, H., Chemisch Magazine, Nov. (1985) 735. Chemtob, E.M. and Beer, G.L., US Patent 4.505.884 (1982). Drechsel, E.K., Chem. Eng. News, 24 (1979) 37. Elmore, K.L., Hatfield, J.D., Dunn, R.L. and Jones, A.D. J. Phys. Chera., 69, 10 (1968) 3520. Elmore, K.L., Mason, C M . and Christensen, J.H., J. Am. Chem. S o c , 68 (1946) 2528. 10. Eyal, A. and Baniel, A., Solvent Extraction and Ion Exchange, 2 (1984) 677. 11. Eyal, A., Hajdu, K. and Baniel, A., Solvent Extraction and Ion Exchange, 2 (1984) 659. 12. Flemmert, G.L., Proceedings of the Fertiliser Society of London, no 163 (1977). 13. Fokin, M.N., Petrovskaya, V.A., Dobrolyubov, V.V., Kurteva, 0.1., Nikolaeva, G.N. and Grabyl'nikova, V.I., Khim. Prom., 9 (1984) 543. 14. Frazier, A.W., Lehr, J.R. and Dillard, E.F., Environ. Sci. Technol., 11, 10 (1977) 1007. 15. Getting rid of Phosphogypsum 2, Phosphorus and Potassium, 89 (1977) 36. 16. Hodges, W.A., US Patent 2.917.367 (1959). 17. Homann, J., Werkstoffe und Korrosion, 37 (.1986) 532. 18. Illarionov, V.V., Smirnova, Z.G. and Knyazeva, K.P., Zh. Prikl. Khim., 36, 2 (1963) 237. 19. Kitchen, D. and Skinner, W.J., J. Appl. Chem. Biotechnol., 21 (1971) 53, 65. 20. Kopylov, V.A., Senetova, G.I. and Pozin, M.E., Zh. Prikl. Khim., 48, 11 (1975) 2455. 21. Kopylov, V.A., Senetova, G.I. and Pozin, M.E., Zh. Prikl. Khim., 49, 5 (1976) 1149. 22. Lehr, J.R., Proceedings of the Environmental Symposium of the Fertiliser Institute, New Orleans, March 6-8, (1978) 277. 5. Charleston, A.G., New Zealand Journal of Science, 27, 3 (1984) 279.

122

23. Miller, F.D. and Biggers, E.D., US Patent 3.193-351 (1965). 24. Ministerie van Economische Zaken, Directie R. en 0., Technieuws Washington W-84-09, Technische Keramiek, 's Gravenhage (1984). 25. Nabiev, M.N., Gafurov, K. and Korosteleva, V.I., Khim. Prom., 6 (1983) 318. 26. Nassif, N., Surf. Technol., 26, 3 (1985) 189. 27. Odintsova, G.S., Guller, B.D., Zhdanova, M.V. and Zinyuk, R.Yu., Zn. Prikl. Khim., 54, 1 (1981) 37. 28. Phosphoric Acid, Outline of the Industry, British Sulphur Corporation Ltd., London, (1984). 29. Pitzer, K.S., Am. Chem. Soc. Symp. Ser., 123,23 (1980) 451. 30. Pitzer, K.S., J. Phys. Chem., 77, 2 (1973) 268. 31. Rushton, W.E., Che. Eng. Progr., 74, 11 (1978) 52. 32. Rysselberghe, P. von, J. Phys. Chem., 39 (1935) 403. 33. Senetova, G.I., Kopylov, V.A. and Pozin, M.E., Zh. Prikl. Khim., 49, 6 (1976) 1371. 34. Senetova, G.I., Novikov, A.A., Kopylov, V.A., Khoipunov, N.F., Repenkova, T.G. and Pozin, M.E., Zh. Prikl. Khim., 49, 6 (1976) 1374. 35. Shape, J.L., Miner, M.L., Harris, L.E. and Greenwood, D.A., Am. J. Vet. Res., 23, 95 (1962) 777. 36. Shr.amban, B.I., Pavlukhina, L.D., Afonina, N.D. and Gorskaya, A.P., Zh. Prikl. Khim., 52, 10 (1979) 2344. 37. Spijker, R., UKF Internal report no. YB0-RP-81-208 (1981). 38. Spijker, R., UKF Internal report no. YB0-RP-83-248 (1983). 39. Teslenko, V.V. and Rakov, E.G., Khim. Prom., 12 (1981) 744. 40. UKF, Private communications. 41. Wertz, D.L. and Cook, G.A., J. Sol. Chem., 14, 1 (1985) 41. 42. Weterings, K., The Utilisation of Phosphogypsum, Proc. of the Fertiliser Society of London no. 208 (1982).

123

7.10 Appendix: Conversion of w% to molalities For only conversion chemically of w$ pure to molalities for a phosphoric acid solution containing phosphoric acid, sulphuric acid and fluorosilicic acid

the following procedure is used: 2 *x x wj P„0_ = Ü mole H-PO.. per 100 grams of solution. (1)

25

.y^

3 *
mole H SO. per 100 grams of solution

y w$ H SO. = --^
d H S0 2 n

(2)

1 z z w£ F = r * r.- mole H„SiF, per 100 grams of solution
b
M„
d 0

(3)

The water content of 100 grams of solution, w is then given by:

luu

d

M^

^ 2 5

H^O^

y

6

MF

H 2 SiF 6

(H>

and the molalities are calculated with the following equations: (5)

x w$ P 0

= 2 * M"--- / w
P

mole H PO^ per kg H 2 0

2°5 / w mole H SO. per kg H?0 (6)

y w? H SO. = - - x

zw*F=jr*-;-/w
D M
r

mole H.SiF, per kg H.0
d O
d

(7)

12H

8. MASS AND HEAT BALANCES OF THE CTPA PROCESS 8.1. Introduction Phosphoric produced process". The
c.

acid,

used

for

the

manufacturing

of

fertilisers is mainly

by digestion of phosphate ore with sulphuric acid, the so-called "wetproduction
D

of phosphoric acid is expected to rise from about 20

million tons P„0._ in 1982 to about 28 million tons in 1990 [26]. In all wet processes, impurities such as cadmium, radium and fluoride ions, originating are sulphate radium content the decay both from the phosphate ore (Ca Q(P0.)gF between the The phosphoric use while the acid + a few w? CaCO and the and quartz), distributed and byproduct, a calcium

modification. fluoride [1]. The

of the byproduct is limited by its phosphate, disposal is hampered by its cadmium the strength of the byproduct, while the

content,

phosphate

reduces

fluoride reduces its hardening time [26]. Fluorides can enter the atmosphere via production of radium process yields too. They are regarded as serious pollutants [26]. The the radio-active radon gas. The most problematic

contaminant is, however, cadmium. It is very toxic and can enter the food chain, via the byproduct and the phosphoric acid. Too high cadmium contents might In most processes the digestion of phosphate ore and the crystallisation of C a S O ^ H g O (DH) or CaSO^-rH-O (HH) take place more or less simultaneously in the same the CdO. reactors [1], The easiest way to remove cadmium therefore seems to be from ore, is This before it is introduced in the process. One method to achieve this of the ore at about 700 °C, the cadmium then evades as the of solubility and radium cadmium of phosphate ore is reduced by calcination plant. while selective of the even prohibit the use of phosphate fertilisers in the future.

purpose producing method

process, however, requires about 20 MW for a 1000 tons P_0_ per day Moreover, the fluoride ions remain in the ore. Another

calcination, is phosphate digestion acid

leaching

from the carbonate fraction of the

ore, which sometimes contains up to 50 \*% of the cadmium, by means of carbonate containing part of the ore with diluted sulphuric

with a high chloride content [9,31]. The chloride ions keep the cadmium as

cadmium-chloride complexes In the solution and thus prevent the precipitation of cadmium either as cadmium sulphate or phosphate. Incorporation of cadmium in the calcium sulphate modification produced can therefore also be reduced by feeding agents, such as halogen!des to the process liquid. These methods, complexing

however, only appear to be satisfactory if the cadmium content of the ore is not

125

too acid

high. or A

Furthermore the leaching

the cadmium still has to be removed from the phosphoric solution. In all cases the radium remains in the

"phosphogypsum". completely process before as HH. different method is based on the separation of the digestion the stages A possibility is created to optimise the digestion and and In be the crystallisation stages, in order to remove the cadmium ions in between. this independently from each other. Moreover, the radium can disadvantage, however, is the large recycle stream of

crystallisation removed precipitated The Acid the phosphoric aim

the majority of the calcium ions from the phosphate ore are

phosphoric acid needed for complete digestion of the phosphate ore. of this new process, referred to as a Clean Technology Phosphoric (CTPA) process is the production of commercially competitive concentrated acid (40 w$ P-0_) with a low cadmium and fluoride content as well as of calcium sulphate hemihydrate (HH) with a low cadmium, production This study

phosphate and radium content. considers the mass and heat balance of the process. It is the first step towards the engineering flow diagram of a production plant, which can be used to compare this process with existing processes. 8.2. Process description 8.2.1. General approach To the meet the foregoing requirements the digestion of the phosphate ore and

crystallisation of the HH are separated in two almost independent stages. A First the digestion of phosphate ore proceeds in recycled phosphoric acid. contains in the precipitate too much. sulphate ions in a concentration dictated by the operating crystalliser. Part of the calcium ions from the ore will as HH. Since more then 2 w? P„0_ is incorporated in this This HH is thus recrystallised into DH to reduce the

simplified flowsheet of the process is shown in figure 1. This acid

conditions therefore HH, the

it cannot be disposed, without lowering the overall phosphate efficiency of process

phosphate content of the crystals to an acceptable low level (< 0.5 w% P 2 0 c ) Before digestion the stage, cadmium together ions with can the be removed, the precipitated HH from the

insoluble residue of the ore, have to be

separated from the slurry to avoid problems in the cadmium removal stage.

126

The phosphate

cadmium (CDHP)

can

be

removed by

from

the almost clear calcium-di-hydrogen-

solution

anion

exchange of cadmium halogenide complexes

formed by addition of either bromide or iodide ions [33].

digestion

1

HH crystallisation

recrystallisahon HH-—DH H2S<H

DH

recycle add

product

Figure 1: Simplified process flowsheet.

The the

CDHP

solution

with a strongly reduced cadmium content is then fed to with the recrystallisation liquid and concentrated

crystalliser,

together

sulphuric acid. In this crystalliser the calcium ions from the CDHP solution are precipitated as HH. . Thereafter the HH is separated by filtration, yielding

concentrated phosphoric acid. About 90 w% of this phosphoric acid is recycled to the digestion stage. The to the the product acid is fed to the iodide or bromide removal stage and finally fluoride removal stage. After the removal of the iodide or bromide and

reduction

of the fluoride level, concentrated phosphoric acid (10 w$ PjCv)

with a low cadmium and fluoride content is obtained.

8.2.2. Digestion of phosphate ore

The tanks with in the

digestion series.

stage is proposed to consist of three equally sized stirred The phosphate ore is introduced in the first tank, together

recycled phosphoric acid and some clay. The clay is used to stimulate

the evasion of fluoride. It is the easiest way to add it here, because it can be mixed with the phosphate ore in advance. The quantity of clay (15 w? SiCv and 38 »% the Al 0.) is determined by the additional amount of active silica needed, above amount already present in the ore, to obtain a molar F/Si ratio of six in

the acid. The composition of the phophate ore used (10 w$ Khouribga, 60 w$ Zin) is

given in table 1. The phosphoric acid must have a concentration of at least 10 w% P 0. for

direct use in the production of mono- or dl-ammonium-phosphate (MAP or DAP) [1].

127

The temperature in the d i g e s t i o n i s l i m i t e d t o 95 °C t o avoid f o r m a t i o n of CaSO4.0H O (AH) .0H2 (AH). 2 The main r e a c t i o n occuring under t h e s e c o n d i t i o n s i s :
Ca

10(PV6F2 + Fluoroapatite component moisture CaO
P

U

H P 3 °4

10 Ca(H 2 P0 4 ) 2 CDHP

2 HF

concentration 1 w%

|

component Cd Cl Na K20 Si02 (total) Si0 2 (active) Hg Pb Organic C

concentration 21 380 0.56 0.08 1.35 0.35 5 2 0.3 mg/kg mg/kg w j t wj wj wj ug/kg mg/kg w%

50.8 wj 31.55 w j t 2.4 vf 4.2

so4
F

2°5

w?

A1 2 0 3
Fe

0.36 w% 0.17 wj 0.33 w* 5.9 w*

2°3

MgO

co2

Table 1: Composition of the phosphate ore (Khouribga/Zin 40/60 w$), The rate of the digestion is found to be determined by diffusion of calcium ions P20 from the surface of CDHP of the ore into the bulk of the solution. The maximum solubility in phosphoric acid can be expressed as 5.5 wj CaO in 40 w?

at about 95 °C [1]. To maintain a safety margin 90 °C, 40 wj P 2 0 ? and only The amount of recycled acid needed, is determined by the w% CaO in the CDHP

5 w$ CaO were chosen as the operating conditions. solution phosphoric as required part soluble minutes. The evasion phase carbonate of is carbon present in the ore evades as carbon dioxide, saturated with dioxide causes excessive foaming. The fluoride in the gas fluoride and water vapour. Due to the presence of organic carbon in the ore, the a mixture of hydrogen fluoride and silicon-tetra-fluoride with a mean after the digestion blinding stage of and the sulphate content of the recycled the ore particles, more than 99 w$ of the

acid. For a sulphate content of the recycle stream below 2 wj H SO., to avoid of the ore (maximum particle diameter 2 mm) is digested within 90

molar F/Si ratio of six.

128

The These

precipitated are

HH

contains

cocrystallised

PpCL, Al, Cd and fluoride. 1 1

species

assumed

to be incorporated as CaHPO^.^H 0, CaAlF .-H_0 and

cadmium ions. It ore is is furthermore assumed that 50 w$ of the fluoride originating from the either cocrystallised with the HH or precipitated as sodium-

fluorosilicate be the deposited HH

(Na.SiF,-). as

Although this fluorosilicate precipitate will partly

scale, it is assumed, that it leaves the digestion stage with

and the insoluble residue of the phosphate ore, which is mainly quartz.

These solids are separated from the CDHP solution by a gravity settler, followed by a decanter centrifuge. Because of the low permeability of the cake obtained

after pressure filtration of this slurry, filtration is not a realistic option. The while stage. The HH, the heat of digestion of the phosphate ore, the heat of crystallisation of heat losses through the vessel walls and the energy dissipation of the stirrers The to all contribute of the at 0 to the overall heat balance of the digestion incoming °C with of and the water outgoing streams are calculated specific heats given in the the almost clear CDHP solution is introduced in the cadmium removal stage, slurry, containing 50 w$ of solids, is fed to the recrystallisation

turbine stage. relative

enthalpies their The

values of

appendices.

heat

evaporation

is taken into account in the

enthalpy of the water vapour stream. 8.2.3- Cadmium removal

The

cadmium The

removal feed

is

assumed

to

be

done

in

a

tubular co-current

adsorption. basic agents anion for

consists resin After in

of the CDHP solution, a slurry of the strongly a CDHP solution and iodide ions as complexing the adsorber, the anion exchange resin is

exchange cadmium.

passing

separated

from

the

solution and almost completely recycled to the entrance of

the adsorber. Part of the anion exchange resin is regenerated with water. The from basic the excess iodide is circulating through the whole process and is removed

product acid, by passing this acid through packed columns of a weakly exchange resin. This last anion exchange resin is regenerated with ammonia, after washing of the resin with water to remove the

anion

concentrated

phosphoric acid.

129

To

prevent

oxidation

of

iodide

during

its

passage

through the whole

process, an adapted amount of iron is added in the digestion stage. The cadmium and iodide removal stages as well as the amount of iron needed, to prevent oxidation of iodide will be reported elsewhere [34]. These stages are not yet Only anion will included in the mass and heat balances in detail. They can be treated, the amount of water needed for the regeneration of the strongly basic resin in the and for the washing of the weakly basic anion exchange step of the HH filter cake washing stage, after however, as black boxes, with very little exchange of mass and heat. exchange be used

resin is roughly estimated. This water comes from the fluoride removal stage and second removal of cadmium from this stream, by either electrolysis or precipitation as

a sulphide. 8.2.4. Crystallisation of calcium sulphate hemihydrate (HH) The main reaction in this stage is: 2 Ca(H 2 P0 1) ) 2 This the + 2 H 2 S0 4 + H20 — > 2 CaSO^.^O + 4 H PO,,

reaction

requires

a single stirred tank in which the CDHP solution,

concentrated sulphuric acid and the liquid from the recrystallisatlon stage To obtain HH in crystals with a good filterability the sulphuric acid

are introduced simultaneously. concentration the crystalliser must be kept constant at about 1.7 wj H.SOj.,
A1

while a residence time of about 30 minutes is recommended [26]. The precipitated HH contains cocrystallised P20c> amount which can be calculated form appendices for all these ions. The most important heat effect in this stage is the heat of crystallisation of HH. The heat of mixing of the acids is quite low, because the major part of is is maintained at about 90 °C, to prevent formation of AH. The the sulphuric acid is almost directly precipitated as HH. The temperature in the crystalliser excess heat removed by evaporation of water in a vacuum slurry cooler. The i
cd and

fluoride in an

the correlations and data given in the

enthalpies of the streams are calculated, relative to their values at 0 °C, with the heat capacities, given in the appendices.

130

8.2.5. Recrystallisation of HH into gypsum The HH formed during digestion of the ore is recrystallised into DH under similar to those prevailing in commercially known HH to DH processes, i.e. at about 60 °C in a solution containing 27 is assumed to consist of three equally sized

conditions, 30 w* P 2 0 The stirred

recrystallisation

and about 5 w$ H ^ O ^ . recrystallisation tanks stage in series. The slurry from the digestion stage, containing about

50 wj CDHP solution, is fed to the first tank, together with the wash water from the HH and the DH filters, concentrated sulphuric acid and half of the DH slurry stream from the third recrystalliser. This slurry stream is recycled to supply enough DH seed material to ensure a high recrystallisation rate of HH into DH. A residence time of about five hours should be sufficient for complete conversion of HH into DH [26]. The an produced The DH also contains cocrystallised P o 0_, Cd, A1 and fluoride in can be obtained from the data and correlations given in the Al, and fluoride are assumed to be incorporated as are caused by the heat of recrystallisation of HH phosphate, heat effects

amount, which

appendices. The

CaHP0^.2H20 and CaALF .2H20 respectively. main into DH, the heat of mixing of sulphuric acid with water and phosphoric acid. To maintain a temperature of about 60 °C in the first recrystalliser, water must be evaporated calculated, by vacuum slurry cooling. The enthalpies of the streams are relative to their values at 0 °C, with the heat capacities given in

the appendices. 8.2.6. Solid-liquid separations A slurry. to avoid belt filter is used for the filtration of both the HH slurry and the DH

The HH as well as the DH crystals are washed three times in counterflow recrystallisation into DH on the filter. This would reduce the

with water. The wash water temperature for the HH washing must be at least 60 °C permeability of the filter cake. The wash water of the DH crystals is assumed to be about 15 °C. The HH as well as the DH crystal cake contain aproximately 30 w$ liquid. Neither HH nor DH is assumed to dissolve in the wash water. The HH and DH crystal cake contain 30 w? pure water after the third wash step. This implies negligible P„0_ losses due to washing. A small amount of water evaporates during filtration of the DH and HH slurry.

131

The is P 0 ) and needed

total amount of water, which can be used as wash water in this process the the sulphuric acid concentration, but also by the amount of water washing of the anion exchange resins. The

not only determined by the required concentration of the product acid (to w$ for regeneration and

washing procedures of the HH and DH cakes are assumed to proceed isothermal. 8.2.7. Fluoride removal After the iodide removal, the fluoride level in the product acid is reduced to about 0.5 with w? the F in a packed stripping column. Stripping is achieved with a off gasses from the digestion stage, fed to a crossflow mixture of carbon dioxide and water vapour of about 90 °C. The stripping gas is, together scrubber, scrubber. in which part of the fluoride is removed from the gas mixture through washing largest with water. A 25 w$ H_SiF, solution is produced in this part of the gas mixture is recycled to the stripping The

countercurrent

column. The residual gas mixture is disposed, after passing a second scrubber to meet environmental requirements. The scrubber water, of to this be applied for the HH cake washing, is used in the second water is further raised by using it in the direct as a scrubbing medium. This scrubber operates at room temperature. The wash

temperature

contact condensor, in which the water vapour from the recrystallisation stage is condensed. Thereafter the temperature is raised to about 60 °C, by applying this wash water for direct contact condensation of the water vapour from the crystalliser. Since not well the heat capacities of the streams in the fluoride removal stage are known, only a rough estimation of this stage is included in the mass

and heat balances. 8.3. Combined mass and heat balances for each stage The balance equations needed to calculate the overall mass and heat

balances of the complete CTPA process are for each stage: - the overall mass balance - the mass balances for the four components CaO, SO,, P20_ and water - the overall heat balance The fixed operating conditions were: - 40 w$ P„0 C in the product acid - 5 wj CaO in the CDHP solution

132

- 1 J 4 H2SOn in tne cystalliser - 5 w$ H SO. in the recrystallisers If the Incoming and outgoing streams of a process stage are known, the overall balance equations of each stage can be written. The mass balances for the components CaO and SO. for each stage, can only be applied to solve the overall mass and heat balances of the CTPA process, if the solubility products of HH and DH (appendix 8.6.1) and the compositions of HH and DH are given. The P„0_ mass balance of each stage can be used to solve the total mass and heat balances, if accurate data on the incorporation of phosphate in the HH and DH are known. These data were either measured (see chapter 5) or obtained from literature and are given in appendix 8.6.2. The composition of the sulphuric acid as well as of the filter cakes and accurate data on the vapour pressure of water above the process streams are needed to be able to use the water balance of each stage. These vapour pressure data are obtained from literature and given in appendix 8.6.3. The heat balance of each stage requires the enthalpies of reaction, which are given in appendix 8.6.7, and the heat capacities or heat contents of the process streams, which are given in appendix 8.6.6. Information about the heats of mixing of the acids with each other and with water are also needed and are therefore given in appendix 8.6.8. For the less important components, from the viewpoint of process control, distribution coefficients are used, which for cadmium, aluminum and fluoride are given in appendix 8.6.2 and appendix 8.6.4. The complete set of mass and heat balance equations can be solved simultaneously with the software of the flowsheeting simulation package TISFLO2, developed by DSM. The number of equations must of course be equal to the number of unknown parameters. In this way the overall mass and heat balances of the complete CTPA process can be obtained as well as the composition of the process streams as shown in appendix 8.6.9. From the results given in appendix 8.6.9 a mass and a heat balance of each stage can be deduced. In the following part of this section the overall mass and heat balances of each stage are given and discussed. First of all the digestion stage will be dealt with. The incoming and outgoing process streams of the digestion stage are given in figure 2. In this figure the most important process conditions are given also.

133

The It to the DH phosphate solid will

mass

and heat

balances

of

this stage are given in table 2a and 2b

respectivily. is important to notice that the solids content of the slurry, to be fed stage, is a critical parameter in this stage. The concentration content of in the recrystallisers will raise above 30 w% P20c> if this slurry is less than 50 w$. This leads to a reduced the recrystallisation

conversion rate of HH into DH. As a consequence the recrystallisation of HH into not be completed before the filtration. This can cause a considerable reduction in the overall phosphate efficiency of the whole CTPA process.

ore
15°C
cta

L:
, 5w%Ca0 40.6 w % P 2 0 5 92.3 °C

vapour (P H Q =0,5 bar)

re\ \ \

y

CDHP solution

recycle phosphoric acid 90.8 °C
Figure 2: The digestion stage. component i n ore inert clay recycle acid 36.7 0.4 0.8 288.0

HH ore' scale

CDHP inert

componen t out vapour CDHP s o l u t i o n H H inert ore scale
CDHP

3.1 300.9 10.1 0.1 0.3 0.2 10.9 325.9

total

325.9

total

Table 2a: Mass balance of the d i g e s t i o n s t a g e (mass s t r e a m s in k g / s ) .

134

The has because

heat

of digestion of the phosphate ore is the second parameter, which The temperature in this stage can be higher in reality,

to be discussed.

the heat of digestion is not accurately known. A twice as high value as

used now will raise the temperature of the CDHP solution, however, at most 2 °C, due to the large heat content of the recycle acid stream. component in ore, inert and clay recycle acid heat of digestion heat of crystallisation 0.1* 67.2 component out vapour CDHP solution HH, inert, ore and scale CDHP heat losses total

2.8
66.7

3.6 2.0
73.2

0.9
2.it

0.»l 73.2

total

Table 2b: Heat balance of the digestion stage (enthalpies in M W ) . After cadmium mass mentioned. the digestion stage, stage This stage, which the almost clear CDHP solution is fed to the

removal

will be reported elsewhere [34], as was already

is regarded as a black box with very little exchange of

and heat.

The most important incoming and outgoing streams are shown in

figure 3, while an estimation of the mass and heat balances is given in table 3a and 3b respectively.

water 60°C CDHP 92.3°C Cd removal CDHP 92.3°C 646 mg Cd/s

60°C " water

Figure 3: The cadmium removal stage.

135

The resin only, and to estimated

water needed for the regeneration of the strongly basic anion exchange the to washing of the weakly basic anion exchange resin, was roughly be about 2.5 kg per 300 kg of CDHP solution. This number is given

be able to deal with the complete process. The amount of water needed

is not yet known accurately. component in CDHP solution water total 300.9 2.5 303.1 component out CDHP solution water total 300.6 2.8 303.4

Table 3a: Mass balance of the cadmium removal stage (mass streams in kg/s). The the from is wash water needed for the regeneration and washing of the resins is part of water for into the HH filter cake. After its use, the cadmium is removed the process again in the second wash step of the HH filer

the water by electrolysis or by precipitation as a sulphide. Thereafter it introduced

cake washing stage, because it will contain an appreciable amount of phosphate. component out 66.7 0.6 67.3 CDHP solution water total 66.7

component in CDHP solution water total

0.6
67.3

Table 3b: Heat balance of the cadmium removal stage (enthalpies in MW). After concentrated streams The of the of the cadmium removal stage, the CDHP solution is introduced into the together sulphuric the with acid. the solution from the recrystalliser and the Figure 4 shows the incoming and outgoing process and the most important operating conditions. The

crystalliser,

crystalliser

mass and heat balances are given in the tables 4a and 4b. most important process parameter in this stage is the sulphate content solution in the crystalliser, because this parameter determines the

136

permeability of the HH cake, obtained after filtration of the slurry. The temperature of the CDHP solution, together with the heat of crystallisation of HH mainly determines the temperature in the crystalliser,

which should not exceed about 92 °C, to avoid AH formation.

92.3°C CDHP 40w% P 2 0 5 15°C 98% H 2 S0 4 59.9°C recr.acid 1.7w% H 2 S0 4 90.8°C

vapour (87°C.PH Q = 0 , ; bar)

M
phosphoric acid

Figure H: The crystallisation stage. The cooler. value the excess heat can be removed by evaporation of water in a vacuum slurry

As was already mentioned, the heat of digestion can be higher than the used in this mass and heat balance. As a consequence, the temperature of

CDHP solution will be higher and more heat has to be removed in this stage. component out 300 .6 28 8 Hi 2
370.6

component i n CDHP s o l u t i o n 98 wj H^Ojj recrystallisation acid total

phosphoric acid vapour HH

333.0 0. H 37.2

total

370.6

Table Ha: Mass balance of the c r y s t a l l i s a t i o n s t a g e (mass streams in k g / s ) . This temperature heat, of however, can adequately be used for a f u r t h e r r a i s e of the

t h e wash water for t h e H H f i l t e r cake. The h e a t removed here i s

137

already

used for that purpose. This heating of the wash water will be discussed

in the fluoride removal stage. To the CDHP avoid local primary nucleation of HH or even of AH at the entrance of

or the sulphuric acid solution in the crystalliser, the mixing of the

contents of the crystalliser has to be thoroughly. component in CDHP solution 98 w* H 2 S0^ recrystallisation acid heat of HH crystallisation 7.5 82.1 7.2 66.7 0.7 component out phosphoric acid vapour HH heat losses heat of acid mixing total 0.1 82.1 77.8 1.0 2.9 0.3

total

Table Mb: Heat balance of the crystallisation stage (enthalpies in MW). The the recrystallisation acid, mentioned in the tables Ha and 4b, comes from

recrystalliser,

in which the HH from the digestion stage is recrystallised

into DH. The incoming and outgoing process streams of the recrystallisation stage

are shown in figure 5. The mass and heat balances of this stage are given in the tables 5a and 5b.

92.3°C CDHP ore + inert HH ♦ scale 15°C 98% H 2 S0 4
IM

vapour (55.6°C. P u ^ r r 0 . 1 4 5 w % H 2 S0; 28 w % P205 60°C

bar>

DH
inert + scale recrystallisation acid

wash water HH 76.3°C wash water DH 36.5°C

Figure 5: The recrystallisation stage. 138

In

this

stage

there

are two important

parameters, which

have to be

controlled.

First

of all, the solids

content of the slurry coming from the

digestion stage must remain equal to or must be higher than 50 w$. If the solids content is lower, more CDHP solution will be fed to the recrystallisatlon stage. This raises the phosphate rate content of the solution, and therefore reduces the into DH and unacceptable phosphate losses can recrystallisatlon occur. component in CDHP solution 98 v% H 2 S0 4 wash water HH wash water DH HH, ore, scale inert total 11.0 63.5 10.9 3.7 27.6 10.3 of HH

component out recryst. illisation acid vapour DH inert scale total 17.5 0.4 11.0 0.4 0.2 63.5

Table 5a: Mass balance of the recrystallisatlon stage (mass streams in kg/s). In obtain of a this mass and heat balances, it is already necessary to feed the wash

water of the DH as well as of the HH filter cake to the first recrystalliser, to phosphate content in the recrystalliser, which is low enough to allow of HH into DH in a reasonable time. A recycle stream of 50 w$ from the third recrystalliser, is fed again into the first recrystallisatlon the DH slurry

recrystalliser to achieve a fast conversion of HH into DH. The the than of second parameter is the heat removal, which is necessary to limit the

temperature

in the recrystallissation stage to a maximum of about 60 °C. Unless
tne

phosphate content in the recrystallisatlon stage is chosen to be much lower 30 v% Pp°c> temperature should not be higher, because then conversion HH into DH will not take place, -as follows from the phase diagram of calcium The excess of heat has to be removed by evaporation of water in a vacuum because the vapour pressure of water is very low under these vapour pressure can be calculated from the correlations given

sulphate ([27], chapter 5, figure 1 ) . slurry cooler,

conditions. This in appendix 8.6.3.

139

Table and the

5b shows that the enthalpy of the wash water of the HH filter cake of the slurry from the digestion stage, mainly determine the

enthalpy

temperature in the recrystallisation stage. If the heat of digestion were higher in reality even more heat has to be removed in this stage. component out recrystallisation acid vapour DH, scale, inert heat losses 0 9 1 0 1.0 12.9 total 12.9 8.3 3.5 0.9 0.2

component in CDHP solution 98 wj H^Oy wash water HH wash water DH HH, ore, scale inert heat of mixing of acids and water heat of recrystallisation 2 4 0 1 6 4 1 1

total

Table 5b: Heat balance of the recrystallisation stage (enthalpies in MW).

req. water60°C *

. . ,,or wash water 60°C

f wash water HH 76.3 °C recycle and product phosphoric acid
Figure 6: The HH filtration and washing stage.

110

After

the of

recrystallisation HH,

of

HH

into

DH

as

well

as

after

the

crystallisation

the crystal slurries have to be filtered. First the HH

filtration and washing stage will be dealt with and thereafter the DH filtration and the washing will be discussed. In figure 6 the incoming and outgoing streams of HH filtration and washing stage are shown. The mass and heat balances are

given in the tables 6a and 6b respectively.

component in

component out

phosphoric acid

HH
wash water wash water from the cadmium removal stage

333 0 37 2
24 8

phosphoric acid

317.0 37.2 16.0 27.6

HH
water wash water HH

2.8

total

397.8

total

397.8

Table 6a: Mass balance of the HH filtration and washing stage (mass streams in kg/s).

component in

component out

phosphoric acid HH wash water wash water from the cadmium removal stage heat of mixing of acid and water

77.9 2.9 6.2

phosphoric acid

7^.0

HH
water wash water HH

2.4 5.2 6.4

0.6

0.5

total

88.0

total

3.0

Table 6b: Heat balance of the HH filtration and washing stage (enthalpies in M W ) .

141

The heat losses on the filter are neglected. So the temperature of the wash water behave going to the recrystallisation the amount stage is assumed to be equal to the temperature of the HH leaving the process. If this stage cannot be considered to isothermal, of heat to be removed in the recrystallisation stage can change considerably. The might liquid HH leaving contain of the process contains 30 w? water. In practice this water an amount of phosphate, which cannot be neglected. The the HH cake can be influenced by process disturbances. It still

content

might be necessary to adjust the amount of wash water used.

wash water 15°C
"

solids

60 °C

recr. acid

F

W
\ wash wat er DH 36.

solids water

36.5 °C

'

1

recrystallisation acid
Figure 7: The DH filtration and washing stage. component in recrystallisation acid DH, inert, scale wash water 47.5 14.6 10.3

component out recrystallisation acid DH, i n e r t , water wash w a t e r D H scale

41 .2 14.6 6.3 10.3 72.4

total

72.4

total

Table 7a: Mass balance of the DH filtration and washing stage (mass streams in kg/s).

142

In and

figure 7 the incoming and outgoing process streams of the DH filtration

washing stage are shown. The mass and heat balances are given in the tables

7a and 7b. component in recrystallisation acid DH, inert, scale wash water heat of mixing of acid and water 0.1 8.3 0.9 0.6 component out recrystallisation acid DH, inert, scale water wash water DH 7.2 0.6 1.0 1.1

total

9.9

total

9.9

Table 7b: Heat balance of the DH filtration and washing stage (enthalpies in MW). This of washing The DH of stage the is also considered to behave isothermal. The phosphate content DH filter cake, the wash water is introduced in the first

the water leaving the process, together with the DH, is neglected too. After

recrystalliser. temperature of this wash water is set equal to the temperature of the leaving the process. This wash water stream, however, will hardly affect the The discussed level water in of last the the step of the CTPA process is the fluoride removal. This stage Is acid, cake while in the second part the heating of the wash with the fluoride containing off gasses, Is

temperature in the recrystallisation stage. in two parts. The first part deals with the reduction of the fluoride product HH filter

discussed. Figure 8 shows the incoming and outgoing process streams of the first part, which consists of a stripping column and the first scrubber. The rough values of the mass and heat balances are given in table 8a and 8b. The the stripping column as well as the first scrubber are assumed to operate isothermal. The heat capacity of the fluorosilicic acid solution is set equal to heat capacity of water and quite rough values for the fluoride distribution are used. So the data given in table 8a and 8b are only coefficient

113

approximations of what will happen in practice.

phosphoric acid SCRUBBER digestion stage gas water 15°C STRIPPING COLUMN

-»~ stripping gas -»► phosphoric acid - * - 25w%H2SiF 6

Figure 8: The stripping column and first scrubber component in phosphoric acid water off gasses from the digestion stage total 3.1 35.0 total 35.0 28.9 3.0 component out phosphoric acid 25 u% H 2 S i F 6 stripping gas 28.9 3.1 3.0

Table 8a: Mass balance of the stripping column and first scrubber (mass streams in kg/s). The first stripping gas is mainly carbon dioxide. Before this gas is recycled to which operates at about 90 °C. A part of the stripping g a s , as content of the gas mixture to be disposed i s lowered in a at room temperature, to meet environmental

the stripping column, the fluoride content of the stipping gas is reduced in the scrubber, The second fluoride scrubber, large as the quantity off gasses from the digestion stage, is disposed. operating

requirements.

1H1(

component in phosphoric acid water off gasses from the digestion stage 2.8 6.8 0.2

component out phosphoric acid 25 w$ H 2 SiF & stripping gas 6.8 0.5 2.5

total

9.8

total

9.8

Table 8b: Heat balance of the stripping column and first scrubber (enthalpies in MW). In figure 9 the incoming and outgoing process streams of the second part of the fluoride removal stage are shown. The mass and heat balances of the second scrubber and the two direct contact condensor are given in the tables 9a and 9b.

stripping gas vapour from HH/DH flasher vapour from HH flasher
j

wast second scrubber and condensors ^ //
i

wash
-■ '/

heat

15°C wafer

Figure 9: The second scrubber and direct contact condensors. Table 9b shows that no external heat is required to raise the temperature

of the wash water for the HH filter cake and for the regeneration and washing of the ion exchange resin, to 60 °C. If, however, a higher temperature is required, external heat must be used to raise the temperature unless the heat of digestion of the phosphate for ore is much higher than used in these calculations. The calculations the mass and heat balances of the fluoride removal stage are

only roughly, and therefore some external heat might be necessary in practice.

115

component in stripping gas water vapour from the recrystallisation vapour from the crystallisation 1.4 0.4 30.2 3.0 25.4

component out waste gas wash water 2.9 27.3

total

total

30.2

Table 9a: Mass balance of the second scrubber and direct contact condensors (mass streams in kg/s). component out 2.5 1.6 3.5 1.0 waste gas wash water 1.8 6.8

component in

stripping gas water vapour from the recrystallisation vapour from the crystallisation

total

8.6

total

8.6

Table 9b: Heat balance of the second scrubber and direct contact condensors (enthalpies in M W ) . The operating as of control proposed possible. unwanted deposition of Si0_ on the walls of the equipment, which is

frequently observed in phosphoric acid plants, can have a large influence on the efficiency of the scrubbers, of the direct contact condensors as well It of is, however, fluoride possible by very adequate temperature to avoid formation of SiO. in the equipment. Therefore, the method from the acid and the off gasses should be the stripper. for removal

146

8.4. Discussion and conclusions

The can be

results put In

given to

in appendix 8.6.9 and presented in the former sections give a mass and a heat balance of the complete CTPA

together table tons 10

process. producing

and 11 the mass and heat balances are given of a plant,

1000

P?0,- per day and operating according to the CTPA process.

The composition of the products is given in table 12. The 99 % overall the phosphate efficiency of the process is calculated to be about amount of phosphate ore used, the amount of phosphoric acid

from and

produced washing

their

phosphate content. The phosphate losses, due to incomplete

of the HH and DH filter cakes are, however, neglected. In practice this

assumption will not be fulfilled. Most of the data and correlations, given in the appendices and used for the calculations, impurities is are not obtained for chemically pure systems. The influence of

accurately known, but hardly any influence on the phosphate

and cadmium incorporation in the HH crystals is expected ([27], chapter 9 ) . In practice, be the overall phosphate efficiency of the process will

therefore, cadmium

less than 99 %, but the specification of the products (a maximum in the phosphoric acid of 5 ppm and in the HH and the DH

concentration

of 1 ppm) can still be reached.

component in phosphate ore clay water
98 v% H^OJJ

component out 37.1 0.8 38.7 32.4 phosphoric acid HH-slurry DH-slurry 25 w$ H 2 SiF 6 waste gas 28.9 53.2 20.9 3.1 2.9
109.0

total

109.0

total

Table 10: Overall mass balance of the CTPA process (mass streams in kg/s).

Table results

11

shows that no external heat is required in the CTPA process. The so and far, show that the production of concentrated and "clean" "clean phosphogypsum" should be possible with the CTPA

obtained acid

phosphoric process.

147

component in ore and clay
98 M% H2S0^

component out

water heat of digestion heats of mixing heats of crystallisation heat of recrystallisation

0.4 0.8 2.4 3.6 1.5 9.5 1.0
19.2

phosphoric acid HH-slurry DH-slurry 25 w% H 2 SiF 5 waste gas heat losses

6.8 7.6 1.6 0.5 1.8 0.9

total

total

19.2

Table 11: Overall heat balance of the CTPA process (enthalpies in MW).

phosphoric acid 40 wj P 2 0 5 1.7 w* H 2 S0 4 0.5 w? F 4 ppm Cd

HH
0.4 ppm Cd 0.2«J P 2 0 5

DH
0.2 ppm Cd 0.3 w$ P 2 0 5

Table 12: Composition of the products of the CTPA process. Additional removal information about the heat of digestion, about the cadmium

stage as well as about the fluoride removal stage is, however, required

to make a complete engineering flow diagram of the CTPA process. A reasonably sized pilot plant, in which all process steps are incorporated is needed to levels confirm the results given here. Only in a process in which all impurity A single are build up, accurate data for the description of the cadmium study CTPA of the investment needed to build a plant operating and to build a plant operating according to a

as well as of the fluoride removal stage can be obtained. preliminary to the filter HH/DH according process

process, with the same production capacity, showed hardly

any difference in investment cost.

148

8.5. Literature 1. 2. 4. 5. 6. Becker, P., Phosphates and Phosphoric Acid, Fertiliser Science and Technology Series, Vol. 3, Marcel Dekker Inc., New York, (1983). Bos, W.S., Private Communications, Windmill B.V., Vlaardingen, (1985). Egan, E.P.jr. and Luff, B.B., Ind. Eng. Chem., 47 (1955) 1280. Egan, E.P.jr. and Luff, B.B., J. Chem. Eng. Data, 11 (1966) 509. Egan, E.P.jr., Luff, B.B. and Wakefield, Z.T., J. Phys. Chem., 62 (1958) 1091. Elmore, K.L. and Farr, T.D., Ind. Eng. Chem., 32 (1940) 580. Farr, T.D., Tennesee Valley Authority, Chem. Eng. Report 8 (1950) 44. Frankenfield, K., Verfahren zur Entfernung von Cadmium aus Phosphaterzen, Chemische Fabrik Budenheim, DE-3332698 A1, 21 maart 1985. 10. Frochen, J., Laine, J., Allyot, H. and Gosse, G., Concentrated Phosphoric Acid Manufacturing Process by Double Crystallisation, Bulletin d*Information HEURTEY, 57 (1972). 11. Gaubert, P., C.r., 197 (1933) 72. 12. Giauque, W.F., Hornung, E.W., Kunzler, J.E. and Rubin, T.R., J. Am. Chem. Soc, 82 (1960) 62. 13. Glazyrlna, L.N., Savinkova, E.I. and Grinevich, A.V., Zh. Prikl. Khim., 53, 11 (1980) 2524. 14. Ivanchenko, L.G., Guller, B.D., Zinyuk, R.Yu. and Peresvetova, S.A., Issled. V. Obi. Tekhnol. Mineral Udobr., L (1983) 58. 15. Kelley, K.K., Southard, J.C. and Anderson, T.C., Techn. Pap. Bur. Mines, nr. 625 (1941) 1. 16. Knobeloch, J.B. and Schwartz, C.E., J. Chem. Eng. Data, 7 (1962) 386. 17. Klocko, M.A. and Kurbanov, M.S., Ivzestija Sektora Fiz.-Chim. Anal., 24 (1954) 252. 18. Laptev, V.M., Kopylov, B.A., Varshavskii, V.L. and Ovsyannikova, L.G., Sbornik Trudov/Leningradskii Tekhol. Inst. Im Lensovita, 4 (1973) 11. 19. Linck, G. and Jung, H., Z. Anorg. Chem., 137 (1924) 407. 20. Perry, R.H. and Green, D.W., Ed., Perry's Chemical Engineers' Handbook, 6th. ed., McGraw-Hill Book Co., New York, 1984.

3. Edukos, A.T. and Ikonomu, E., Zh. Prikl. Khim., 58, 9, (1985) 1937.

149

21. Rakshit, J.N., Z. Electrochemie, 32 (1926) 276. 22. Riddell, W.C., Rock. Prod., 53 (1950) 68, 102. 23. Rosincky, V. and Kockta, J., Spisy Priradovedeckou Fak. Musarykovy Univ., nr. 210 (1935) 3. 24. Skauge, A., Fuller, N. andHepler, L.G., Thermochimica Acta, 61 (1983) 139. 25. Slack, A.V., Ed., Phosphoric Acid, Fertiliser Science and Technology Series, Vol. 1, Marcel Dekker Inc., New York, 1968. 26. Sluis, S. van der, Meszaros, Y., Wesselingh, J.A. and Rosmalen, G>M> van, Proc. Fertiliser Society of London, nr. 249, (1986). 27. Sluis, S. van der, PhD Thesis, Technical University of Delft, Delft, 1987. 28. Smith, A. and Huffman, E.O., Ind. Eng. Chem. Chem. Eng. Data Ser., 1, 1 (1956) 99. 29. Sokolik, S., Z. Physik. Chem., A158 (1932) 305. 30. Spencer, L.J., Mineralog. Mag., 21 (1926/1928) 337. 31. Spijker, R. and Hovenkamp, H., UKF-rapport YBO-ME-85-3974, 12 december 1985. 32. Taperova, A.A., J. Appl. Chem. USSR., 18 (1945) 521. 33. Tjioe, T.T., Weij, P. and Rosmalen, G.M. van, Proc. World Congress 111 Chem. Eng., Tokyo, Japan, Vol 2, (1986) 925. 34. Tjioe, T.T., PhD Thesis, To be published, Technical University of Delft. 35. Tutundzic, P.S., Liler, M. and Kosanovic, D., Glasnik. Hem. Drustva. Beograd., 20 (1955) 1. 36. Wakefield, Z.T., Luff, B.B. and Reed, R.B., J. Chem. Eng. Data, 17, 4 (1972) 420. 37. Weast, R.C. and Astle, M.J., Handbook of Chemistry and Physics, CRC Press, Cleveland, Ohio, 59th. ed. (1979). 38. Weterings, K., The Development of a Clean Technology Phosphoric Acid Process, DSM Research B.V., Report of 5 april 1985. 39. Wulff, P. and Schaller, A., Z. Krist., 87 (1934) 43. 40. Yudenkova, I.N. and Ishchenko, N.A., Zh. Prikl. Khim., 55, 5 (1982) 1162. 41. Zinyuk, R. Yu., Rogova, G.I. and Pozin, M.E., J. Appl. Chem. USSR., 44, 10 (1971) 2316.

150

8.6. Appendices 8.6.1. The solubility of HH and DH The solubility product K H H for HH, defined as: ie = wj CaO * v% SO., is calculated from data given in literature [12, 13, 14, 18, 25, 32] as: y HH
=

« „ » .((-1277 + 36 * w* P 0 )/T) 3 2 5 ,
the weight percentages, are those present in s o l u t i o n and T i s the

where The

absolute temperature. solubility product KD„ for DH, defined a s : w? Ca * (w$ SO. ) n , i s given by Becker [ 1 ] a s : w* P O , KDH = 0.160 * " Q Q - - 2 * ( ( 2 . 4 0 - l o g ( T - 2 7 3 ) ) / 0 . 9 1 2 ) , in which n = 1.25 - 0.01 * (T-273). The weight percentages a r e t h o s e i n s o l u t i o n and T i s the a b s o l u t e t e m p e r a t u r e .

8.6.2. Incorporation in HH and DH 8.6.2.1. Incorporation in calcium sulphate hemihydrate The phosphate incorporation in HH can be expressed as [26]: wj P„0C in HH . , vt% Po0,. in solution 2_5 1 1 » 10 » w* SO in HH ' w* SO in solution The cadmium incorporation in HH was estimated by [26]: 52i_Q5_BêE_!$B_öü =„ i * 1 0 - 3 * 52i_Sd_per_kg_solution moï Ca per kg HH . mol Ca per kg solution In the presence of 240 ppm I-, the value of 1 * 10 must be replaced by -4 5 * 10 , because the given iodide content reduces the cadmium incorporation by about a factor two ([27], chapter 5 ) .

151

Data obtained in the bench-scale plant ([27], chapter 9) revealed that: wJ_Al_in_HH wjj Al in solution Since ?SO^
= k

the fluoride in the HH crystals is incorporated as AlF^ in the HH lattice ([27],chapter 5 ) , the

2-

, which replaces

fluoride content of the HH

crystals also follows from the former equation. 8.6.2.2. Incorporation in calcium sulphate dihydrate According to Frochen e.a. [10], the phosphate incorporation in DH is given by

the equation:

w$ P o

d o

i„ D H - 0.01 * e ( -°- 0 5 5 i t ' ° ' 3 2 7 6 *

fsc

* °'0218 *

fsc2)

,

in which fsc « percentage of free sulphuric acid in the solution. The free sulphuric in the acid content of a solution equals the total sulphate expressed as mol per kg, minus the calcium concentration solution,

concentration in the solution, also expressed as mol per kg. The cadmium incorporation in the DH is given by: p_Dm_Cd_in_HH ppm Cd in solution ~ which value has . ' ' found the in a commercial plant, operating under similar of 240 ppm iodide the value of 0.1 must be

been

conditions

[38]. In

presence

replaced by 0.05, due to the reduction of the cadmium incorporation by formation of cadmium-iodide complexes. The incorporation of Al and F is assumed to be the same as for HH. 8.6.3. Vapour pressure of the P.0 -H„0 system
. .
do

d

The

correlations,

used

for

predicting the vapour pressure of phosphoric acid

solutions in the CTPA process are based on data measured by Farr [8].

152

l o g P - - (2935.61 - 0.122287 * n + 0.022738 * n 2 )/T - 4.9373 * log T +
1.6939 * 10~ 5 * T + 4.874 * 10 " 8 * T 2 + 25.5525 - 1.1237 * 10~ 3 * n + 1.1216 * 1 0 " 5 * n 2

for 0 £ w* P„0C 2 23-5 and l o g P = - (2944.79 - 1.6128 * n + 0.02113 * nc)/T - 4.9373 * log T + 1.6939 * 1 0 - 5 * T + 4.874 * 10 " 8 * T 2 + 25.4825 2.3186 * 10~ 5 * n 2 for 23.5 £ w$ P.0 C i 38.2 and l o g P = - (3667.44 - 33.802 * n + 0.42947 * n2)/T - 4.9373 * log T + 1.6939 * 10~ 5 * T + 4.874 * 10 " * T 2 + 25.7501 - 5.0125 * 1 0~3 4.4405 * 10~ 5 * n 2 for 38.2 £ wj P.0,. £ 6 3 . 7 ,
in which P = water vapour pressure in Pa T = temperature in K n = w$ p_0,. in the solution ^ D These correlations are used for all the streams in the CTPA process. Sulphuric 2.7695 * 10

acid or other species, present in the solution, were treated as water. In acid 1 the digestion stage, the vapour pressure of water above the phosphoric

is equal to the partial vapour pressure of water. The absolute pressure of is the sum of the partial vapour pressure of water and the vapour

bar

pressures of carbon dioxide and the various fluoride compounds.

8.6.4. Fluoride distribution coefficients

8.6.4.1. Liquid-gas

If

the

composition

of the solution is known, the concentration of fluoride in

the gas phase can be estimated by the equation ([27], chapter 7 ) :

153

in H = 32.4 + -f- * ln(m(H )) - -\3 3

* ln(m(H„SiF,)) + 0.156 * m(HoP0„) +
Q^n
2
2 6 3

*

m(H2SiF5) + 0.457 * mCHgSO,,) - ^ - , in which H - 2S FJ.1 ^.Y§B2ur mol H SiF, / kg H O m(x) = mol of species x per kg of water in the solution T = temperature in K

For the digestion, the crystallisation and the fluoride removal stages a value 4 3 of 10 mg F/m vapour/w% F in the solution was used, while a value of 100 mg F/ m vapour/w$ F in the solution was used for the recrystallisation stage.

8.6.4.2. Liquid-solid The total amount of fluoride deposited as Na SiF,, K2SiF, and NaKSiF,, is

difficult

to estimate, because a supersaturated solution of these compounds can

easily be maintained. It was therefore quite arbitrary assumed, that in the CTPA process, half of the fluoride present in the ore, leaves the process as solids, as was also found in a commercial single stage HH process [2]. The incorporation of fluoride in the HH and the DH has already been defined (8.6.2.1.). The amount of fluoride precipitating with the HH and DH is less than 50 w% of the fluoride present in the phosphate ore. So the remaining part of the fluoride, to be precipitated, will be deposited as a fluorosilicate precipitate, also only called scale. Furthermore, it is assumed that, this scaling will be formed in the digestion as stage, where the fluoride is added and in the stage, where the temperature is lowered from 90 to 60 °C. The scale, is assumed to be sodium fluorosilicate only. The

recrystallisation fluoride deposited

fictitious solubility products used in the separate stages are: K(digestion) = [Na+] * [SiFg2"] = 1.766 * 10 _ 2 mol2/kg2 K(recrystallisation) = 3.295 * 10~3 mol2/ kg2 The clay, introduced values of sodium ions. in the digestion stage, was assumed to contain no sodium the solubility products have to be used, if the clay The fluoride deposited as scale as well as the fluoride

ions. Other contains

incorporated in the HH and DH is assumed to leave the process with the HH and DH

154

respectively.

In

practice

the

scale

will

be

deposited on the walls of the

reactors and cleaning of the reactors is needed frequently. 8.6.5. Density correlations 8.6.5.1. Phosphoric acid The density of chemically pure phosphoric acid was derived from literature data
and

[4,17]

fitted

between

0

-

95

°C and 0 - 70 wj Po0,_ with the following
c- D

correlation:
p = ( ( - 6 . 1 3 5 * w - 1.2450) * 10 - 1 1 * (T - 273) 0.4258 * w
2 +

1.0073

+

0.7487 * w +

+ 0.3237 * w ) * 10

3

3

i n which p = d e n s i t y of phosphoric acid in kg/m w = w$ P.0 C i n s o l u t i o n T temperature in K 8.6.5.2. Sulphuric acid The density of sulphuric acid was derived from literature data [20] and fitted

between 0 - 100 °C and 0 - 100 w$ H-SO^ with the following correlation: (0.83222 * w - 0.00046944 * (T - 273) + 6.9128) P = e . (-14.9985 + 0.069634 * (T - 273) + (24.484 - 0.086606 » (T - 273)) * w)

in which p = density of sulphuric acid in kg/m w = w$ SO. in solution T = temperature in K 8.6.5.3. CDHP solutions The following 0 correlations were obtained by fitting the literature data [7,28] 70 w$ P.O., 0 - 95 °C and between 0 w? CaO and the saturation

between

concentration of CaO in the solution: p(T,w,c) = p(T,w) + c * fc * 103

155

in which p(T,w,c) = density of the CDHP solution, containing w w$ P o 0 c , c w$ CaO 2 D at a temperature of T kelvin. p(T,w) = density of chemically pure phosphoric acid at the given temperature and phosphate content c fc T = w% CaO = 1.05 + 0.00225 * (T - 273) + 1.9 * w = temperature in K

8.6.5.4. H PO^-H SOjj-HgO mixtures

According

to

Tutundzic

e.a. [35] and Yudenkova and Ishchenko [40], the sum of

the fractional contributions of the pure components can be used.

8.6.5.5. Calcium sulphate hemihydrate (HH)

HH form CTPA

can occur in two different modifications, the so-called a and B forms. The ( 5 is dehydrated gypsum, while the a form develops from solutions. So in the the a form of HH is precipitated. The density of the a form is

process

taken to be the mean value of the data given in literature [11,15,19,23]:

p = 2746 kg/m 3 , st. dev. 11 kg/m 3

8.6.5.6. Calcium sulphate dihydrate (DH)

The is:

mean

value

of the density, obtained from literature data [15,20,21,30,39]

3 3 p = 2 3 1 2 kg/m , st. dev. 6 kg/m 8.6.5.7. The phosphate ore

The density of the Zin phosphate ore was determined to be approximately 3 2700 kg/m , as measured by the pyknometer method ([27], chapter 4 ) .

8.6.5.8. Water

From

literature

data [37] the following expression for the density of water is

156

obtained: p = 1006,287 - 0.12876 * (T - 273) 3 in which p = density of water in kg/m and T = temperature in K 8.6.6. Heat capacities and heat contents 8.6.6.1. Phosphoric acid From literature data [6,36] the following correlation was obtained for

chemically pure phosphoric acid: cp = (3725.80 + 2.23326 * (T - 273) " 32.5439 * w - 0.00310846 * (T - 273) 2 + 0.0236263 * w2 + 0.00887146 * (T - 273) * w) * 10~3 in which cp = heat capacity in kJ/kg/K, w T = temperature in K = w$ P?0_ in sollution and

8 . 6 . 6 . 2 . Sulphuric acid According sulphuric to acid literature is data [29], the heat capacity of chemically pure

n e a r l y temperature independent and can be approximated with

the following c o r r e l a t i o n :
cp = 1.19 * (1 (9.8177 * 1 0 - 3 * w - 4.9327 * 10~ 5 * w2 + 1.5081 * 10~ 7 * w 3 ) )

in which cp = h e a t capaciry in kJ/kg/K w = wj SO In s o l u t i o n

8 . 6 . 6 . 3 . CDHP s o l u t i o n s From literature data [5], the following equation was obtained for chemically

pure CDHP s o l u t i o n s : cp = (4175.09 - 49.1067 * c - 45.1056 * w + 1.59092 * c * w + 0.0974336 * w2 - 0.0270606 * c * w2 + 2 * (T - 298)) * 10~ 3

157

in which cp = heat capacity in kJ/kg/K, w = w$ P O in solution and

c T

= M% CaO in solution, » temperature in K

8.6.6.1. H POjj-H^O^-HgO mixtures For After lack of data on t h i s system, the c o r r e l a t i o n given i n 8 . 6 . 6 . 1 was u s e d . The all calculations [16], made were performed, a r e i n v e s t i g a t i o n of t h e data g i v e n in it p o s s i b l e t o d e r i v e the following e x p r e s s i o n f o r the

s u l p h u r i c a c i d c o n t e n t of t h e s o l u t i o n was n e g l e c t e d and c o n s i d e r e d t o be w a t e r . literature

heat c a p a c i t y of t h i s m i x t u r e s : cp = (x * (18.0726 - 4.4635 * 10~ 3 * T + 6.7299 * 10~ 5 * T 2 0.2)0'05

1.4873 * 10 - 7 * T 3 ) / 18.0152 + x 2 * (32.07 + 3.923 * 10~2 * T) / 98.0774 + x 3 * (0.1568 + 8.748 * 1 0 - " * T - 2.316 » 10~7 * T 2 )) * (x 3 / i n which cp = h e a t c a p a c i t y in c a l / g / ° C , T x 1 = w* H 2 0, x 2 = wjt H 2 S0 4 and x The deviations between the = temperature i n °C = wit PgO

experimental v a l u e s , between 30 -90 °C, and those

p r e d i c t e d by the c o r r e l a t i o n given above i s maximal 3 %. 8 . 6 . 6 . 5 . Calcium sulphate hemihydrate (HH) The heat c a p a c i t y of t h e a form of H H i s given by [ 1 5 , 2 2 ] and e q u a l s : cp = (488.4 + 1.13 * T) * 10~3 in which cp = heat capacity in kJ/kg/K and T 8.6.6.6. Calcium sulphate dlhydrate (DH) According to Riddell [22], the following correlation, based on data of Kelley = temperature in K

[15], can be used to estimate the heat capacity of DH: cp = (530.7 + 1 .84 * T) * 10~3 in which, cp is given in kJ/kg/K and the temperature in K.

158

8.6.6.7. The phosphate ore According to literature data [6], the following expression can be used to

estimate the heat capacity of phosphate ore: cp = (937.6 + 0.1189 * T - 20.25 * 10 6 * T~2) * 10~3 in which, cp is given in kJ/kg/K and the temperature in K. 8.6.6.8. Water The heat content data, given by Weast and Astle [37], are used to derive the

following expression for the heat content of water, relative to 0 °C: H = 4.80296 * 10~ 2 + 4.2003 * (T - 273) " 5.05431 * 10 _6 * (T - 273) 2 + 4.10118 * 10 - 6 * (T -273)3 in which H = heat content in kj/kg and T = temperature in K. 8.6.6.9. Water vapour The with heat content of water vapour can be c a l c u l a t e d from l i t e r a t u r e d a t a [20,37] the following e q u a t i o n , obtained from TISDATA, the databank for p h y s i c a l

parameters of DSM:
H = (44861.1 + 36.8545 * (T - 273) - 506.193 * P + 2.88044 * (T - 273) * P " 1.351176 * 10~ 2 * (T - 2 7 3 ) 2 14.1243 * P 2 ) / 18.0153

in which H = h e a t c o n t e n t i n k j / k g , T = t e m p e r a t u r e i n K and P = vapour p r e s s u r e of water in bar 8.6.6.10. Carbon dioxide From the databank of DSM, TISDATA, the following expression for the heat

capacity of carbon dioxide was obtained [20]:

159

cp = (21.3548 + 6.425188 * 10

2

* T - 4.103002 * 10~ 5 * T 2 ) /

14.01

in which cp = heat c a p a c i t y i n kJ/kg/K and T 8 . 6 . 6 . 1 1 . Other compounds The to contribution while kJ/kg/K. 1 0.75 of of SiF ü and all HF

= temperature in K

to t h e h e a t c a p a c i t y of the gas streams i s

neglected, value

t h e heat c a p a c i t y of the Na ? SiF, s c a l e i s a r b i t r a r y s e t equal After c a l c u l a t i o n s were performed, i t was found t h a t a i s more r e a l i s t i c [ 2 0 ] . The h e a t c a p a c i t y of clay i s 0.94

kJ/kg/K

kJ/kg/K [ 1 7 ] . This v a l u e i s used, because t h e t y p e of c l a y t o be used i s not yet known. If t h e type of clay t o be applied i s known, then t h e h e a t c a p a c i t y of the clay, and as a function of the t e m p e r a t u r e , can probably be obtained from t h e data given equal by to Skauge the e . a . [ 2 4 ] . The h e a t c a p a c i t y of the HpSiFg c a p a c i t y of w a t e r , because t h e r e a r e no is set heat correlations

solution

l i t e r a t u r e d a t a found for t h i s s o l u t i o n . 8 . 6 . 7 . E n t h a l p i e s of r e a c t i o n 8 . 6 . 7 . 1 . D i g e s t i o n of phosphate ore

Ca

10(P04)6F2

+

1lt H

3 P °4 "

_ >

1

°

Ca(H

2PV2

+

2

HF

A H = - 100 kJ/kg ore [ 3 ] 8 . 6 . 7 . 2 . C r y s t a l l i s a t i o n of calcium s u l p h a t e hemihydrate (HH) 2 Ca(H 2 P0 1) ) 2 + 2 H^Ojj + H20 > 2 CaSO^.^O + 4 H^O^

AH = -200 kJ/kg HH [41] 8.6.7.3. Recrystallisation of HH into DH 2 CaSO^.^O + 3 H20 —> 2 CaS0 r 2H 2 0

AH = - 100 kJ/kg HH [22]

160

All v a l u e s a r e rough a p p r o x i m a t i o n s , because they a r e mainly determined i n water and no accurate These data data, are a v a i l a b l e a t t h e c o n d i t i o n s p r e v a i l i n g in the CTPA process. however, w i l l be measured in the near f u t u r e and for t h e

time being, t h e values of the h e a t s of r e a c t i o n , given above a r e used. 8 . 6 . 8 . Heat of mixing i n t h e H-P0^-H2S0^-H2O system 8 . 6 . 8 . 1 . General procedure Knobeloch and Schwartz [ 1 6 ] , have given a method t o c a l c u l a t e t h e heat of mixing in a t e r n a r y system, from the h e a t s of mixing in the t h r e e binary systems ( s e e figure 1).

H70

H70

H 2 S0 4

H3PO4

H 2 S0 4

H3P0 4

H 2 S0 4

H 3 PO if

Figure 1: The t h r e e binary systems, in which the t e r n a r y system can be s p l i t up The binary heats of mixing have t o be c a l c u l a t e d i n each b i n a r y system a t t h e

following compositions:

A

1 H 12 = A H 1 2 ( x 1 ' A,H13 = AH13(x1t

1

"V 1-Xl)

A 1 H 23 = AH 2 3 (x 2 /(x 2 + x 3 ) , x 2 / ( x 2 + x ))

2 H 12 = ^ H l 2 ( 1 " x 2 , x 2 ) A2H13 = A H 1 3 ( x 1 / ( x 1 + x 3 ) , x l / ( x 1 A2H23 = A H 2 3 ( 1 - x 2 , x 2 )

A

+ x 3 ))

161

A 3 H 12 = A H 1 2 ( x 1 / ( x l + x 2 ) , x l / ( x 1 + x 2 ) ) A 3 H 13 = A H ^ O - X - . x - ) A 3 H 23 = A H 2 3 ( 1 - x 3 , x 3 ) i n which x x x AH = mole f r a c t i o n w a t e r , = mole f r a c t i o n H„SO., = mole f r a c t i o n H PCL, A. A. A, = h e a t s in binary system 1 = h e a t s i n binary system 2 = h e a t s i n binary system 3

= h e a t of mixing component 1 (water) and 2 (H S O . ) , e t c .

For each b i n a r y system a t e r n a r y h e a t of mixing can be o b t a i n e d from the t r i p l e t of binary h e a t s of mixing:

* 1 H 1 2 3 - x-%--x 3 * V l 2
A H

+

x

2

- h - * *1 H 13
A H

+ / ( 1

'X1)

*

A H

1 23

2 123 " x j T x - * * 2 H 1 2

+

x--%2-x-- *

2 23

+ /(1

" X 2 ) * *2H1 3

A H

3 123 " X-4-X-- * V l 3

+

x-;-!-x-- * A3H23

+

^ " V

* A3H12

The

heat of mixing in t h e t e r n a r y system i s then s e t equal t o t h e mean v a l u e of

t h e t h r e e t e r n a r y h e a t s of mixing for the binary systems:

123 " AH

3

is given in c a l o r i e s per mol m i x t u r e .

The binary h e a t s of mixing a r e given in the s e c t i o n s 8 . 6 . 8 . 1 t o 8 . 6 . 8 . 3 Although all also calculations be used at are based on a temperature of 25 °C, t h e s e c o r r e l a t i o n s may higher t e m p e r a t u r e s , because only a s l i g h t i n f l u e n c e of the

temperature

was found [ 1 6 ] . The d i f f e r e n c e s between t h e experimental v a l u e s and

t h e c a l c u l a t e d values of the t e r n a r y h e a t of mixing a r e found t o be s m a l l e r than 10 %, if t h e mole f r a c t i o n of water in t h e system exceeds 0 . 5 . 8 . 6 . 8 . 2 . Binary heat of mixing in t h e H PO.-H 0 system From l i t e r a t u r e data [ 8 ] , t h e following e x p r e s s i o n was obtained for the h e a t of

162

mixing of chemically pure phosphoric acid and water: AH 1 3 = (F - 5.87) * x 3 in which F = 56.968 * w - 2.9512 * w 2 + 0.09298 * w 3 1.1159 « 10 - 3 * uH + H.8388 * lo"6 » w 5 AH. _ = heat of mixing in cal. per mol mixture w = w$ H^PO^ in solution and x- = mole fraction H^PO,. in solution

8.6,8.3. Binary heat of mixing in the H^SO^-H-O system The data given by Giauque e.a. [12], were used to derive the following expression for the heat of mixing of chemically pure sulphuric acid and water: AH = w * (100 - w) * (0.35801 - 5.639 * )0~H * w + H.3483 * 10~k * w 2 8.5131 * 10~ 6 * w 3 + 8.2961 * 10~ 8 * w 4 )

with w = wj H.SOy in solution and AH.. = heat of mixing in cal. per mol mixture. 8.6.8.1. Binary heat of mixing in the H PO^-H-SO^ system The expression for calculating the binary heat of mixing of chemically pure phosphoric acid and sulphuric acid is [16]:
AH = x

23

2 * x3 *

(1935

"

26i)1

*

(x

2 " x3) +

510,5

*

(X

2

+x

3)2)

in which

x ? = mole fraction sulphuric acid in solution x- = mole fraction phosphoric acid in solution AH_, = heat of mixing in cal per mol mixture

2 The last term in the correlation, given above, i.e. 510.5 * (x + x ) , is probably a printing error in the original article, because x ? + -x_ equals 1 in the binary system phosphoric-sulphuric acid. No significant error was found, however, in the ternary heat of mixing, if the above correlation is assumed to be correct.

163

8.6.9. Total mass and heat balances of the CTPA process The 1268 In total linear figure 1 mass or the 2 and heat balances of a 1000 ton P„Cv per day producing plant, to the CTPA process was obtained by simultaneously solving equations. This large number of equations was

operating

according

linearized largest shows the

necessary to obtain the composition of all process stream. part of the flowsheet of the CTPA process is given, fluoride removal stage. The numbers given on the while figure and

flowsheets, represent equipment are

either an amount of heat, a process stream or a piece of below. The composition of all process streams as

explained

well as the mass and heat streams are given in table 1. List of equipment A1 A2 C1 C2 El F1 F2a,2b F3a,3b R1 R2 R3 R4 R5 R6 R7 51 52 53 SH T1 U1 First fluoride scrubber and stripping column Second fluoride scrubber Direct contact condensor for the vapour from the flasher in the recrystallisation stage Direct contact condensor for the vapour from the flasher in the crystallisation stage Heat exchanger for heating the wash water of the HH washing stage Solid-liquid separation by gravity and a centrifuge after the digestion DH filtration and washing respectively HH filtration and washing respectively First digester Second digester Third digester First recrystalliser Second recrystalliser Third recrystalliser Crystalliser Product acid splitter Sulphuric acid splitter DH slurry recycle splitter Wash water splitter Filter feed tank for HH slurry Cadmium removal unit

164

Figure 1: Flowsheet of the CTPA process (except the fluoride removal stage),

165

G02
G01 G03 L51 A2 G52r

— * LA 1 1 G32 -rL59 *

^i7G51>

L52

6 1 1 . C1 L53
G31

>

" C2 L32
i

'

Figure 2: Flowsheet of the fluoride removal stage of the CTPA process. List of process streams (kg/s) CD D, DR E G H I K L
S

= Cadmium = Calcium sulphate dihydrate (DH) = Phosphate ore (soluble part) = Off gasses = Calcium sulphate hemihydrate (HH) = Inert (insoluble part of the ore) = liquid = liquid
= clay

SC, SCR = s c a l e T01 T02 = E01 + 101 = E02 + H02 + 102 + K02 + SC02

T03
TOU T11 T12 T13 T14 T15 T16

= E03 + H03 + 103 + K03 + SC03
= E04 + H0>i + 1014 + K01 + SC04 = E11 + H11 + 111 + K11 + SC11 = D12 + H12 + 112 + K12 + SC12 = D13 + H13 + H 3 + K13 + SC13 = DIM + 1 1 1 + K i t + SC1H = D15 + 1 1 5 + K15 + SC15 =' D16 + 116 + K16 + SC16

166

^

T17 T18 T31 T32 T33 T3H

« ■ D17 + 117

+

K17 + SC17

= D18 + 118 + K18 + SC18 = H31 + K31 = H32 + K32 = H33 + K33 = H34 + K34

List of heat streams (kJ/s)

QE1 QF2 QF3 QR1 QR2 QR3 QR1 QR5 QR6 QR7 QT1

-Q1E1 =Q1F2 =Q1F3 =Q1R1 + Q2R1 + Q3R1 + Q1R1 =Q1R2 + Q2R2 + Q3R2 + Q^R2 =Q1R3
+

Q2R3 + Q3R3 + Q4R3

=Q1R4 + Q2R1» + Q3R4 + Q4R4 + Q5R4 =Q2R5 + Q3R5 + Q4R5 =Q2R6 + Q3R6 + Q1R6 =Q2R7 + Q3R7 + Q1R7 + Q5R7 =Q1T1 + Q2T1

Q1R1-Q1R4 Q2R1-Q2R3.Q2R7 Q2R4-Q2R6 Q3R1-Q3R7.Q1T1 Q4R1-Q4R7.Q2T1 Q1E1

= h e a t of d i g e s t i o n of phosphate ore = h e a t of c r y s t a l l i s a t i o n of HH = h e a t of r e c r y s t a l l l s a t i o n of H H into D H = Heat l o s s e s through t h e w a l l s = Power input by the s t i r r e r s = H H wash water h e a t i n g

Q5Rt,Q5R7,Q1F2,Q1F3 = h e a t of mixing

Table 1: The CTPA p r o c e s s : Composition of the process streams as well as the mass and heat s t r e a m s .

167

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174

9. THE BENCH-SCALE PLANT

9.1. Introduction

In

the of

early bulk

stages

of

the

development batch

of a new process for e.g. the experiments are performed on a

production laboratory

chemicals, In these

mainly

scale.

experiments

small parts of the total process are

studied. Such experiments are relatively cheap and simple, so the exploration of different possible. However, predominant, a major especially in processes where the role of impurities is process conditions and optimalisation of parts of the process is

as in phosphoric acid production processes, these experiments have because the results might not be representative for a

drawback,

continuous Many shape of

process. In a continuous process Impurity levels build up with time. impurities the of are known for and their striking influence on the size and therefore also on the for filterability and

growing these

crystals, crystals.

washability

This

counts

the calcium sulphate

hemihydrate (HH) crystals precipitated during phosphoric acid production. Neither pure in batch experiments nor in continuous experiments with chemically

reagents these impurity levels are completely imitated. Even by purposeful of impurities, which are known to be released from the phosphate ore

addition some like

minor impurities might be overlooked. Trace amounts of specific impurities e.g. cerium [4] can already have a strong impact upon the growth kinetics

of the developing crystals. For this reason the performance of at least a few experiments, in which the real process is closely simulated on a bench-scale, is strongly recommended. The most were plant periods relevant therefore is (> parts of the new Clean Technology Phosphoric Acid (CTPA) process tested in a bench-scale plant. The flowsheet of the bench-scale

shown in figure 1. This plant has been operated for sufficiently long 100 hours) to obtain an idea of the steady state behaviour of the

CTPA process. The aim of this study was not only to determine the influence of impurities on the permeability of the calcium sulphate hemihydrate (HH) cake obtained by

filtration on the

of the HH-phosphoric acid slurry, but also to determine their effect

cadmium and phosphate uptake by the HH crystals at the selected optimal

operating conditions.

175

AIR
ORE FEE OER

98w%H 2 SO/ +

\
D1 D2

»- n,

mO
T

.

CRYSTALLISER

.

1,

"
ANTIFOAMING AGENT PRESSURE FILTER PRESSURE FILTER 2 FILTER

H2O

' ♦
'

'
i

CDHP BUFFER VESSEL

ACID BUFFER VESSEL

-*

RETURN ACI 3

PRC )0UCT ACID

Figure I: Flowsheet of the bench-scale plant. 9.2. Experimental 9.2.1. Process conditions The scale process conditions to be maintained during the operation of the bench-

plant are given in table 1 and can be obtained from the chapters 4, 5 and

8 of this thesis: - at least 10 wj P.O.- has to be produced for direct use of the phosphoric acid 2 D for the production of mono- or di-ammonium-phosphate (MAP and DAP). - the maximum solubility of CaO in phosphoric acid containing HO u% P.O,. at
d. D

90 °C is about 5 w$ CaO. This solubility, together with the sulphate content of the return acid determines the quantity of recycle acid needed for complete digestion of the phosphate ore. - in separate digestion studies no reduction in the digestion rate due to blinding of the phosphate ore was observed if the sulphate content of the return acid was less than 2 w% H_S0 Ü . - in separate crystallisation studies no AH formation occurred if concentrated sulphuric acid was fed directly into the crystalliser.

176

I crystalliser / return acid: | digesters / CDHP solution :

HO v% P 2 0 5 > 2 u% H ^ O ^ , 90 °C HO w% ?20 , H.5 w$ CaO, 90 °C

| |

Table 1: Process conditions to be maintained in the bench-scale plant. The CaO concentration in the CDHP solution was chosen to be 1.5 w$ CaO

instead of 5 w$ CaO to maintain a reasonable safety margin. 9.2.2. Chemicals The thorough phosphate ore used was a mixture of Khouribgha and Zin HO/60 w%. After mixing the phosphate ore was sieved and all particles larger than 2 mm

were removed. The composition of the phosphate ore is given in chapter 8 of this thesis, table 1 . The excessive anti-foaming foaming solution to be added during the digestion to prevent was a 50/50 vol$ mixture of distilled water and anti-foaming

agent (defoamer A-50 of Chemy B.V., Emmerich). The sulphuric acid used was chemically pure 96 w% H.SCv. By a P 0 using a special acid mixture, which already contains a basic impurity level, steady was and state can be by reduced. The acid mixture used for the startup of the mixing commercially wet process phosphoric acid (53 u% for the startup of the plant, the operating time of the plant needed to approach plant prepared

H w$ H SO., produced from the same mixture of phosphate ores), water

and technical grade phosphoric acid (62 w$ P ? 0 ^ ' I n t n i s w a v t n e startup solution was obtained, containing 10 w% P.O., about 2 w% H_S0n and a basic
2 5
c.
A

impurity level. 9.2.3. Equipment The digestion fed into flowsheet of the bench-scale plant is shown in figure 1 . Separate

studies showed that three digesters were needed for digestion of more the first digester by an "Accu-rate" feeder of TARCO BV, Vleuten. The

than 99 % of the phosphate ore within one and a half hour. The phosphate ore was weight of the feeder and the phosphate ore together was registered with time to

control the phosphate ore feed.

177

The air stream needed to prevent condensation of water in the ore feed pipe was supplied by a separate air compressor. The pump anti-foaming solution supply vessel was a magnetically stirred stop erlenmeyer with a volume of 500 ml. A 10 rev/min Watson Marlowe peristaltic tube equiped The Marlowe mm). All three digesters were double walled, thermostated vessels made of glass with a polypropene lid and a volume of about 2.5 litre. All stirrers were six bladed turbine stirrers made of a Hastelloy B rod and covered the digester. The third closed digester slurry from The the first digester was led through a glass pipe (inside diameter 3 cm) to the second digester and in the same way from the second to the digester. by a and third digester was equiped with an outlet, which could be valve (inside diameter 1 cm). The pump between the third glass with PVDF. The diameter of the stirrers in the digesters was 1.5 cm and speed varied from 1500 rpm in the first to 1200 rpm in the third stirring with a Viton B tube (inside diameter 0.8 mm) was used to feed the acid was fed to the first digester with a 100 rev/min Watson anti-foaming solution into the first digester. return peristaltic tube pump equiped with a Marprene tube (inside diameter 3.2

the pressure filters was a 100 rev/min Watson Marlowe peristaltic

tube pump equiped with a Marprene tube (inside diameter 3-2 mm). Pressure CDHP solution walled, The (diameter after filters were needed for separation of the HH/ore residue from the because a few vacuum minutes filtration filtration. caused The severe boiling of the CDHP pressure filters were double

solution,

thermostated filter 11.1

and made of PVDF. Two valves were installed at the top of consisted 121 of a perforated Hastelloy C support plate

each pressure filter, one for the CDHP slurry feed and one for airation. medium cm) with holes of 3 mm diameter, a terylene 23-12 filter

cloth and a precoat layer. This precoat layer was necessary to avoid the passage of small particles through the filter cloth at the start of the filter procedure and consisted of 10 grams of Dicalite 1.15.8, put on the filter as a 10 w? slurry in water. The precoat layer was protected against the CDHP slurry stream

fed to the pressure filter by a Hastelloy C break plate. . The of nitrogen gas used to squeeze the largest part of the CDHP solution out

the pressure filter cake was supplied from a nitrogen bottle through a backThe CDHP solution from the pressure filters was led through a Viton B tube diameter 8 mm) to the double walled, thermostated CDHP solution buffer

wash vessel made of perspex and connected with a manometer. (inside

178

vessel

made

of

glass

and

equiped with a polypropene lid. The volume of this

buffer vessel was about 3 litre. The stirrer diameter was 1.5 cm and the stirrer speed was about 600 rpm. A tube This The 100 rev/min Watson Marlowe peristaltic tube pump equiped with a Marprene (inside diameter 3.2 mm) was used to pump the CDHP solution from this

buffer vessel through a glass pipe (inside diameter 1 cm) into the crystalliser. glass pipe was covered with "Heat by the Yard" heating tape, and isolated. current A tube the 50 through rev/min the heating tape was set at 1.2 A by adjustment of the

voltage with a variac. Watson Marlowe peristaltic tube pump equiped with a Viton B (inside diameter 0.8 mm) was used to feed the sulphuric acid solution from supply vessel at room temperature into the crystalliser. The weight of the acid solution was supply vessel with a volume of about 3 litre, was

sulphuric The with a The diameter standing filters of

registered as a function of time to control the sulphuric acid solution feed. crystalliser a double walled, thermostated vessel made of glass, volume of about 3 litre and equiped with a polypropene lid. The stirrer slurry 2.5 made from the crystalliser was led through a PVC tube (inside

diameter was 5 cm and the stirring speed was 1200 rpm. cm) into the HH filter baskets made of terylene 23_1I2, which were of glass. Thereafter the liquid was assembled in double walled,

on P. porous glass plates at the bottom of double walled, thermostated round flasks, made of glass and placed underneath the filters. Two also called filter holders, were connected with each other by a diameter 8 mm) and a three-way valve (inside diameter 1

thermostated round Viton

these filtration units were used to be able to operate them alternately. The flasks, B tube used (inside

cm). The filter baskets were used to move the HH quickly from the filters to the equipment the for the HH washing procedure (appendix 9.6.3.). The liquid from filter holders was periodically fed through the three-way valve and a Viton

B tube (inside diameter 8 mm) to the return acid buffer vessel. The return acid buffer vessel was a double walled, thermostated vessel with a At acid fed volume the as into To tape and be of about 2.5 litre, made of glass and equiped with a polypropene lid. a was first valve was installed to be able to withdraw the excess return phosphoric digester acid. The stirrer diameter was M.5 cm and the about 600 rpm. From this buffer vessel the return acid was through the same type of glass pipe as used for product speed the bottom

stirring

feeding the CDHP solution into the crystalliser. able to heat all thermostats, equipment, slurries, liquids, heating other materials to 90 °C, to stir each vessel and to weight the

179

phosphate

ore

feeder

and

sulphuric

acid

solution supply vessel a new 20 kW

electricity supply-cable was installed. In only table 2 the residence times in each vessel are given. These times are

average in

values, since owing to adjustments in the process streams and the the liquid levels in the buffer vessels, fluctuations in the

variation

residence times were unavoidable.

apparatus

residence time in minutes

first, second digester third digester CDHP solution buffer vessel crystalliser HH filters and filter holders return acid buffer vessel

40 10 60 30 10 40

Table 2: Estimated residence times in the vessels in the bench-scale plant.

The use of relatively expensive materials, such as PVDF, Hastelloy B and C, Marprene and Viton B, was necessary to avoid excessive corrosion during the

operation of the bench-scale plant.

9.2.1. Procedures

9.2.4.1. Safety

Before

the

start

of

a

run

with

the

bench-scale plant, each operator

recieved an instruction map. This map contained not only the working procedures, but also names and phone numbers of persons qualified to give medical assistence and additional safety instructions. For shields the to sake protect of safety, the whole bench-scale plant was covered with PVC the operators against potential acid disposure in case of

malfunctioning. The off gasses from the plant were removed by a ventilator, installed in

the upper part of the plant. Furthermore protective clothing for all operators was bought, like face

shields, acid resistant overalls and handshoes.

180

The

cadmium plant of

containing phosphoric acid and phosphogypsum, produced in the were the removed TU Delft by in the "DAAS", who take care for disposal of such a way that environmental pollution

bench-scale waste

products

remains minimal.

9.2.1.2. Startup procedure

First

a

mass

balance

was calculated for the bench-scale plant. The most

relevant values of the process streams are given in table 3.

phosphate ore sulphuric acid return acid CDHP solution anti-foaming solution

150 g/hr 100 g/hr 3690 g/hr 3910 g/hr 20 ml/hr

Table 3: Process streams in the bench-scale plant.

A impurity operate

rough

estimation in the

was made of the operating time needed to build up the bench-scale plant. It was found that the plant had to

levels

at least 100 hours to approach a steady state, unless the acid used for

the startup of the plant already contained a basic impurity level. Therefore the so-called acid acid. Reserve materials and equipment were ordered or made for the equipment used in the plant, in case replacement was expected to be necessary during the run. In addition the ICP apparatus was made available for analysing the samples startup from solution was made from commercially wet process phosphoric

produced

the same ore mixture, water and technical grade phosphoric

day and night at regular intervals of 3 to 1 hours. About 150 glass sample bottles for the HH samples from the crystalliser and the HH/ore residue samples from the pressure filter were consecutively numbered. Also 200 plastic sample and bottles for the liquid samples from the

crystalliser, numbered distilled and

CDHP

solution

return acid buffer vessel were consecutively

weighted. was

Thereafter an accurately weighted amount of about 3 ml in the plastic sample bottles. This amount of

water

introduced

181

water A run

was

needed

to

prevent

precipitation

of

calcium

sulphate or calcium

phosphate from the liquid samples before their analyses. work-schedule the was made for the operators needed to perform a continuous with To and bench-scale plant of about 100 hours. Each 24 hours three shifts the process, all thermostats were filled with distilled water about 90-95 °C. Approximately 20 kg of the startup solution was

were operating with in each shift four operators. initiate to heated

heated to about 90 °C also. The thermostats had to be put on at least four hours before In foaming the real start of the run to heat the startup solution and the equipment the meantime solution 5 the phosphate ore feeder was filled with about 8 kg of to the desired temperature of 90 °C. phosphate ore, the anti-foaming supply vessel was filled with about 400 ml antiand the sulphuric acid solution supply vessel was filled with kg of 96 w? H-SOj.. The ventilator used for removal of the off approximately

gasses was put on. The presence of sufficient sulphuric acid (> 50 k g ) , Dicalite 4.15.8 (> 2.5 kg), phosphate Now the together current ■1.2 A. Then the CDHP solution buffer vessel was filled with startup solution. From this vessel it was pumped into the crystalliser, HH filters and filter holders. One The of the pressure for filters was made ready for operation by the precoat the each HH washing equipment was put on and two stop procedure (appendix 9.6.2.1.) thermostat were erlenmeyera A in the filled with about 65 ml of distilled water, closed and the with through ore (> 50 kg), anti-foaming agent (> 3 kg) and sodium-hydrogenreturn of the acid buffer vessel was filled with startup solution. When this solution was 90 °C-, the return acid pump was started, phosphate ore, air and anti-foaming solution supply. The carbonate (> 25 kg) was checked. temperature

the heating tape around the return acid supply pipe was set at

allowed to heat to 90-95 °C in the thermostat. stop erlenmeyer was filled with about 100 grams of water, closed and put thermostat next to the pressure filters to have wash water for the

pressure filter cake at the right temperature available. After pump to about one and a half hour the third digester was half filled and the the pressure filter was started. Then the second pressure filter was

made'ready for filtration by the precoat procedure (appendix 9.6.2.1.). The CDHP solution hour, buffer vessel was almost completely filled after about one and a half the CDHP solution and sulphuric acid pumps were started. The whereafter

182

current 1.2 the A.

through In

the heating tape around the CDHP solution feed pipe was set at

about half an hour the HH crystals from the crystalliser had filled filter basket and the run proceeded further according to the working

first

procedure. 9.2.1.3. Working procedure During the the run with the bench-scale plant each three or four hours solid

and liquid samples were taken for analyses. After analyses of the liquid samples sulphate, phosphate and calcium ion concentrations in the CDHP solution and acid were to known. If these concentrations differed from the process be maintained, these differences were used to adjust the process return

conditions

streams in the plant. Problems recognized Therefore 9.6.1.). The plant was further operated according to the pressure filter procedures the for The run one operator was responsable for the HH washing procedure, the pressure operator process filter made the procedures service and and one operator for the repaired from the damaged other over rounds, took (appendix 9.6.2.) and the HH washing procedure (appendix 9.6.3.). During one operator analyses. equipment, a if caused so-called by faillure in advance round service of to the was equipment made each in the plant had to be of the process.

possible

avoid

disturbances

half an hour (appendix

fourth

corrected

disturbances

operators, if they had to leave for a while. The last step of a run with the bench-scale plant was the stop procedure. 9.2.1).4. Stop procedure First samples of the solids and the liquids were taken for the last time. - the stop procedure started by stopping the supply of phosphate ore, antifoaming solution and air to the first digester. The return acid pump was put in reverse to empty the return acid feed pipe. - the current through the heating tape around this pipe was turned off as well as the return acid pump, after the return acid pipe was empty. - the contents of the return acid buffer vessel was siphoned over into the product acid storage vessel.

183

- the contents of the first digester was siphoned over into the third digester, after the stirrer was stopped. - if the third digester was almost empty, the contents of the second digester was siphoned over into the third digester, after the stirrer was stopped. - when the third digester was empty again, the pump between this digester and the pressure filter was stopped as well as the stirrer. - thereafter the phosphate ore feeder and anti-foaming solution supply vessel were emptied in the appropriate vessels. - the digestion stage as well as the pressure filters were cleaned with a sodium-hydrogen-carbonate solution in water and thereafter with potable water. - In the meantime the CDHP solution buffer vessel was empty and the CDHP solution and sulphuric acid pump were stopped and the current through the heating tape around the CDHP solution feed pipe was turned off. - the contents of the crystalliser was siphoned over into the HH filter baskets. - the sulphuric acid supply vessel was emptied in the appropriate vessel. - all return acid was recovered as product phosphoric acid. - the tubes were removed from the pumps. - thereafter all equipment, inclusive the HH wash equipment and the materials used for taking samples were cleaned with a sodium-hydrogen-carbonate solution in water and then with potable water. - after everything was cleaned, the ventilator was turned off and a list was made of the materials and equipment, which were damaged and had to be repared or replaced before the next run. 9.2.5. Analyses The during its liquid or run the samples taken from the CDHP solution buffer vessel and the

crystalliser

return acid buffer vessel were analysed with the ICP technique with the bench-scale plant. The CDHP solution was analysed for

P20,-, CaO, Si and Cd content, while the return acid or the liquid from the The solid samples were analysed with the ICP technique for their P20j- and a few liquid and solid samples were analysed with the ICP

crystalliser were analysed for its P-Cv, H„SO„, Si and Cd content. Cd content after the run. Sometimes The INAA technique for their Al and Fe content. technique was used to determine the radium content of some solid and liquid samples.

181

9.3. Results and discussion 9.3.1. The performance of the bench-scale run
Ca0 and Cd

The solution time. The

Po°5' buffer

concentrations

during

the last run in the CDHP

vessel

are plotted in the figures 2, 3 and 4 as a function of concentrations in the crystalliser and the P 0 and

P 2 0 5 > H2SOi(

and Cd

Cd concentration in the HH samples from the crystalliser are plotted versus time in the figures 5 to 9. The solution constant. cadmium figures in the 2 to 7 clearly demonstrate that the operating conditions were crystalliser in and that their average values were reasonably oscillating around the preset process conditions in the CDHP solution and in the Due to the oscillation of the operating conditions the phosphate and incorporated the HH samples as shown in the figures 8 and 9, also

show an oscillating behaviour.
w % P 2°5 50-1 w %CaO 6-

4030-

^^Ww/W

5-

f\l
3- ^

A/lyV/v/^W V y\

20101 1

210 1 50 time (hours) 1 100

()

50 time (hours)

100

C

Figure 2: P_0_ concentration in the CDHP solution in the buffer vessel.

Figure 3= CaO concentration in the CDHP solution in the buffer vessel.

The impurity

consequences levels

of

the operating

conditions

in combination with the

reached

in the bench-scale plant on the phosphate and cadmium

185

incorporation

in the H H as well as on the permeability of the f i l t e r cakes will

be discussed in the following s e c t i o n s . ppm Cd 30w %P70c 50-1 4030201010n 50 time (hours) Figure 5: P„0_ concentration in the solution in the crystalliser. ppm Cd 30-1 2520154102_1 j _

vs/V^A/vWV
20-

^^A/vTW/VY

50

100 time (hours)

1 100

Figure 4: Cd concentration in the CDHP solution in the buffer vessel. w %H7S0, 10-, 8-

5 —I T" 50 100 time (hours) Figure 7: Cd concentration in the solution in the crystalliser.

50

100 time (hours)

Figure 6: H SO. concentration in the solution in the crystalliser.

186

w %P205 0.4-,

ppm Cd 10-, 8-

0.3-

60.2-

4
0.1-

2H
-I 50 T 100 time (hours)

0.0-

0

I 50 100 h'me (hours)
HH crystals from the crystalliser. | cadmium | incorporation KCd

1

Figure 8: P_0C concentration in the 2 5 HH crystals from the crystalliser.

Figure 9: Cd concentration in the

run | w% C a O in the | conditions in the crystalliser | CDHP solution | w j P 2 0 w$ H ^ O ^ ppm Cd

ppm Cd

« I
I * . 6 I 7 I 5

4.9 4 4 4.2

|

37

2.3 2.5 2 2.1

18 25 19 23

4.5 6 6 6

0.25 0.24 0.32 0.26

I
| I

36
40 40

Table 4: Cadmium incorporation in H H during the bench-scale r u n s . * addition of Dicalite 4.15.8 a s body feed. .

9.3.2. T h e cadmium incorporation in H H

The

results

of

the cadmium incorporation in the H H precipitated from the

crystalliser during the last r u n , as well as those obtained from former runs are given in table 4. T h e w ? C a O in t h e CDHP solution is only given as a measure f o r the the s o l i d s c o n t e n t in the crystalliser, w h i l e also the KCd v a l u e s , representing cadmium concentrations in the HH divided by the corresponding cadmium

concentrations in the solution, a r e presented.

187

The of improve The

KCd

value obtained in the 6th run might be influenced by the addition 4.15.8. This was added in the digestion stage as body feed to

Dicalite

the separation of the HH/ore residue mixture from the CDHP solution by cadmium incorporated 2 and in the HH from the digestion stage (< 0.07 w$ 3 ppm at a cadmium concentration in the CDHP

pressure filtration. HpSOj.) varied digestion stage. 9.3.3. The phosphate incorporation in HH The results of the P.0,. uptake in the HH, precipitated in the crystalliser between

solution of 20-25 ppm. This implies a KCd value of about 0.1 for the HH from the

during the last four runs with the bench-scale plant are given in table 5. run I w? CaO in the I conditions in the crystalliser | w% P_0C incorporated
1 1
' d o

I CDHP solution | w$ P 2 0 4.9 4 4 4.2 37 36 HO 40

wj H 2 S0 4 2.3 2.5 2 2.1

| I I I |

in the HH 0.13 0.2 0.6 0.2

Table 4: Phosphate incorporation in the HH formed in the crystalliser during the bench-scale runs. * addition of Dicalite 4.15.8 as body feed. From of possible that change this of this table it can be concluded that the addition of SiO in the form

Dicalite 4.15.8 strongly influences the phosphate incorporation in the HH. A explanation in ratio the can be that the addition of silica influences the Al-F-Si solution. The molar F/Al ratio will change and it is known the growth kinetics of the HH crystals [1]. This

equilibrium

influences

the molar F/Al ratio may cause a higher supersaturation and thus an

increase in the phosphate incorporation (chapter 5 ) . The without value Dicalite of the 4.15.8 phosphate addition, incorporation is about 0.2 to be expected in practice, in the HH from the w$ P 0

crystalliser.

188

The

amount of phosphate incorporated in the HH obtained from the digestion in all four runs.

stage appeared to be about 3"3-5 w$ P 0

9.3.4. The permeabilities of the filter cakes The slurries runs around with permeability is were the obtained of the HH cake obtained by filtration of the HH from the according to the procedure given in chapter 6. The from the overflow of the crystalliser. The directly

crystalliser

determined

values of the permeability are given in the tables 6, 7 and 8 for the last three bench-scale plant. The oscillation of the operating conditions the preset process conditions, as already mentioned, is clearly visible

in these tables. The influence of the CaO content of the CDHP solution on the w% solids in the solution in the crystalliser is, for example shown in table 7.

conditions in the crystalliser | permeability of the w% P 2 0 5 39 39 wj H 2 S0 4 3.7 3.5 w? solids 7.3 7.3 | | | HH cake * 1 0 1 2 m 2 16.5 22.7

Table 6: Permeability of the HH cake obtained by filtration of the HH slurry from the crystalliser in the 5th run with the bench-scale plant. c o n d i t i o n s in t h e c r y s t a l l i s e r J w? P 2 0 5 39 40 37
140 • w$ H 2 S 0 4

p e r m e a b i l i t y of t h e H H cake * 1 0 1 2 m2 4.5 2.0 3-0 5.1 0.9

w % solids

|

H.2 2.0 2.2 3.0 1.6

5
9.1 10 6.3 10.2

I
| | | |

39

Table 7: Permeability of the HH cake obtained by filtration of the HH slurry from the crystalliser in the 6th run with the bench-scale plant. In this run Dicalite 4.15.8 was added as body feed.

189

conditions in the crystalliser | w$ Pp0 5 u% HgSOjj w? solids |

permeability of the HH cake * 1 0 1 2 m 2

40 40 39 140 40

2 3 3 2.5 2

6.7 6.6 7.1 6.7 7.1

Table 8: Permeability of the HH cake obtained by filtration of the HH slurry from the crystalliser in the 7th run with the bench-scale plant.

In table 9 the permeability is given for the DH cake obtained by filtration of a DH-phosphoric acid slurry from a commercial single filter HH/DH (Nissan H)

process.

conditions in the recrystalliser | permeability of the v% P_0C 2 5 26.4 wj H„S0„ 2 4 3.2 w$ solids I DH cake * 1 0 1 2 m 2

34.5

|

1.0

Table 9: Permeability of the DH cake obtained by filtration of the DH slurry (at 60 °C) formed after recrystallisation of HH into DH in a commercial single filter HH/DH (Nissan H) process

These permeability obtained and 8 a

results of the

indicate HH cake

that

addition

of

Dicalite

4.15.8

lowers

the

significantly to about 20 % of the permeability
_i 2

under normal operating conditions. By comparing the results of table 6 mean by the permeability of about 15 * 10 CTPA process, m
p

is obtained for the HH cake

produced

where the sulphuric acid concentration in the

crystalliser cake produced

is about 2 wj H SO.. This mean value of the permeability of the HH by the CTPA process will approach the value to be obtained in a

commercial CTPA process, because the influence of impurities on the permeability is taken 9 into shows account in these bench-scale runs. Comparison with the value in that the permeability of the DH cake is less than 10 $ of the

table

190

value

for

the

HH

cake

under

the operating conditions prevailing in the two

different processes. The permeability of the HH/ore residue cake obtained by pressure filtration of in the the slurry from the digestion stage, consisting of a HH/ore residue mixture CDHP solution, could not be measured directly, due to its extreme low

value. If, however, some basic data given in table 10 are

used for an estimation ~11 2 of the permeability of the HH/ore residue cake, a value of about 5 * 1 0 m is obtained, which is even less than 10 times the permeability of the DH cake.

viscosity of the CDHP solution density of the CDHP solution filter area cake height pressure drop over the cake mass stream of CDHP solution filtered

3 * 10 1500

J

Pa * s kg * m 2 m m kPa kg * hr

9.5 * 10 2.5 100 3.7

Table 10: Data used for the calculation of the permeability of the HH/ore residue cake, obtained by pressure filtration of the CDHP slurry from the digestion stage in the runs with the bench-scale plant.

9.3.5. Additional results

Some the

additional information could be deduced from the continuous runs with plant. For the HH precipitated in the crystalliser from a

bench-scale

solution Al and

containing

37 w% P-,0,. and 2.3 w$ H.SO.., distribution coefficients for

Fe ions could be derived. For Al a K-value of approximately 0.H and for

Fe a K-value of about 0.05 was obtained. Furthermore during patent the a run the with radium the no. content of some solid and liquid samples taken

bench-scale plant, was determined. According to a DSM 8006946 dd. 16-6-1982) all radium should precipitate in

(NL-Patent

digestion were

stage, if 10 $ of the total amount of sulphuric acid used in the fed into acid the is digestion stage. In our process about 20 % of the indirectly fed into the digestion stage with the

process required

sulphuric

return acid.

191

The measured radium concentrations in the various phases are given in table 11 for the 5th run with the bench-scale plant. The process conditions maintained during this run are given in table 12. Compound phosphate ore HH from the crystalliser HH/ore residue from the digestion stage product phosphoric acid radium content (Beq/g) 1.3 0.7 1.2 0.2

Table 11: Radium concentrations in the feed material and products of the 5th run with the bench-scale plant. process stream CDHP solution return acid w? P 0. 36 36 wj CaO 4 2.5 w? H-SCL

Table 12: Process conditions during the 5th run with the bench-scale plant. These because return process, the acid results do not confirm the findings reported in the patent, probably sulphuric acid was fed into the first digester after dilution with and the the results given reported in table 11 are obtained in a continuous in the patent are obtained in batch results

while

experiments. The radium concentration in the HH precipitated in the crystalliser in this process obtained and given in table 11 is comparable with the radium content of the DH by recrystallisation of HH in a commercial single filter HH/DH (Nissan

H) process [3].

192

9.4. Conclusions From the continuous runs with the bench-scale plant the following conclusions

can be drawn: - the cadmium incorporation in the HH precipitated in the crystalliser in the presence of impurities during the runs with the bench-scale plant is only slightly higher than in HH produced from chemically pure reagents (KCd » 0.25 and 0.2 respectively). - the phosphate incorporation in the HH precipitated in the crystalliser in the presence of impurities during the runs with the bench-scale plant is also hardly different from the incorporation found in the HH produced from chemically pure reagents (w$ P?0,- = 0.2 and 0.15 respectively). - The permeability of the HH cake obtained by filtration of the HH slurry from the crystalliser in the bench-scale plant, i.e. by filtration of crystals formed in the presence of impurities, is a factor five less than the values obtained for the HH cake produced in experiments with chemically pure reagents. This clearly shows the striking influence of impurities on the permeability of the HH cake. For this reason pilot plant data normally are used to obtain a reasonable estimation of the permeability of the filter cake to be formed in a commercial process. -12 (the permeability was 15 * 10 2 w$ H So and 65 * 10 -12 m 2 respectively) P201'

- under the conditions prevailing in the CTPA process (90 °C, 40 w? or 4.5 w$ CaO) corrosion is a serious problem.

- running a bench-scale plant is a tough job, due to the consequences of even small variations in feed, process streams or concentrations. - the search for a method to remove radium from the HH or to prevent the coprecipitation with the HH has to be continued. 9.5. Literature 1. Becker, P., Phosphates and Phosphoric Acid, Fertiliser Science adn Technology Series, Vol. 3, Marcel Dekker Inc., New York (1983). 2. Slack, A.V., Phosphoric Acid, Fertiliser Science and Technology Series, Vol. 1, Marcel Dekker Inc., New York (1968). 3. Weterings, K., The Utilisation of Phosphogypsum, Proceedings of the Fertiliser Society of London, nr. 208 (1982).

193

4. Witkamp, G.J., Schuit, S.P.J. and Rosmalen, G.M. van, Recrystallisation of Calcium Sulphate Modifications in Phosphoric Acid, Condensed Papers of the Second International Symposium on Phosphogypsum, Miami, Florida (1986) 106. 9.6. Appendices 9.6.1. Service round Use a wake-up signal to perform the following actions each half an hour. 1. Control the air supply 2. 3. 4. 5. 6. 7. 8. 9. Control the amount of phosphate ore in the ore feeder and refill if necessary. Control the ore supply to the first digester. Control the return acid and anti-foaming solution supply to the first digester. Report caking of phosphate ore in the first digester and suspend it in the solution. Control the amount of anti-foaming solution in the supply vessel and refill if necessary. Control the stirring speed in the three digesters. Control the slurry overflow from the first and the second digester. Control the pressure on the operating pressure filter.

10. Control the flow of the CDHP solution into the buffer vessel. 11. Control and report the height of the CDHP solution level and the stirring speed in the CDHP solution buffer vessel. 12. Control the temperatures in the orystalliser, third digester, return acid and CDHP solution buffer vessel and report deviations from 90 °C. 13. Control the supply of CDHP solution and sulphuric acid to the orystalliser. 14. Control the slurry overflow from and the stirring speed in the orystalliser. 15. Control the amount of sulphuric acid in the supply vessel and refill if necessary. 16. At the end of each shift the water levels in the thermostats are controlled and adjusted, if necessary, by feeding distilled water.

194

9.6.2. Pressure filter procedures 9.6.2.1. The precoat procedure - 10 grams of Dicalite 't. 15.8 are suspended in 90 grams of distilled water. This slurry is thoroughly mixed and poured into the pressure filter. - The break plate for the CDHP slurry stream is put in the filter. - The CDHP slurry supply pipe through the lid of the filter is cleaned with a rod. - The filter lid is put on the lower part of the filter and the whole is screwed up. - The CDHP slurry supply tube is cleaned with water and fitted to the pressure filter valve. - The pressure filter valve is opened. - The airation valve is closed. - The pressure filter is ready for the filter procedure. 9.6.2.2. The filter procedure - The pump between the third digester and the pressure filter is started. - After about one hour the pressure in the pressure filter is 1.8 to 2.0 bar excess. - Now the filter change procedure is started. 9.6.2.3. The filter change procedure 1. The pressure filter valve is closed. 2. 3. H. 5. 6. 7. 8. The pump is put in reverse. If the tube between the pressure filter and the third digester is empty the pump is stopped. The valve near the third digester is closed. The tube is removed from the pump and the third digester. The tube connected to the second pressure filter is put into the pump and fitted to the third digester. The pump is started, pumping in normal direction. The valve near the third digester is opened.

195

9.

The CDHP solution in the loaded pressure filter is almost completely squeezed out by supplying nitrogen gas to maximal H bar excess.

10. The nitrogen supply is stopped. 11. The pressure filter is airated by opening the airation valve. 12. The pressure filter is opened. 13. About 100 grams of distilled water per hour operating time of that pressure filter is put into the filter. 14. The stop erlenmeyer is filled with 100 grams of distilled water, closed and put in the thermostat again. 15. After removing the break plate, the cake and the water are stirred gently. 16. The pressure filter and the airation valve are closed. 17. Repeat point 9 to 12. 18. A sample of the upper part of the cake is taken. 19. The remaining solids are removed from the filter with a spoon in the residue storage box. 20. The residue storage box is weighted and the weight, date and time are noted down 21. Now the precoat procedure starts. 9.6.3. The HH washing procedure Each quarter of an hour a filter basket filled with HH slurry is removed from

the filters located after the crystalliser in the bench-scale plant. All filters are made of glass, so be carefulll! - the contents of the filter basket is spread out over the filter. - during one minute the slurry is filtered by suction and in the meanwhile firmly pressed by a stamper to squeeze almost all acid out of the cake. - the suction is turned off and the wash water erlenmeyer, containing the wash water of the second wash step of the former washing procedure is emptied on the filter. - the cake and the solution are stirred gently. - during one minute the slurry is filtered by suction, while the cake is firmly pressed by a stamper to squeeze out the liquid.

196

- the suction is turned off and the erlenmeyer underneath the filter is emptied in the filters placed after the crystalliser In the bench-scale plant. - the wash water erlenmeyer is put underneath the filter. - the stop erlenmeyer containing about 65 grams of distilled water is removed from the thermostat and emptied on the filter. - the stop erlenmeyer is filled with 65 grams of distilled water and put into the thermostat again. - The cake and the water are stirred gently. - the slurry is filtered one minute by suction, meanwhile firmly pressing the cake with a stamper to squeeze out the liquid. - the suction is turned off and the wash water erlenmeyer is removed, closed and put into the thermostat. - a sample is taken from the upper part of the HH cake. - the HH cake is removed with a spoon into the HH storage box. - the HH storage box is weighted and the weight,date and time are noted. - the first erlenmeyer is put underneath the filter again. - the filter basket is cleaned with water and set apart for later use on the filters placed after the crystalliser in the bench-scale plant. - The HH washing procedure can start again.

197

SUMMARY The fertiliser industry is the main user of phosphoric acid produced by

digestion of phosphate ore with sulphuric acid. Impurities, ore are In disposed phosphoric such as the heavy metal ion cadmium, originating from the phosphate between this high the phosphoric acid and the byproduct, a calcium byproduct, Due to cadmium the so-called as well phosphogypsum, as is distributed

sulphate modification. the Netherlands, in the acid river with a Rhine. environmental restrictions the. use of content the disposal of

phosphogypsum with a high cadmium content will be prohibited in the near future. The Dutch Government therefore started a project in cooperation with DSM and the TU-Delft phosphoric In phosphate same digestion between. In this of thesis the results are presented of an investigation of the technological aspects of this new process. First ore all the mechanism which controls the digestion rate of phosphate phosphoric acid was determined to be the diffusion of calcium in recycled to develop a Clean Technology Phosphoric Acid (CTPA) process, in which acid is produced with less than 5 ppm cadmium and phosphogypsum with acid the processes route operating nowadays the digestion of the

less than 1 ppm cadmium. phosphoric ore and and crystallisation of calcium sulphate takes place in the selected for the CTPA process has separate stages, thus enabling removal of the cadmium in

reactors. The

process

crystallisation

ions from the surface of the ore into the bulk of the solution. The masstransfer coefficients were determined as a function of the phosphoric acid concentration the cadmium and phosphate incorporation in calcium sulphate and the temperature. Thereafter hemihydrate of (HH) formed in the crystallisation stage was measured in dependence

the process parameters. The cadmium incorporation increased with an increase

in the sulphate content of the solution in the crystalliser, while the phosphate content of the HH crystals decreased. Furthermore, The permeability sulphate the filtration of this phosphoric acid-HH slurry was studied. of the HH cake obtained in HO vi% P.Cv is maximal, if the

content of the solution in the crystalliser is about 1.8 w$ H„SCv at a

residence time of about 20 minutes.

198

An

aditional

study

was

performed to determine the fluoride distribution acid solutions and the ambient air. An

coefficients as a

between

phosphoric

expression was determined, which predicts the fluoride distribution coefficients function of the temperature, the fluoride, phosphate and sulphate content of the phosphoric acid solutions. Finally additional operating This plant all results according was the results used to be to obtained to in the former studies as well as some

were

solve the mass and heat balances of a plant self was supporting with respect to energy build in which the influence of

the CTPA process and producing 1000 tons P ? 0_ per day. nearly plant

found a

consumption. Furthermore impurities bench-scale on the cadmium and phosphate uptake in the HH crystals as well as on

the permeability of the HH cake obtained by filtration of the phosphoric acid-HH slurry were studied. The influence of impurities on the incorporation of cadmium and the phosphate of HH The The cake ions obtained point in the from out HH crystals was hardly detectable, experiments, but the permeability the HH cake was about five times less than the permeability of separate that a crystallisation CTPA process in which

chemically pure reagents were used. results is in principle feasible. Validation on a pilot plant scale is, however, still required. feasibility of the cadmium removal section will be reported elsewhere (PhD Thesis T.T. Tjioe, Technical University of Delft, 1987).

199

SAMENVATTING Fosforzuur, In metaal cadmium dat gemaakt is door het ontsluiten van fosfaaterts in

zwavelzuur, wordt voornamelijk gebruikt door de kunstmest industrie. het fosfaaterts bevinden zich veel verontreinigingen, waarvan het zware ion cadmium,, er een is. Tijdens het ontsluiten van het erts verdeelt het zich over het fosforzuur en het bijproduct, een gehydrateerd Dit bijproduct, fosfogips genaamd wordt in Nederland geloosd in

calciumsulfaat. fosforzuur De dan 5 In

de Nieuwe Waterweg. Tengevolge van milieutechnische bezwaren zal het gebruik van met een hoog cadmium gehalte evenals het lozen van fosfogips met een Overheid en schoon heeft daarom samen met met DSM en de TU-Delft een dan de 1 ppm cadmium te van het hoog cadmium gehalte in de nabije toekomst verboden worden. Nederlandse ppm de cadmium project opgestart, om een mogelijkheid te vinden om schoon fosforzuur met minder fosfogips minder vindt produceren. hedendaagse en De de proces fosforzuur route, die processen van het ontsluiting fosfaaterts reactoren. kristallisatie calciumsulfaat plaats in dezelfde

geselecteerd is voor het Schone Technologie

Fosforzuur Proces (STFP) berust op een scheiding van deze twee stappen, waardoor het mogelijk is om het cadmium tussen deze twee stappen in te verwijderen. In naar dit proefschrift worden de resultaten gepresenteerd van het onderzoek de technologische aspecten, die voor de ontwikkeling van dit nieuwe proces Als eerste is de ontsluitsnelheid van fosfaaterts in fosforzuur onderzocht. Er bulk is gevonden van de dat diffusie van calcium ionen van het erts oppervlak naar de de als snelheidsbepalende functie stap is. Ook zijn de van de fosforzuur concentratie en de oplossing

onderzocht moesten worden.

stofoverdrachtscoefficienten temperatuur bepaald. Daarna (HH), is dat is de

cadmium en fosfaat inbouw in het calciumsulfaat hemihydraat wordt in de kristallisatie stap van het proces,

geproduceerd

onderzocht. De invloed van verschillende proces parameters op de mate van inbouw bekeken. Het bij een is meest opvallende resultaat is dat de cadmium inbouw in het HH stijgende zwavelzuur concentratie in de oplossing in de toeneemt

kristallisator, terwijl de fosfaat inbouw juist afneemt. Verder P_0_ wordt de filtreerbaarheid van deze HH kristallen onderzocht. In HO w?
die

wordt de maximale permeabiliteit van de HH koek bereikt, als de HH gevormd in een fosforzure oplossing (MO wï P20c)> ongeveer 1,8 w$ H-SOn bevat

bij een gemiddelde verblijftijd in de kristallisator van circa 20 minuten. 200

Omdat om als de bepalen.

fluor een waardevol byprodukt is, is nog een apart onderzoek opgezet van fluor en van tussen het het fosforzuur en de lucht te fluoride, het fosfaat en het Een uitdrukking voor deze fluorverdelingscoefficient is afgeleid, die van de temperatuur

verdelingscoefficient

functie

zwavelzuur gehalte van het fosforzuur, voorspelt wat de concentratie in de lucht zal zijn. Tenslotte volgens gegevens resultaten Als het uit van is STFP de een werkt massa en en warmte balans opgesteld voor een fabriek, die 1000 ton P_0 C per dag produceert. Hierbij zijn gebruikt en aangevuld met beschreven onderzoeken

hierboven

additionele proeven en gegevens uit de literatuur. Deze fabriek

blijkt ongeveer in zijn eigen energie behoefte te kunnen voorzien. laatste onderwerp worden de resultaten gepresenteerd van een onderzoek met een fosforzuur fabriekje op laboratorium schaal. In dit fabriekje is gekeken naar de invloed van verontreinigingen op de cadmium en fosfaat inbouw in het HH. Tevens is gekeken op van naar de de filtreerbaarheid en fosfaat van dit HH. De invloed van verontreinigingen perméabiliteit koek, cadmium inbouw was erg klein, maar de

de HH koek was ongeveer een factor vijf lager dan van de HH

die geproduceerd werd in de afzonderlijke kristallisatie proeven, waarbij

chemisch zuivere reagenten gebruikt werden. Alhoewel een pilot plant stadium zeker niet overgeslagen kan worden, is wel vast komen te staan dat het STFP in principe een haalbaar proces is. De 1987). haalbaarheid worden van de cadmium verwijderingsstap zal op een andere plaats (Proefschrift T.T. Tjioe, Technische Universiteit Delft, gepresenteerd

201

PUBLICATIONS Various chapters of this Thesis have been published or are submitted for

publication: A Clean Technology Phosphoric Acid Process S. van der Sluis, Y. Meszaros, J.A. Wesselingh and G.M. van Rosmalen. Proceedings of the Fertiliser Society of London, nr 219, 1986. The Predigestion Stage of a New Phosphoric Acid Process S. van der Sluis, Z. Murach, J.A. Wesselingh and G.M. van Rosmalen. Proceedings of World Congress III of Chemical Engineering, Tokyo, Japan, Volume U (1986) 96. The Digestion of Phosphate Ore in Phosphoric Acid S. van der Sluis, Y. Meszaros, W.G.J. Marchee, J.A. Wesselingh and G.M. van Rosmalen. Submitted to Industrial and Engineering Chemistry Research. Crystallisation of Calcium Sulfate in Concentrated Phosphoric Acid S. van der Sluis, G.J. Witkamp and G.M. van Rosmalen. Journal of Crystal Growth 79 (1986) 620. Fluoride Distribution Coefficients in Wet-Phosphoric Acid Processes S. van der Sluis, J.H.M. Schrijver, F.P.C. Baak and G.M. van Rosmalen. Submitted to Industrial and Engineering Chemistry Research. Mass and Heat Balances of a Clean Technology Phosphoric Acid Process S. van der Sluis, J.M.P. Oomens, Y. Meszaros, J.A. Wesselingh and G.M. van Rosmalen. The Second International Symposium on Phosphogypsum, Miami, Florida, December 10-12 (1986).

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