‘in petroleum refining. i I
in the manufacture of coal-tar, dyes and anumber of pharmaceuticals. | |
in the manufacture of explosives. | :
in the textile, paper and dyeing industries. I
for cleansing metals before enameling, electroplating, galvanizing ete.
in storage batteries.
in the manufacture of sulphates,
in the laboratory as an important reagent and as a -drying and
dehydrating agent.
CHTORTC AGID, HCl
bisulphates and sodium carbonate.
2.8, ¥.
Hydrochloric -acid is one of the basic cl
applications. The major uses are In petroleum,
plastic industries. Hydrogen chloride is a gas a
aqueous solution is known as hydrochloric acid.
28.1 Preparation { ;
Mostly hydrochloric ‘acid! production results as:a by-product of various organi:
chlorination reaction reactions. Such as the chlorination of benzene to chlorobenzene
Other similar sources include the cracking of ethylene dichloride to yield vinyl chloride,
the catalytical crackinig of 1,1,2,2:tetrachloroethane to trichloroethylene, and production
Of linear alky] benzene. : = i
Direct synthesis include two process
a), Selt-Sulphuriec acid
hemicals which has a long range of
metallurgy, leather, textile, dyes. and
| room temperature and pressure. Itz Applied Chev Hc) 4 Na,So,
: The combustion gases, céntaining hyde lori i ‘
ee née at akc ee ee 8 -nydrogen chloride (approximafely' 30% HC),
“= water; and leave the Goolers at‘ab
- ‘water and discharged to the atmospheré.The more recently designed plants have been use
of impervious graphite and structural plastics for absorbers and cooler.
A few plants use thé Laury furnace;'a: horizontal rotary kiln, in'which the reacting
‘mass comes into contact: with fuel. combustion: gases.-These gises, containing as little ag
5% hydrogen chloride, leave the firnace at 300°C, and are zooled and then recovered in
the manner described previously. : s es a fe 4
In making potassium sulphate from potassium chloride, hydrochloric acid results
s co-product. The reactions aré analogous, with: potassium chloride in place of sodium
chloride, - 2 p:% 280 y ihe Ra sagst fc
Coke Tower
aye he forest 5 HySOg 2 HEL
Fig 2.5. Flow chart for HCl manufacturing by salt-sulphire acid process
i "
Froi
ral d: for example, the
Several tj f burners, are used:, for 6: : :
trurnerthe eraphite burner, and’ the waterjacketed stell burner. The last: mentio
burner cannot of course be used with wet gases.’ !
(ak eas p
Hydrogen and hlorina! ig of hydrogen to drogen chloride
e is burned ina slight. excess of Eysdrogtn ds prodee ne eal
met
Ag UR Clg es 2HCl Basie Chemical Industries 51
A submerged combustion burner, operating beneath’a surface of muriatic acid,
as been developed. The’ burned gases, Practically pure hydrogen chloride, are cooled,
absorbed, and Scrubbed ina system essentially the same as that used in the salt process,
‘phe purifying coke tower,. however, is ‘omitted and.in some ‘systems (where the gas
‘yoncentration approaches 100%HCl) the scrubber may be omitted. ‘Strong HCl (35%) is
oved directly: from the bottom of the cooler by means of a trap, and weak acid (28%)
feaves the boftom:.of thé absorber. Recently installed absorbers have been built of
italum and structural carbon, as well as silica. This process readily gives a water-white
uct. 2 ast agers
ane concentration. of hydrogen chloride in burner gases generally depends on the
jegree of chlorine utilization... With 0.03%-or less chlorine in-the product gases, hydrogen
loride concentration. may be as high as 98.5%. Where 0.1%, chlorine is allowable,
drogen chloride ‘concentration may reach 99-99.55%. Manufacturers often insist on
100% chlorine utilization, in which case éxit gases maybe only 90% hydrogen chloride
jacause of the 5-10% excess hydrogen used. poets Lome
Cooling.
waters
gases
Hydrochloric Acid “Waste
6; Flow chart for HCL manufacturing from hydrogen and chlorine
@ manufacture of soda ash is one of
The m of the most im
dustries. It is used for the production of soap, detergents, fibe:
ulp and paper, fertilizers, explosives and other chest
anufactured by four methods. rv emenle. 8
@). Leblane Process 3
Electrolytic process. ‘
Solvay process
‘The first three procgsees are usually used and would be discuissed over here,
mitre es
This is an obsolete method and described hero
lethod following three stages are invol
Sodium chlor
portant heavy chemical
rs, glass, petrochemicals,
‘adium carbonate can be
just for knowledge:
volved to propare sida ash. 8" AcCoPding to
¢ ie reated with sulphuric acid to produce godiuim sidlphate,
2NaCl + H,SO/—> Na,S0,'+ SHC1 ° Cu, 400°C
CH,OH + [0] ——--»_ HCOH + H,0
200 atm ;
Cu, 400°C
HCHO + [0] ———» HCOOH
7 : 200 atm. *
.» Oxalic acid is an organic compound with the formula CoH2Ou or (COOH)s It is a
rless crystalline solid that forms a colorless solution in water. Its condensed formula is
100CCOOH, reflecting its classification as the: ‘simplest dicarboxylic acid. Its acid
trength is much greater than that of acetic acid. Oxalic acid is a reducing agent and
conjugate. base known as oxalate C,0., is achelating agent for metal cations. “dried. The mother liquor is reused as make-up in subsequent batches.
db + Appuea.cnemusiry. 5
‘Typically, oxalic acid occurs as the dihydrate with
ingestion of oxalic acid or prolonged skin contact.can be dangerous.
eK re ¥ i: | iy { is
st a ey of salts of oxalic’acid from plants had been Inown,|at tn lates
gince 1745. when the Dutch botanist and physician Herman Boerhaave os a sa
——t ; =H
the folmula CaH04 = Exfessi
from sorrel, By 1773, Frangois Pierre Savary of Fribourg, Switzerland hed isolate oxal
acid from its, salt in sorrel. Swedish chemists Carl Wilhelm Scheele and TorbernOk
Bergman produced oxalic acid by reacting sugar with concentrated nitric acid. There ai
many methods available for the production of oxalic acid which may involve its productio
either from sodium formate or from the oxidation of carbohydrates. fd
9) From Sodium formate fel :
375°C fie |
2HCOONa. ——» FOON? 4 Hy
COO'Na ke oH
“ot . I :
GOO'NA 4. CalOH), ——» (COO),Ca + 2NaOH] |
coo'Na | |
: fa
= (COO),Ca +HySO, . ——-» (COOH),.+ CaSO, | 7
80-90% Yield
| ee
Sodium formate is produced by the reaction pf solid sodium hydroxide (97-98%
and carbon monoxide at 200°C and 150 psi in an autoclave (the process used in the
~ ‘manufacturing of formic acid). After the reaction is cbmpleted, the pressure’ is reduced in
autoclave and the temperature is raised to 400°C. The. sodium formate is converted into
sodium oxalate, and the hydrogen formed is exhausted from the autoclave. When the
evolution of hydrogen ceased, the reaction is complete. 7 |
‘The reaction mixture (crude sodium oxalate) is transferred |to a ‘precipitator,
where calcium hydroxide is added with thorough agitation. The calcium oxalate formed is
filtered off, and the sodium hydroxide solution is concentrated for reuse. The filter cake,
containing crude sodium oxalate and small amounts of calcium carbonate, is run to an
acidifier, where it is reacted with dilute sulfuric acid. A large percentage of calcium is
’ precipitated as calcium sulfate dihydrate (CaSO.2H20). The solution is concentrated,
precipitating more calcium sulfate, which is filtered off. The mother: liquor is run to,
crystallizer, where it is concentrated to a gravity of 30°Be and (cooled, Oxalic acid’
crystallizes out in the form of the dihydrate (HOOCCOOH. 2H:20), which is washed and
. The yield of oxalic
acid dihydrate is about 80% by weight based on sddium formate. It is generally sold and
used as dihydrate, but anhydrous oxalic acid may|be formed by heating the dihydrate to
100°C, where it loses 2 molecules of water. ' | el Pe
directly to oxalic acid
‘The sodium oxalate formed in the autoclave may be acidified c r ¢
by mixing one part of sodium oxalate with 3 parts,of methanol. To this slurry aaa a3
a
. part of concentrated sulfuric acid, After thorough ‘agitation. Insoluble ‘sodium. si
precipitated out from the methyl oxalate-methanol-s ai
sulfate is filtered off, and the mother liquor is hydroly:
= |
wulfurie acid golutioh. The sédius
zed by the agai of 3.5 parts 0 Ged for rouse. The erude oxalic acid residue 8 concentrated}and th.
e : f s
is di fo |
acid ergstallizet iat cium. oxalate-caustic soda slury fi
rocess variation, the cal xalat fon
In a * encted directly with carbon monoxide in an autoclave, Bore tne
precipitator if Ttnonoxide renct to yield sodium formate. The caltium dralate ij
soda red from the formate solution by filtration. The oxalates go forward ay dogo
separa ly; the-sodium formate solution is concentrated by evaporation, dried, nq =
viously; , i.
prove material for sodium oxalate manufacturing. |
" Hydrogen Ca(OH), Dil.H,80, |
|
. HCOONG, Autoclave Precipitator ‘Acidiffier |
Filter
NaOH Soln. Caso, Make up Oxalic Acig
| liquor
Fig 2.9.Flow Sheet for oxalic acid preparation. from sodium formate
=< p) From Carbohydrate fetes
ce De ee GsHiz05 + HNO, > - 3(GOOH} + 6NO-+ 60
Oxalic acid is prepared by the oxidation of carbohydrates such aé glucose. sucrose
‘starch, dextrin and cellulose by nitric acid. The alkali (potassium and sodium hydroxides)
fusion of carbohydrates also yields oxalic acid. The fusion method is particularly
applicable in the utilization of waste cellulosic materials, such as sawdust, corn cobs
‘cornstalks and oat hulls. ‘ ae ‘ \.
Raw starch (85%) is dispersed by slurrying it in approximately an equal amount
11% oxalic acid solution at 167°F to. 176°F. After refluxing for approximately Ghr,
¥irtually all the starch is hydrolyzed to'a monosaccharide, chiefly glicose. The hydrolyzed
starch solution containing about 60% is mixed with oxalic acid mother liquor recovered
‘from the filtration step of previous run. This mother liquor is enriched with small
* amounts of sulfuric acid and catalysts to compensate for process losses: that is; 1 to 2 %'9t
» 100% sulfuric acid based on the weight of recovered mother liquor. The adjusted mother:
pee solution contains approximately 50% sulfuric acid, 5% oxalic acid,0.5% ferric ion
i
“(ferric sulfate) and 0.005% vanadium (as vanadium pentaoxide). i
The glucose-mother liquor solution is heated to about 160°F with good agitativn in
@ reactor. Nitric acid (65-95%)\is gradually added at a rate suited td maintain the
temperature 160°F. Some external cooling is generally used to facilitate the acid solution.
The ratio of glucose (60%) solution-nitric acid (90%)- mother-liquor (50% sulfuric acid) is !
‘0 2.5 to 7.5 Oxides of nitrogen|evolved during the reaction are adsorbed in a suitable
piric acid absorption system. The nitric acid produced from the system i concentrated
Be reuse. When the oxidation is completed, the solution is run into a crystallize?
_cgutntrated for reuse. When the oxidation ia completed, the solution is rum int {)
Pera zer, when it is cooled (75 to 90°F) wit agitation. The resulting shury is filter?’
} the mother liquor is recycled for subsequent runs. i | 3
I i A eachtained by dissolving the crude product, in
filtered, the mother-liquor is reborn e solution is cooled to 175°F, the slurry is
<1506F and the resulting wzalic arnt ie Meiee lnsolving tank. The-filter cake is dried below
Oxalic acid may also the obtained by the diroct notte at nitete ack
Hion of nitric acid on the corn
cobs, oat hulls, or saw dust and other cellulosic materials. One part by weight of ground
corn cobs; oat, hullé or saw dust is added to 3 parts by weight of cold 96% niteie acid. After
the initial reaction has moderated, the mass is heated to dissolved the cellulose. The
mixture is cooled and 0.1 pre-cent vanadium pentoxide and 3 parts (based on the original
weight of corn cobs or oat hulls) of 50 to 56 per cent nitric acid are added. The mixture is
allowed to stand for several days at room temperature -to complete thé Sxalic ucid
; formations and crystallization. The nitrogen “oxides are adsorbed and reconverted to
~ concentrated nitric acid: The’ crystals of oxalic acid are filtered and purified as deserihed
previously. The average yield of oxalic acid dehydrate is about 1 ton of acid per ton of cobs
and 1.1 to'1.2 tons of acid per ton of oat bulls.” .
: The alkali fusion of carbohydrates yield oxalic acid plus other organic acids such
as acetic acid. The general procedure is to. mix saw dust or corn cobs with about 2.5 to 3.0
times their: weight of sodium lydroxide plus a small amount of water. The mixture is
~- slowly heated to @ temperature of 400 to 47°F: The lemon yellow fusion mass is cooled
and then lixiviated. & a ; 5 3
The resulting oxalate salt is netutralized by sulfuric acid. The yield of oxalic acid is
25 to 35-per cent based on the weight: of oat hulls, corn cobs, cornstalks and saw dust.
About 15'to 25 per cent volatile acid are also obtained. These comprises acetic acid (12 to
18 per cent) and formic acid (3 to 10 per cent).
‘Oxalic acid is also produced by fermentation of the sugars.
HS, Make up <=
HNO,
“Glucose Mother liquor
Filter”
{Dyer
Oxalic Acid
Crude’ Oxalic Acid
Solution
‘Tank
Fig. 2.10 Flow sheet diagram for oxalic acid prepa
Ee apap 40 ANESDIRDDY eis the organic compound with the formula CiHa(CO}O. Le is
ido i inci ial form of
the anhydride of phthalic acid. Phthalic anhydride ie Brincipal « commercial form of
phthalic acid. It was the first anhydride of a dicarboxylic ack Wo 1 “ee en
‘This colourless solid is an important industrial chemical, especially aa
wins
ation from carbohydrates , Basic Chemical Industries 59
——Tation of plasticizers for plastice..‘The primary use: of phthalic anhydride i
e: real intermediate in the production of plastica from vinyl chloride. Pelt tee
[i Mhich function’'as plasticizers, are derived from Phthalic Anhydride. Phthalate
bi jcizers are used for the production of flexible PVC producta such as cables, pipes and
‘hoses, leather cloth, shoes, filin for packaging ete. Phthalic anhydride has another major
jot. the production of polyester resins and other minor uses in the production of alkyd
sae used in paints and lacquers; certain dyes (anthraquinone, phthalein, rhodamine,
“Halocyanine, fluorescin, arid xanthene dyes); insect repellents; and polyester polyols
pe olyurethanes. Its also utilized as a rubber scorch inhibitor and retarder.
7.1. Preparation : es
On large scale, phthalic anhydride is produced by oxidation of naphthalene and
rthoxylene: ;
a) From Oxidation of Naphthalené
~ V205
“ 4.502 |; >
: 675 - 850°F
; ob
Naphthalene :if melted and pumped to a vaporizer, where it is vaporizer, where it
vaporized by bubbling primary preheated air through the ‘molten imaterial. Additional
Gs added to the primary air-naphthalene vapor steam in a’ inixing section in the exit
ipe from the vaporizer to bring the air-naphthalene ratio to, 18-22:1 by weight. This
“vapor mixture is then led to a converter, consisting of multiple tubes filled with supported
‘vanadium pentaoxide catalyst. Heat is removed from outside of the fixed catalyst, either
py boiling mercury‘under suitable pressure or by pumping molten salt across the tube
Stank. In the converter the naphthalene is oxidized to phthalic anhydride, carbon dioxide
.d water. Optimum temperature in the reactor is 675-850°F--
Exit gases through a vapor cooler that reduces the gas temperature to just above
‘the dew point (about 260°F) and: then enter the recovery system. Phthalic anhydride
‘crystallizes on the. walls of large air-cooled condensers. The crude product obtained is
‘refined by distillation in a stainless steel vacuum still. The purified phthalic anhydride is
ustially melted and flaked for storage and packaging: Maleic anhydride, formed as a by-
‘product, may be removed by working up the crystals in the last compartment of the
condenser box system or by scrubbing the tail gases from the condenser boxes. Most
‘commercial phthalic anhydride contains 0.25-0.40 percent maleic anhydride.
Raced belle maces pentaoxide catalyst possess a long life, acting satisfactory for
aon or ‘inuous operation. The amount of phthalic anhydride is produced is at
‘ast 20,000 times the weight of the catalyst present before reactivation is necessary.
ee
'O <4 20024 2H,0 60 Applied Chemistry
‘Naphthalene Phthalic
[easier }—~Joo0 Anhydride
fused
Melting
kettle
Pt a stack
Gases
Vapor (Condenser
cooler Box
I
Secondary Air
Waste
Fig 2.11. Flow Chart for Phthalic anhydride preparation from naphthalene oxidation
|b) From Oxi ation of Orthoxylene!) : ag
CH3 V,0;
Oe O + 3H,0
0°F
cris 100
! Oo
Orthoxylene is vaporized and mixed, with pre-heated air. About 10 times the
theoretical requirémeit of the air is used in order to avoid operating within the explosive
limits. The mixture is then fed into the reactor which is similar to the ane described
previously for the oxidation of naphthalene. Vanadium pentaoxide based catalyst is used,
and the heat of the reaction is removed by circulating molten salt outside the cata
tube. The conversion temperature greater than 1000 Fahrenheit, and the contact time of
the order of 0.1-0.15 second.
‘The reaction gases, consisting of phthalic anhydride, carbon dioxide, and water,
are cooled in heat exchangers, condensed distilled, flaked and packed in similar manner
as discussed on naphthalene oxidation’ method. The finished material is of high purity
analyzing about 99.5% phthalic anhydride.
Salt Cooler Stack gases
Onylens Vaporizer Reactor _}+[ Vapor cooler }4Caderse"1_af “Met Tank Fisker
1S
Preheater Waste *
| Phinale
| Annydtide
Fig 2.12. Flow chart for the preparation of phthalic anhydride by o-xylene oxidation
fee & paints, pharmiaceuticals,
treat.‘Treatmient methods
clude : advanced ‘oxidation
vitrification, ‘incineration chemicalimmobilization or |
eee is ne ee ean: usually. be ‘neutralized dias > controlled “conditions.
: Neutralization’ frequently produces a precipitate that will require treatment‘as,a solid
residue that may also be toxi¢..In some 'cases, gases may be evolved requiring treatment
“for the’ gas” stream. Some other forms “Of. treatment’ are’ usually required following
© Geutralization.
“TE Qiaaaaaetvay ee
and grease can be recovered from opent water surfaces by skimming devices,
2.15.8. Treatment of chromium
--Chromium,. present ‘in tannery effluént 4 is Ginoved: by using. “Chromium salts
(Chromitam: chloride. as_ adsorbate) and cement (aiwaste from white. cement
industr) oe aceon 7 setae pit:
12.18.
‘pest th Gan be very diffi
me ohen, pes to the materia! being treated. Methods:
essing, distillation,adesrbtion,
ie
~'Asig UNIDO has been. actively looking for methods to improve coriventional: treatment
J »processes which simultaneously reduce the nitrogen content and give: the possibility of
‘dealing with TDS/chlorides, present in the effluent. The following technologies relating to
the issues nientioned were implémented in pilot demonstration ‘units:
Reverse osmosis (RO) of treated tannery effluent
“Iniproved solat evaporation * E
Carbon dioxide’ (CO2) deliming in’a small scale taniiery, to shtucs ashinonical
nitrogen. -~ zh
F Linancvieied wet land treatment system, ee
e logics for treatment of tannery "effluent are generally energy.
a& chemical atten ead: contifudus ‘process ‘inonitoring and control, are’ required to
chieve’ optimum: results. ‘In séarch for alternatives; robust, easy.-to, operate and low
‘maintenance ‘technologies, constructed. wetland ‘system, also known. as\ root zone
‘treatment system; using reeds for treatment of effluent; has been considered a possible
Sption: This system: is ‘widely used in Europe and elsewhere to. treat. municipal sewerage-
However, there was no practical experience, ‘at least at semi-industrial scale, about its
Pplicability in. purification. of tannery. effluents. Accordingly, in cooperation with willing
“fnneriea a and, management 6 of common effluent treatment plants (CETP) in Tamilnadu,
~; India, UNIDO, ‘under its Regional Program, éstablished four pilot and demonstration reed
beds, each with different features, to deal: with effluent of different characteristics. Some
ame Pollutants, their sources and health effects on human are shown in Table 12. ‘Blue
Green
Colour:
Paper and Leather Industries
0sed. variously by different scientis:s in the nineteenth
‘Century, the famous ‘one which was the Russian Chemist Dmitri Mendeleev and the
French chemist Marcell» Berthelot. At that time, the biogenic nypotheses have lost
iground to the dominant view that petroleum is a fossil fuel. According to this theory,
patutal petroleum was formed at the time of the formation of earth from deep carbon
deposits.Within the mantle, carbon may exist in different form such as carbonates,
