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United Arab Emirates University

Faculty of Chemical Engineering

Industrial and Waste Water Treatment CHME441

Removal of sulphur compounds from wastewater

Student Name ID

Noran Mousa & Albaina AlDhaheri


201450098 201202649
Project advisor: MD Monwar Hossain

(Fall 2017/2018)

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Summary
The invention relates to a process for removal of sulfur compounds from
wastewater, which process provides recovery of elemental sulfur. The process is
carried out in two separate anaerobic reactors. In the first reactor organic
compounds are converted to acid compounds and sulfur compounds are converted
to sulfide compounds. The sulfide compounds are stripped from said first reactor
with a stripping gas. Subsequently, the effluent of the first reactor is fed to a
second anaerobic reactor, in which organic compounds, such as the acid
compounds, are converted to produce biogas, while any unconverted sulfur
compounds from the previous step are converted to sulfide compounds as well.
Finally, the sulfide compounds are removed from the second reactor in a stripping
system, and converted to elemental sulfur in an absorber.

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Introduction
Anaerobic biological processes for the treatment of wastewater having a high
COD (chemical oxygen demand) value are known in the art. In such known
processes, organic compounds are converted to biogas (a gas mixture comprising
CO2 and CH4) at temperatures above about 25° C. When wastewater contains
high amounts of sulfur compounds (e.g., more than ca. 100 mg S/dm3), such as
sulfates, problems may occur in operating such anaerobic reactors due to the
presence of sulfide, which is formed under anaerobic conditions from sulfate.
Sulfide may inhibit the methane formation. Also sulfide will give rise to H2S
formation at pH<9. H2S is a toxic and corrosive gas and requires measures to
control odor. The sulfide may be reoxidized into sulfate, but this requires an
additional aerobic step. Furthermore, regulations often impose a strong limitation
on the amount of sulfur compounds that can be discarded into the environment.
The anaerobic reactor in known processes is operated at a relatively high pH (8-
8.5), in particular when alkaline wastewater is treated having a pH of 9-12. As a
result, the stripping of H2S is slow, since H2S dissolves more easily in water at
higher pH. To compensate for this, equipment of a large volume has to be
employed, in particular the stripper column, which has to be operated with large
volumetric flows. An example of such a process employing an external stripper is
found in U.S. Alternatively, acid, such as formic acid, can be added. Both
alternatives bring about high equipment and/or operating costs. Another result of
operating the anaerobic reactor at a relatively high pH is that carbonate may
precipitate in the stripper, which leads to fouling and clogging of the equipment.
[1]

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Processes with review on recent technologies
As a consequence, there is a need for processes to remove sulfide from
wastewater. In the art different approaches have been suggested for sulfide
removal processes.

Firstly, an anaerobic process in which H2S is stripped from a methanogenic reactor


using a stripping gas. The H2S rich stripping gas is fed to a scrubber where the H2S
is converted into elemental sulfur. The scrubber is operated with a regenerable redox
liquid that contains an iron(III) chelate or an iron(III) complex. During this
absorption process sulfide is converted to elemental sulfur, while Fe(III) is reduced to
Fe(II). Fe(II) is reoxidized to Fe(III) by air in a separate aerator. This known process
is particularly suited for the treatment of alkaline wastewater, such as tannery
wastewater. However, the known processes have a number of drawbacks, for
example, the elemental sulfur that is formed does not accumulate exclusively in the
sulfur settling tank, but also forms deposits on walls of the tubing, vessels, sprayers,
blowers, pumps, packing material, etc., which causes the need for regular cleaning of
the equipment.[1]

Secondly, the batch adsorption of sulphur compounds from petroleum refinery


wastewater on a chemically modified activated carbon (MAC). The modification
technique enhances the removal capacity of carbon and therefore decreases cost-
effective removal of sulfide from refinery wastewater. [2]

Figure (A) : Breakthrough curves of sulphide onto different MAC, columns wastewater
contained 1000 mgL−1 of sulphide.

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Fig. (B): Freundlich fitting for the equilibrium isotherm data of the sulphide adsorption on
different MAC Adsorption experiments were carried out in batch mode using 0,4 g of
modified activated carbon.

Fig. (C): Langmuir fitting for the equilibrium isotherm data of the sulphide adsorption on
different MACAdsorption experiments were carried out in batch mode using 0,4 g of

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modified activated carbon and 100 mL of sulphide solution (100–1000 mg L−1). Samples
were agitated for 24 h at 25°C.

Thirdly, biological oxidation of hydrogen sulphide by aerobic Thiobacillus-like


bacteria has been described. The hydrogen sulphide is oxidised into sulphur particles
which are in the submicron range. The colloidal properties of these sulphur particles
are compared with those of a standard LaMer sulphur sol. The biologically produced
sulphur particles are composed of a core of elemental sulphur covered by a layer of
natural charged polymers, presumably proteins.[3]

Fig.(D). Biological sulphur cycle.

Fig. (E). Scanning electron micrograph of the surface of a sulphur-excreting Thiobacillus at


−180°C. Sulphur excretion on the cell surface is visible (arrows)

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Fig.(F). Hexadecane–water partition test. Biologically produced sulphur remains in the
lower water phase (1) whereas standard hydrophobic “sulphur flower” remains in the upper
hexadecane phase (2).

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Principles of the main process

This process uses an alkaline scrubber to remove sulfide from the stripping gas in
the first reactor. A wastewater influent is fed to a first (acidifying) reactor. By
bubbling stripping gas through the first reactor the sulfide produced in the first
reactor is stripped from the reactor. In the alkaline scrubber the stripping gas is
desulfurized by contacting it with an alkaline solution. This produces a stream
comprising hydrosulfide, which can be used for further processing and clean
stripping gas which is recycled to the bottom of the first reactor. To prevent under
pressure in the stripping gas recycle of the first reactor (e.g. as a result of
absorption of gases in the reactor) or overpressure in this reactor (e.g. as a result of
methane production), it may be useful to connect this stripping gas circuit with the
biogas effluent from the second reactor. The liquid effluent from the first reactor
is passed to a settler tank, in which the sludge settles and is recirculated to the
reactor, while the liquid is fed to the second (methanogenic) reactor. The liquid
effluent of the second reactor is sprinkled from the top of a stripper column, which
is fed at the bottom with a mixture of combustion off-gas and air. The liquid
effluent of this stripping column, which is essentially desulfurized, may be
discharged. The biogas produced in the second reactor is passed to the top of an
absorber (Absorber 1) in which it is contacted in co-current with fresh redox
liquor.

The purified biogas leaves Absorber 1 at the bottom. Optionally it can be mixed
with hydrogen gas. This hydrogen gas can be produced by an electrochemical
reactor, as is described in EP-A-0 766 650. The stripping gas from the stripper
which is used to desulfurized the liquid effluent of the second reactor is fed to
another absorber (Absorber 2). In Absorber 2 the sulfide loaded stripping gas is
brought into contact with fresh redox liquor to convert sulfide to sulfur. Absorber
2 is operated in countercurrent. The purified gas leaving at the top of absorber 2 is
vented. The redox liquors in both absorbers are obtained from the same
recirculating system. The bottom products of the absorbers, containing elemental
sulfur, are fed to a coagulation tank, a flocculation tank and to a sulfur settling
tank. The sulfur is obtained as slurry from the bottom of the settling tank.[1]

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Fig (G) describes a preferred embodiment of the process of the invention.

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Advantages

The low CO2 production in the first reactor is very favorable. Since only little
CO2 is produced, the sulfide loaded stripping gas will be relatively low in
CO2 content.
Another important aspect of the present invention is that the sulfide is removed
from the first reactor by feeding a stripping gas through the liquid in the reactor,
e.g. by bubbling. This makes the use of an external stripper superfluous, thus
saving on installation and operation costs.
Also, by using a stripping gas, no H2S will accumulate in the headspace of the
first reactor, which would occur when the liquid was fed to an external stripper.
Another advantage of flowing stripping gas through the first reactor is that it
enables a good mixing of the water, the anaerobic sludge flocs and the gas,
whereby the sludge may be suspended in the water by the gas. [1]

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Disadvantages and limitations of the work
The anaerobic reactor in known processes is operated at a relatively high pH (8-
8.5), in particular when alkaline wastewater is treated having a pH of 9-12. As a
result, the stripping of H2S is slow, since H2S dissolves more easily in water at
higher pH. To compensate for this, equipment of a large volume has to be
employed, in particular the stripper column, which has to be operated with large
volumetric flows.
Moreover, the formation of carbonate salts due to the presence of CO2 in the
stripper equipment may give rise to fouling and clogging. The precipitation of
carbonate salts may be prevented by lowering the pH, however, this lowers the
rate of absorption and reaction of H2S, as a result of which larger absorbers and
volumetric flowrates are required.
This recirculation results in further disadvantages, since the anaerobic reactor is
operated at a higher hydraulic loading rate, which may lead to rinsing out of
methanogenic sludge from the reactor. Yet another disadvantage of known
processes is that the elemental sulfur that is formed does not accumulate
exclusively in the sulfur settling tank, but also forms deposits on walls of the
tubing, vessels, sprayers, blowers, pumps, packing material, etc., which causes the
need for regular cleaning of the equipment.[1]

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Any new/recent addition to the technology
(Process for reduction of sulfide from water and wastewater )
The instant application is directed towards methods for removing sulfide from a
wastewater stream. The pH of the wastewater stream is adjusted to between 7.0
and 8.0. A first oxidizing agent is mixed with the wastewater stream, oxidizing the
sulfide to elemental sulfur. The wastewater stream is then softened by mixing lime
with the wastewater stream. The addition of lime further raises the pH of the
wastewater stream to 10.0 or higher, and converts the elemental sulfur to soluble
sulfide (S2-) and/or thio-suflate. Calcium carbonate is precipitated and sulfide
(S2-) and/or thio-suflate is adsorbed thereon. Thereafter, the wastewater stream is
directed to a solids-liquid separation process, which separates the calcium
carbonate and adsorbed sulfide (S2-) and/or thio-sulfate from the wastewater
stream. The solids-liquid separator produces an effluent that includes residual
elemental sulfur. The effluent is then mixed with a second oxidizing agent, which
oxidizes the residual elemental sulfur to sulfate, producing a treated effluent.

A two-step oxidation process for removing sulfide from a wastewater stream is


provided. In the first step, an oxidation reagent is mixed with the wastewater
stream. At least some of the sulfide is oxidized to elemental sulfur. Thereafter, a
softening reagent is added to the wastewater stream. The softening agent increases
the pH of the wastewater stream. The increase in pH converts the elemental sulfur
to soluble sulfide (S2") and/or thio-sulfate, and causes hardness compounds to
precipitate. Soluble sulfide and/or thio- sulfate thereafter adsorbs onto the
hardness compound. After the first step, the wastewater stream is directed to a
solids-liquid separator. The solids-liquid separator removes the hardness
compound having the sulfide and/or thio-sulfate adsorbed thereon and producing
an effluent that includes residual elemental sulfur. In the second step, an oxidizing
reagent is mixed with the effluent from the solids-liquid separator, causing the
residual elemental sulfur to be converted to sulfate. After the second step, the
wastewater stream may be further treated or discharged. [4]

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UAE/GCC relevance (Application of the work to the
local/regional industry)
The presence of sulfur in the treated water will cause several problems such as,
corrosion and can damage the pipelines in plants and industries; moreover it has a
negative impact to the environment and human being. Sulfur removal in
petroleum refinery wastewater in different companies in UAE such as, Emirates
Refinery LLC, Abu Dhabi Oil Refining Company and ENOC Processing Company.
The removed sulfur can be used in manufacturing a lot of products like fertilizers
and other chemicals. Sulfuric acid is one of the sulfur products; it is used as one of
the most important intermediate in many processes. [5]

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Possible future work that could follow the report
(Water recovery from flue gas of furnaces and boilers in oil industrial
refineries)

Combustion of fossil fuels produces water, which is expelled as waste along with the
flue gas. Every fossil fuel power plant needs a massive amount of water to operate.
Some plants take in up to 50 million gallons of water each day. For some power
plants, it can be difficult to obtain enough cooling water for its processes. Other
plants are looking to limit their impact on the environment and the local marine life.
Yet power plants release a large amount of water vapor into the atmosphere through
the stack. The flue gas is a potential source for obtaining much needed cooling water
for the plant. Water is a natural product of combustion. Depending on the fuel being
burned, the flue gas can contain up to 20% moisture (by volume). If a power plant
can recover and reuse a significant portion of this moisture, it can lower its total
cooling water intake requirement. The most practical way to recover this water is to
use a condensing heat exchanger. In doing so, the plant can also recover lost heat. A
plant's overall thermal efficiency directly depends on how much heat it releases to the
atmosphere. In addition, harmful acids exist in the flue gas which are normally
released through the stack [6]. Some of these nitrogen and sulfur acids can conceivably
be condensed out along with the water.so our report will help in the removal of sulfur
compounds from the recoved water from flue gas.

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Conclusions

Water is the single largest waste stream in oil and gas production
worldwide. Wastewater streams come from a variety of sources, the largest of
which is associated or production water.
The process of the invention thus aims to provide an improvement to anaerobic
wastewater treatment with elemental sulfur recovery.
In accordance with the present invention, there is provided a process for removal
of sulfur compounds from wastewater, comprising the steps of: a) converting in a
first anaerobic suspended sludge reactor organic compounds present in the
wastewater to acid compounds, forming an effluent comprising the acid
compounds; b) converting the sulfur compounds to sulfide compounds in the first
reactor, the remainder of the sulfur compounds being also comprised by said
effluent; c) removing sulfide compounds in said first reactor with a stripping gas,
forming a gaseous effluent; d) converting the acid compounds in said effluent to
biogas in a second anaerobic reactor; and e) converting sulfur compounds in said
effluent to sulfide compounds in the second anaerobic reactor, forming a second
liquid effluent.
The organic compounds present in the wastewater are converted to acid
compounds, in particular organic (carboxylic) acids, such as (lower) fatty acids.
The conversion of organic compounds to acid compounds, as well as the
conversion of sulfur compounds to sulfide is established using microorganisms
known to the skilled person. For acidification of organic compounds bacterial
species.

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Formulation of mathematical model and its solution is
required for BS-MS students
Mathematical Model
Hydrodesulfurization of crude oil is one of the most attractive options in oil refinery.
The main stage of this process is the reaction of sulfur compound with hydrogen gas
which will be held in packed bed reactor. The catalyst is a major part of the reactor
and it consists of impregnation of Co and Mo on sol-gel B-Al2O3. [7]
For the selected reactor type, the following design parameters required to be
determined:
 Weight of the catalyst.
 Volume of the reactor
 Diameter and length of the reactor
The following are some general assumptions that will be used to create the
mathematical model:
 No radial concentration gradient
 Steady state operation
 One dimensional heterogeneous model
 Isothermal/isobaric reactor
Reaction Conditions:
The sulfur compound enters the reactor which is operating under temperature of
300 oC and pressure of 30 bar. The sulfur compound conversion is 90%. The system
is assumed to be an isobaric an isothermal and this will be achieved by adding
heating jacket. Also the pressure drop through the bed will be neglected since the
catalyst particles are relatively large.
Sample Calculations for the reactor:
Hydrodesulfurization reaction:

1. Design equation (PBR):

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𝑑
𝑑

2. Rate law:
( ) ( )
( )
In order to calculate the rate constant, Arrhenius equation will be used:

( )

( )

Where, A is Arrhenius pre-exponential factor, 𝑎 is the activation energy ( 𝐽/


𝑚𝑜𝑙𝑒), is the gas constant ( k𝐽 /k𝑚𝑜𝑙𝑒. ) and is temperature (K).
Table 2 : The required parameters to calculate the rate constant.
Parameter m n
Linear 0.4656 1.149 48010.02 1293.75

For the rate constant of Hydrodesulphurization reaction:


𝐽
𝑚𝑜𝑙𝑒 𝑎 𝑚 𝑚𝑜𝑙𝑒
( )
𝐽
𝑚𝑜𝑙𝑒

𝑚𝑜𝑙𝑒 𝑎 𝑚
( )
𝐽
𝑚𝑜𝑙𝑒

3. Stoichiometry: (Liquid phase – Isothermal)

( )

( )

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= 0.9
4. Parameter evaluation

𝑚𝑜𝑙

𝑚𝑜𝑙

5. Catalyst

The catalyst used for the HDS process in the work was the commercial cobalt-
molybdenum on alumina (Co-Mo/ ) type catalyst. the catalyst used was
extrudates with a cylindrical shape and an equivalent diameter of 1.8mm. the surface
area, pore volume of the catalyst, bulk density and mean particle length are 180 𝑚
,0.5 𝑐𝑚 ,0.67 𝑐𝑚 and 4mm, respectively.

Table 3: cobalt-molybdenum - Al2O3 catalyst


specifications
Parameter Value
Catalyst diameter 1.8mm
Catalyst density 0.67 𝑐𝑚

To find the volume of the reactor the equation was used:

Where,
V: the total volume of the of all tubes inside the reactor (m3)
w: Total weight of the catalyst (kg)
𝜌𝑏: bulk density (kg/m3)
The bulk density calculated from this equation:
𝜌𝑏 = 𝜌𝑐 (1 − )
Where:

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𝜌𝑐: catalyst density(kg/m3),
: void fraction

The volume of tube will be equal to:

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Results and discussions
1.1. Experimental Results

A series of experimental work for hydrodesulurization of crude oil were carried out
under the following operating condition:
 Temperature:335-400C
 (LHSV) Liquid hourly space velocity :0.5-1.5h-1
 Pressure: 4-10 MPa
 H2/oil ratio :250 L/L

The experimental results in tabular form are presented in Table (4). Figure(1) shows
the effect of reaction temperature on the sulfur content in products at different
pressure and liquid hourly space velocity. it has been observed that the sulfur content
in all products decreased with increasing in temperature and pressure and decreasing
in liquid hourly space velocity as shown in Figure (1).
The high removal of sulfur at high temperature are due to several reasons such as the
high effectiveness of thiophenic sulfur compounds found in the heavy cuts of crude
oil. Also , the increase in temperature raises the activation energy leading to increase
the number of particles of sulfur compounds interacted .this leads to cleavage of the
long -sulfur compounds and spread within the catalyst. Increased sulfur removals by
decreasing in LHSV are attributable to increased contact time (residence time)
between the molecules of reactants and catalyst, and provide sufficient time for
reaction process. The reason for increasing in sulfur removal by increasing in
hydrogen pressure is attributed to the contact between the hydrogen and hydrocarbon
and catalyst.

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Table (4): The experimental results in tabular form are presented
Experimental results
LHSV P(Mpa) T© sulfur wt% conversion%
0.5 4 335 0.67 66.5
1 4 335 1.11 44.5
1.5 4 335 1.36 32
0.5 4 400 0.229 88.5
1 4 400 0.64 68
1.5 4 400 0.93 53.5
0.5 10 335 0.43 78.5
1 10 335 0.9 55
1.5 10 335 1.2 40
0.5 10 400 0.082 95.9
1 10 400 0.376 81.2
1.5 10 400 0.64 68

Experimental data variation of outlet sulfur Vs LHSV at


different reactor T and P.
1.6
1.36
Sulfur concentration in products

1.4
1.11 1.2
1.2

1 0.9 0.93

0.8 0.67 0.64


0.64
0.6
0.43
0.376
0.4
0.229
0.2
0.082
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
LHSV (hr-1)

Figure1 : Experimental data variation of outlet sulfur Vs LHSV at different reactor T and P.

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Figure 2: Polymath for weight of Co-Mo/𝜸𝑨𝑰𝟐 𝑶𝟑 catalyst determination in FBR (without
pressure drop)

X Vs. W
1
0.9
0.8
conversion X%

0.7
0.6
0.5
0.4
0.3
0.2
0.1
0
0 10000000 20000000 30000000 40000000 50000000 60000000 70000000

Weight of the catalyst (g)

Figure 3: Obtained graph for weight of Co-Mo/γAI O catalyst determination in FBR (without
pressure drop).

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From Figure 3 the weight of cobalt-molybdenum on alumina catalyst in FBR at 90%
sulfur-compounds conversion is:

To find the volume of the reactor (Total volume of the tubes) based on the weight of
the catalyst equation was used, and the volume will be:

( )

Study the relation between conversion and CA (Ar-S) as conversion increase the CA
which is the concentration for reactant decrease.

Figure 4: Obtained graph for concentration Vs CA

Study the relation between conversion and CB (H2) as conversion increase the CB
which is the concentration for reactant decrease.

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Figure 5: Obtained graph for concentration Vs CB

Study the relation between conversion and Cc (H2S) as conversion decrease the Cc
which is the concentration for product increase.

Figure 6: Obtained graph for concentration Vs CC

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References
[1] PATENT US6709592 - REMOVAL OF SULFUR COMPOUNDS FROM
WASTEWATER

https://www.google.com/patents/US6709592 [Accessed 30 Nov. 2017].

[2] Removal of sulfur compounds from wastewater.


https://www.google.com/patents/US6709592 [Accessed 30 Nov. 2017].

[3] Janssen, A., Lettinga, G. and de Keizer, A. (2017). Removal of hydrogen sulphide from
wastewater and waste gases by biological conversion to elemental sulphur.

[4] Janssen, A., Lettinga, G. and de Keizer, A. (2017). Removal of hydrogen sulphide from
wastewater and waste gases by biological conversion to elemental sulphur.

[5] Google Books. (2017). Patent WO2017142899A1 - Process for reduction of sulfide from
water and wastewater. [online] Available at:
https://www.google.com/patents/WO2017142899A1?cl=enhttps://www.lenntech.com/periodic/
elements/s.htm [Accessed 30 Nov. 2017].

[6] Recovery of water from boiler flue gas, 2008 (Accessed 5 Sept. 2017)
http://preserve.lehigh.edu/cgi/viewcontent.cgi?article=1988&context=etd

[7] Umich.edu. (2017). Packed Bed Reactors (PBRs). [online] Available at:
http://www.umich.edu/~elements/fogler&gurmen/html/asyLearn/bits/pbr/index.htm
[Accessed 21 Nov. 2017].

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