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54545A
United States Patent (19) 11 Patent Number: 5,354,545
Buisman 45 Date of Patent: Oct. 11, 1994
(54 PROCESS FOR THE REMOVAL OF FOREIGN PATENT DOCUMENTS
SULPHUR COMPOUNDS FROM GASES
81347 5/1895 Fed. Rep. of Germany ...... 423/514
(75) Inventor: Cees J. N. Buisman, Harich, 2305630 9/1973 Fed. Rep. of Germany ... 423/576.4
Netherlands 2831209 2/1979 Fed. Rep. of Germany ...... 423/54
2328501 5/1977 France .
73) Assignee: Paques B.V., Harich, Netherlands 5348094 5/1978 Japan ................................... 423/232
25204 11/1914 Netherlands ........................ 423/514
21) Appl. No.: 70,336 880.009 11/1989 Netherlands .
711142 1/1980 U.S.S.R. ........................... 423/576.2
(22) PCT Filed: Dec. 4, 1991 Primary Examiner-Gary P. Straub
86) PCT No.: PCT/NL91/00250 Assistant Examiner-Timothy C. Vanoy
Attorney, Agent, or Firm-Young & Thompson
S371 Date: May 26, 1993 57 ABSTRACT
S 102(e) Date: May 26, 1993 A process for the removal of sulphur compounds from
87, PCT Pub. No.: WO92/10270 a gaseous effluent, comprising the steps of: a) contacting
the gaseous effluent with an aqueous solution wherein
PCT Pub. Date: Jun. 25, 1992 sulphur compounds are dissolved; b) adjusting the con
(30) Foreign Application Priority Data centration of buffering compounds such as carbonate
and/or bicarbonate and/or phosphate in the aqueous
Dec. 4, 1990 NL Netherlands ........................ 9002661 solution to a value between 20 and 2000 meq/l; c) sub
jecting the aqueous solution containing sulphide to sul
51) Int. Cl. .............................................. C01B 17/00 phide-oxidizing bacteria in the presence of oxygen in a
52 U.S. Cl. ................................. 423/242.1; 423/232; reactor wherein sulphide is oxidized to elemental sul
423/243.01; 423/576.2; 42.3/576.4; 423/DIG. phur; d) separating elemental sulphur from the aqueous
17; 210/601 solution; and e) recycling the aqueous solution to step
58) Field of Search ..................... 423/221, 232, 242.1, a). This process is suitable for removing H2S from bi
423/243.01, DIG. 17,576.2, 514; 23/293 S; ogas, ventilation air etc. It can be used for removing
42.5/576.4 SO2 from combustion gases by introducing the addi
56) References Cited tional step, after step a) and before step c), of subjecting
the aqueous solution containing the sulphur compounds
U.S. PATENT DOCUMENTS to a reduction of the sulphur compounds to sulphide.
2,138,214 7/1935 Shiffler ............................. 423/576.4 H2S and SO2 removal is further enhanced by a residual
3,839,549 10/1974 Deschamps et al. ............... 423/514 sulphur content in the washing liquid of 1-50 g/l.
4,242,448 12/1980 Brown, III ............................ 435/42
4,579,727 4/1986 Cronkright et al............. 423/573 R 7 Claims, 1 Drawing Sheet
U.S. Patent Oct. 11, 1994 5,354,545
 1.
5,354,545
2
which is typically below 5.8. The dissolved SO2 is usu
PROCESS FOR THE REMOVAL OF SULPHUR ally oxidised and separated as calcium sulphate (gyp
COMPOUNDS FROM GASES sum).
The invention relates to a process for the removal of 5 SUMMARY OF THE INVENTION
sulphur compounds from a gas flow, in particular from The invention provides an integrated process for the
biogas, wherein the gas is washed with an aqueous removal of sulphur compounds, such as H2S and SO2,
washing liquid and the spent washing liquid is treated from gaseous effluents, wherein chemical scrubbing and
with oxygen and is subsequently reused as a washing biological oxidation are combined. The process results
liquid. 10 in an effective purification without the need to continu
BACKGROUND OF THE INVENTION ously add alkali or other chemicals to the washing liq
uid or to add oxygen to the gas flow and without danger
The presence of sulphur compounds in gas flows is of explosion.
undesirable, because of their toxicity and their smell. The process of the invention is characterized by car
Hydrogen sulphide (H2S) is a harmful compound that is 15 rying out the steps of:
frequently present in gas flows, especially in biogas a) contacting the gaseous effluent with an aqueous
originating from anaerobic waste treatment. Sulphur solution wherein sulphur compounds are dissolved;
dioxide is another noxious sulphur compound that is b) adjusting the concentration of buffering com
present in gas flows resulting from the combustion of pounds such as carbonate and/or bicarbonate and
fossil fuels. Other harmful sulphur compounds that may 20 /or phosphate in the aqueous solution to a value
be present in gas flows include sulphur trioxide, carbon between 20 and 2000 meq/1;
disulfide, lower alkyl mercaptains etc. Gaseous effluents c) subjecting the aqueous solution containing sul
containing these sulphur compounds must therefore be phide to sulphide-oxidizing bacteria in the presence
purified, before they can be discharged into the atmo of oxygen in a reactor wherein sulphide is oxidized
sphere. 25 to elemental sulphur and hydroxide;
A process for removal of H2S from a gas flow by d) separating elemental sulphur form the aqueous
scrubbing with a washing liquid and subsequently oxi solution; and
dising the absorbed sulphide is known from European e) recycling the aqueous solution to step a).
patent application 229,587. According to that process, When the gaseous effluent contains appreciable levels
sulphide absorbed in the washing liquid is oxidized 30 of oxidized sulphur compounds, in particular sulphur
non-biologically, in the presence of a catalyst, to prod dioxide, the process comprises, after or before step b),
ucts including elemental sulphur which is separated the additional step of subjecting the aqueous solution
from the system. However, loss of catalyst occurs in containing the sulphur compounds to a reduction of the
such a process, which is an environmental drawback sulphur compounds to sulphide.
and which increases costs. The known process is also 35 DESCRIPTION OF THE INVENTION
relatively expensive because oxidation takes place using
pressure. The first step of the process according to the inven
A process frequently used is washing biogas with an tion consists in contacting the gaseous effluent with an
aqueous liquid having an increased pH, typically a pH aqueous washing liquid. This step can be perfomed in a
of about 11. This increased pH may be adjusted by the gas scrubber which ensures an effective contact be
addition of sodium hydroxide or other alkalis. Such tween the gas flow and the washing liquid.
processes are known for example from European patent An important feature of the present process is that the
application 229,587. A drawback of scrubbers of this washing liquid is buffered, preferably at a pH between
type is their high consumption of chemicals, resulting in 6.0 and 9.0, depending on the nature of the gas flow to
relatively high operational costs. The price of sodium 45 be treated and especially on the nature of the sulphur
hydroxide has been increasing strongly recently as a compounds to be removed. The buffering compounds
result of a reduced production of chlorine. For many must be tolerated by the bacteria present in the oxida
industries, savings in sodium hydroxide will therefore tion reactor. Preferred buffering compounds are car
become important. Another disadvantage of this pro bonates, bicarbonates, phosphates and mixtures thereof,
cess is that it results in aqueous effluent contaminated 50 especially sodium carbonate and/or sodium bicarbon
with sulphide. According to NL-A-8801009 spent ate. The concentration of the buffering compounds
washing liquid from H2S removal from gases can be depends on the nature of the gas flow, and is generally
regenerated by subjecting it to sulphur-oxidizing bac adjusted to a value within the range of 20 to 2000 meg/l.
teria in the presence of oxygen. When sodium carbonate is the buffering compound, its
Another method consists in mixing the biogas with 55 concentration is preferably adjusted to about 1 to 70 g/l.
air or oxygen then conveying it into an oxidation reac Where in this specification reference is made to bicar
tor, wherein the sulphide is converted to sulphur, as is bonate and carbonate concentrations, these are ex
known from European patent application 224,889. A pressed as the concentration by weight of HCO3 and
drawback of this method is that the reactor becomes CO3 - ions respectively.
rather expensive, because the mixture of biogas and 60 Addition of buffering compounds can be done after
oxygen is explosive, requiring safety precautions. The the washing liquid has left the gas scrubber, but also
reactor should also be rather large because the conver before it is fed into the scrubber. In case of carbonate/-
sion rate is strongly reduced by the low concentration bicarbonate, the buffering compound can advanta
of oxygen which is allowed in connection with the gas geously be added in the form of carbon dioxide, for
effluent requirements (explosion standards). 65 example in the gas scrubbing step, when the gaseous
Known processes for the removal of sulphur dioxide effluent contains high levels of carbon dioxide.
from gaseous effluents involve washing the gas flow Known autotrophic aerobic cultures, such as cultures
with an acidic aqueous washing liquid having a pH of the genera Thiobacillus and Thiomicrospira, can be
 5,354,545
3 4.
used as bacteria oxidizing sulphide to elemental sulphur CO2 which is present in the (bio)gas will also partially
(herein referred to as sulphide-oxidising bacteria) in the be absorbed in the washing liquid. As a result of the
treatment of spent washing liquid in the presence of recycling of the washing liquid a carbon dioxide equi
oxygen in step c). librium will be established according to the following
The amount of oxygen fed into the washing liquid in reactions:
the oxidation reactor is adjusted in such a way that the
oxidation of the absorbed sulphide predominantly leads
to the production of elemental sulphur. Such a process
for the controlled oxidation of sulphur-containing waste The concentration of the dissolved carbonates pro
water is described in Netherlands patent application 10
880 1009. duced depends of course on the CO2 concentration in
The production of sulphur in the oxidation reactor the gas to be purified. The carbonate concentration is
will result in a sulphur slurry which is drawn off. The about 4-70 g/1, when the CO2 concentration in the gas
sulphur from this slurry is separated and processed by is between 10 and 20%. The process is found to operate
drying and optionally pruifying, and utilized. 15 particularly effectively at such concentrations. A car
It has been found to be advantageous when not all bonate concentration of more than 70 g/l is not suitable,
sulphur is drawn off, and thus the separation is carried since it will adversely affect the activity of the bacteria
in the oxidation reactor.
preferably out discontinuously or partially, resulting in In a conventional scrubber absorbing H2S and CO2 at
a washing liquid still containing sulphur. The sulphur high pH, the level of CO2 absorption is much higher
concentration in the washing liquid is generally kept than in a scrubber as operated according to the present
between 0.1 and 50 g/l, preferably between 1 and 50, invention. The total amount of CO2 absorbed depends
and more preferably between 10 and 50 g/l (1-5% by on the CO2 content of the gas flow, the pH of the scrub
weight). In particular, the sulphur separation rate is bing liquid and the gas flow conducted through the
adjusted such that the washing liquid is recycled to the 25 scrubber. In a conventionally operated scrubber the
largest extent possible. The liquid recovered after pro CO2 saturation value (i.e. the HCO3 and CO3 con
cessing of the separated sulphur can be returned to the
washing liquid. centration) is not reached, because of the high pH and
The advantages of the present process are: the short contact time between gas and washing liquid.
In the present process however, the carbonate and bi
1. there is hardly any need for chemicals (sodium 30 carbonate concentrations of the washing liquid will be
hydroxide); equal to or close to the saturation level, because of the
2. no catalyst is needed; relatively low pH (and thus the relatively low satura
3. the required equipment is simple; tion value, which is about 3-5 g/1 for HCO3- and about
4. energy consumption is low; 0.1-0.3 g/1 for CO3- at pH 8.5) and low gas/liquid
5. no CO2 is absorbed (after equilibrium has been 35 flow ratio, and because the system is cyclic.
established); After an equilibrium has thus been established, the
6. no waste effluent results, the sulphur may be sold. washing liquid will no longer absorb CO2 and no more
Experiments have shown that the high (bi)carbonate or very little alkali will be needed for neutralizing the
concentrations do not negatively affect the bacterial CO2. The CO2 which is stripped in the oxidation step
activity. can be replenished in the absorption step.
REMOVAL OF HYDROGEN SULPHIDE When the CO2 content in the gas is lower, CO2 or
(bi)carbonate may be added, preferably to a level of
When H2S or other reduced volatile sulphur com 100-1500, more preferably 200-1200, and most prefera
pounds such as lower alkyl mercaptains or carbon disul bly between 400 and 1200 meq/1.
phide, have to be removed, e.g. from biogas, the spent 45 As to sulphide oxidation:
washing liquid containing the sulphur compounds can As a result of the oxidation of sulphide with oxygen
be directly fed into the reactor containing the sulphide the concentration of sulphide in the washing liquid will
oxidising bacteria. These reduced sulphur compounds, not increase. The sulphur content in the liquid will
when dissolved, are referred to herein as “sulphide', increase instead, according to the following reactions,
but this term will be understood to include other re 50 which illustrate why the pH of the washing liquid does
duced sulphur species such as dissolved hydrogen sul not decrease.
phide (H2S or HS), disulphide, polysulphides, thiocar
bonates, alkanethiolates, etc.
The pH in the system is preferably kept at about 8-9,
particularly at about 8.5. When the pH is lower, the H2S 55
scrubbing efficiency is insufficient, whereas a higher pH
inhibits the activity of most of the bacteria. At the start
of the process according to the invention, an alkaline
washing liquid will be used, or alkali will be added in
the initial stage of the process. It was found surprisingly The sulphide concentration in the spent washing
that, after an initial period, no alkali needs to be added liquid having a pH of about 8.5 will normally be about
any more, in particular when the gas flow also contains 80-100 mg/l, expressed as sulphur. This is a lower con
carbon dioxide such as in biogas. centration than the concentration that is obtained in a
The composition of the washing liquid is determined conventional H2S scrubber operating at a pH of 10 to
by: 65
1. the pH 11. Therefore, the scrubber will have to be larger than
2. the oxidation of sulphide a conventional scrubber and a higher water/gas flow
As to the pH: ratio will be used, for example a water flow to gas flow
ratio of 0.1 to 0.2.
 5
5,354,545
6
It was found that a sulphur concentration of 0.1-50 between 0.1 and 50 g/1, preferably between 1 and 50,
g/l, in particular 1-50 g/l in the washing liquid im and most preferably between 10 and 50 g/l.
proves the removal of H2S from the biogas, while at the
same time an effective sulphur separation is ensured. DESCRIPTION OF THE FIGURES
The improved H2S removal results from polysulphide The process for removing H2S and other reduced
production according to the reaction: sulphur compounds such as lower alkyl mercaptans is
HS--Sn->HS(n+1) which causes the absorption illustrated with reference to FIG. 1. Biogas contami
equilibrium to shift towards increased absorption. At a nated with H2S (1) enters the scrubber (2) at the bottom
sulphide concentration of 90 mg/l in the spent washing and is treated with washing liquid (9). Purified gas (3)
liquid, at least half of the sulphide will be bound as O leaves the reactor at the top. The washing liquid (10)
polysulphide. which is now contaminated with sulphide leaves the
The present process has the advantage that neutraliz reactor at the bottom and is fed into the oxidation reac
ing agents are not necessary to lower the pH after the tor (5), where sulphide is converted to sulphur by the
scrubber, and therefore no salts are built up in the recir 15 bacteria present therein and oxygen. The reactor is
culating washing liquid. supplied with oxygen by an aeration device (4). Spent
REMOVAL OF SULPHUR DOXDE air (6) will have to be treated in a compost filter (7)
because of its stench. The treated air (8) can be dis
When the gaseous effluent contains appreciable levels charged without problems. The production of sulphur
of sulphur compounds having higher oxidation states, 20 will result in a sulphur slurry (11) which is partially
particularly sulphur dioxide, but also sulphur trioxide or drawn off. The sulphur (12) from this slurry can be
other oxidised sulphur compounds, an additional pro dried and utilised. The separated aqueous solution (13)
cess step is required to reduce the sulphur compounds is recycled as much as possible in order to save nutrients
to sulphide. and alkalinity. If necessary, alkali may be added to flow
These sulphur compounds having higher oxidation 25 (9).
states, when dissolved, are referred to herein as "sul The process for removing SO2 and other oxidised
phite', but this term will be understood to include other sulphur compounds is illustrated with reference to FIG.
oxidised species such as dissolved sulphur dioxide, hy 2.
drogen sulphite (bisulphite), sulphate, thiosulphate, etc. The combustion gas containing SO2 (14) enters the
Reduction of sulphite to sulphide can be performed 30 scrubber (2) in a similar way. The washing liquid (15)
by chemical means, but preferably a biological reduc containing sulphite is fed into the reduction reactor (16)
tion is carried out using an anaerobic reactor. Suitable wherein sulphite is converted to sulphide by anaerobic
bacteria for use in the anaerobic reactor to reduce sul bacteria. A part of the spent washing liquid may be
phite to sulphide include bacteria reducing sulphur directly returned to the washing liquid (9) by a short
compounds (herein referred to as sulphur-reducing bac 35 cut (17). The reduced washing liquid (18) is then treated
teria) such as species of the genera Desulfovibrio, in the oxidation reactor (5) as in the process of FIG. 1.
Desulfotomaculum, Desulfomonas, Desulfobulbus, An electron donor, e.g. alcohol, is added through (19).
Desulfobacter, Desulfococcus, Desulfonema, Desul Fresh carbonate solution may be added through (19) or
fosarcina, Desulfobacterium and Desulformas. In gen elsewhere in the cycle.
eral, these bacteria are available from various anaerobic Any gaseous effluent that can be treated with an
cultures and/or grow spontaneously in the anaerobic alkali scrubber can also be purified with the process
reactors. described herein, provided that the temperature is not
The pH of the washing liquid is preferably main too high for the biological activity. The process accord
tained at a level of about 6 to 7. This is higher than in ing to the invention is therefore not restricted to biogas.
conventional SO2 scrubbers in processes wherein the 45 It can also be used for treating combustion gases and
sulphur dioxide is fixed as gypsum, which typically use ventilation air; in the latter case a phosphate buffer
a pH below 5.8. This increased pH results in a more having a concentration of about 50 g/l is preferred.
efficient SO2 scrubbing. The pH may be adjusted by the EXAMPLE
addition of buffering agents. Preferably, carbonate or
bicarbonate is added to a level of 20-100 meq/1, for 50 An operating example for H2s removal is presented in
example about 30 meq/1. Table A; numbers in the table correspond with the
The washing liquid may be conducted through the numbers in the accompanying FIG. 1.
scrubber several times before being regenerated. In The oxidation reactor (5) is a "fixed-film' reactor or
such a process, the (bi)carbonate concentration of the a "trickling filter' and contains about 6 m3 of carrier
washing liquid is preferably higher, e.g. 50-200 meq/l. 55 material having a surface area of 200 m2/m3. The di
When SO2 is removed from gaseous effluents, the mensions of the scrubber (2) are (diameter)xheight)
presence of sulphur in the washing liquid was also 0.5X2.5 m. The reactor is filled with Bionet 200 rings
found to be advantageous. Reaction of sulphur with (NSW company).
SO2 (or with HSO3) results in thiosulphate formation. TABLE A
In the absence of sulphur, SO2 may be further oxidized 60 flow
to sulphate by the oxygen which is often present in
combustion gases as well. As sulphate requires more 1.
concentration H2S
concentration CH4
0.8-1.0%
79%
reduction equivalents (electron donor) than thiosul l concentration CO2 20%
phate does, less electron donor (such as alcohol) is re 1 flow rate 200 m/h
quired in the reduction reactor as a result of the pres 65 3 concentration H2S 150 ppm
ence of sulphur in the washing liquid. In addition, the 3
3
concentration CH4
concentration CO2
79%
20%
absorption capacity of the washing liquid is increased 10 flow rate 200 m3/h
by the conversion to thiosulphate. The sulphur level is 10 sulphide concentration 89 mg/1
 5,354,545
8
TABLE A-continued ence of oxygen in a reactor wherein sulphide is
flow oxidized to elemental sulphur;
10 bicarbonate concentration 7 g/1 d) separating elemental sulphur from the aqueous
10 sulphur concentration 3% Solution, so that the aqueous solution contains
10
10
pH
flow rate
8.2
30 m3/h
0.1-50 g of elemental sulphur per 1; and
9 sulphide concentration <5 mg/ d) recycling the aqueous solution to step a).
9 sulphur concentration ca. 3% 2. Process of claim 1, wherein the concentration of
9
9
pH
flow rate
8.4
30 m3/h
buffering compounds in step b) is adjusted to a value
10 between 100 and 1500 meq/1.
3. Process of claim 2, wherein in step b) the buffering
I claim: compounds comprise carbonate and/or bicarbonate the
1. Process for the removal of sulphur compounds concentration of which is adjusted to a value between
selected from hydrogen sulfide, alkyl mercaptans and 200 and 1200 meq/1.
carbon disulfide from a gaseous effluent, comprising the 15 4. Process according to claim 1, wherein the pH of
steps of: the aqueous solution is adjusted to between 8 and 9.
a) contacting the gaseous effluent with an aqueous 5. Process according to claim 1, wherein in step a) the
solution wherein sulphur compounds are dissolved; gaseous effluent contains carbon dioxide.
b) adjusting the concentration of buffering com
pounds selected from carbonate, bicarbonate and 20 6. Process according to claim 1, wherein after step d)
phosphate in the aqueous solution to a value be the aqueous solution contains 1-50 g of elemental sul
tween 20 and 2000 meq/1 and maintaining the pH phur per 1.
of the aqueous solution to between 6 and 9 7. Process according to claim 6, wherein in step e) the
throughout the process; aqueous solution contains 10-50 g of elemental sulphur
c) subjecting the aqueous solution containing sul 25 per 1.
phides to sulphide-oxidizing bacteria in the pres c e s :

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