CN102452643A - Technology for reacting hydrogen sulfide with oxygen to generate elemental sulfur by accelerated catalysis - Google Patents
Technology for reacting hydrogen sulfide with oxygen to generate elemental sulfur by accelerated catalysis Download PDFInfo
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- CN102452643A CN102452643A CN2010105133425A CN201010513342A CN102452643A CN 102452643 A CN102452643 A CN 102452643A CN 2010105133425 A CN2010105133425 A CN 2010105133425A CN 201010513342 A CN201010513342 A CN 201010513342A CN 102452643 A CN102452643 A CN 102452643A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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Abstract
The invention relates to a technology for reacting hydrogen sulfide with oxygen to generate elemental sulfur by accelerated catalysis. The technical system consists of a bioreactor and a chemical reactor which are connected in series with each other, wherein a reaction liquid phase system is circulated between the two reactors; and H2S gas to be reacted and air pass through the chemical reactor and the bioreactor from bottom to top, and the process of reacting the hydrogen sulfide with the oxygen to generate the sulfur is accelerated under the mild action of a catalysis system consisting of microorganisms and Fe<3+>. The technology can be widely applied to chemical reaction and analysis, desulfurization treatment of the hydrogen-sulfide-containing gas, and the like.
Description
Technical field
The present invention relates to a kind of technology of quickening catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur.Specifically a kind of is the acceleration catalysis hydrogen sulfide of catalyzer and the technology that the oxygen reaction generates elemental sulfur with the acidophilia iron-oxidizing bacterium, belongs to the gas purification technique field.
Background technology
Hydrogen sulfide (hydrogen sulfide) is to have pungency and asphyxiant colourless hypertoxic gas, and the reaction of hydrogen sulfide and oxygen produces this process of elemental sulfur and in industrial production, has important value, that is:
H
2S?+?O
2=?S↓+?H
2O ①
Utilize the effectively hydrogen sulfide contamination in the Purge gas of this reaction, simultaneously also can production high purity sulphur, however under normal condition, this speed of reaction is very slow, can't satisfy the needs of actual industrial.
In order to quicken this reactions step, what generally adopt at present is the claus reaction technology, and its know-why is following:
H
2S?+?O
2=?SO
2+?H
2O ②
SO
2+?2H
2S?=?3S↓+?2H
2O ③
Be that hydrogen sulfide earlier generates sulfurous gas with oxygen combustion, sulfurous gas that generates then and hydrogen sulfide under the effect of 120-150 ℃ hot conditions and catalyzer, the generation elemental sulfur.Yet this operation condition is harsh, and catalyzer costs an arm and a leg, and equipment is had bigger corrosion, and complex disposal process, and investment of devices volume and working cost are high.Although a large amount of scholars has carried out a lot of research (200810047108.0 1 kinds of reactive systems that the Claus tail-gas hydrogenation desulfurization catalyst is estimated fast to claus reaction and catalyzer; 200810022175.7 the technology of inside and outside water-cooled Claus tail gases recovery sulier and qualified discharge; 200710049014.2 improvement low-temperature Claus sulfur recovery method; 200710052787.6 nickel base crouse vent gas hydrogenation catalysts and co-precipitation preparation method thereof; 200710052788.0 nickel base crouse vent gas hydrogenation catalysts and preparation method thereof; 200710111295.X the catalyst for clause recovering sulfur of an acid gas-containing and preparation method), however its high cost, high energy consumption, operational condition harshness etc. are the bottlenecks of claus reaction always.
Summary of the invention
In order to overcome the technological deficiency of existing claus reaction, the present invention provides a kind of new acceleration catalysis hydrogen sulfide and the technology of oxygen reaction generation elemental sulfur.This technology adopts immobilized iron protoxide hook end spirobacteria (Leptospirillum ferrooxidans), thiobacillus ferrooxidant acidophilia iron-oxidizing bacteriums such as (Acidithiobacillus ferroxidans) as biological catalyst, and these acidophilia iron-oxidizing bacteriums can be with the Fe in the sour environment
2+Change Fe into
3+, the energy of its growth is kept in acquisition.The iron ion of two kinds of valence states can be used as reaction intermediary, and accelerated cure hydrogen and oxygen reaction produce sulphur, and its reaction mechanism is following:
2FeSO
4+ 1/2O
2+ H
2SO
4→ Fe
2(SO
4)
3+ H
2O is (catalysis of acidophilia iron-oxidizing bacterium) 4.
H
2S+Fe
2(SO
4)
3→Fe
2(SO
4)
3+H
2SO
4+S↓ ⑤
Total reaction, that is:
H
2S?+?O
2=?S↓+?H
2O ①
4. and 5. can find out from equation, in entire reaction course, introduce Fe
3+As catalyzer, quicken the reaction of catalysis hydrogen sulfide and generate elemental sulfur, mikrobe makes catalyst Fe again rapidly in reaction process
3+Be able to regeneration,, greatly quickened the speed of reaction that the reaction of hydrogen sulfide and oxygen produces elemental sulfur-sulphur through such reaction mechanism.In order to realize this reaction mechanism better; The technology that the present invention has set up a kind of new acceleration catalysis hydrogen sulfide and reaction generates elemental sulfur with oxygen, specifically a kind of with biological-chemical two-stage reactor technology is basis, the acidophilia iron-oxidizing bacterium is catalyzer the acceleration catalysis hydrogen sulfide and the technology (seeing Figure of description 1) of oxygen reaction generation elemental sulfur.The biological-chemical two-stage reactor is composed in series by biological respinse and chemical reaction two-stage reactor, fills immobilized acidophilia iron-oxidizing bacterium particle in the bio-reactor, and two-stage reactor internal recycle liquid phase is made up of inoculum, its staple Fe
2+Be the energy derive of bacterium, in bio-reactor, carry out equation reaction 4., the Fe that reaction generates
3+Flow into reaction apparatus, at reaction apparatus Fe
3+And H
2S carries out equation reaction 5. and generates elemental sulfur-sulphur, Fe
3+Be transformed into Fe
2+, circulation fluid is behind bio-reactor, and the catalyzer in the solution is able to regeneration, i.e. Fe
2+Change Fe into
3+, flowing into reaction apparatus again, thereby realized under mild conditions, accelerated cure hydrogen and oxygen reaction produce the reaction process of elemental sulfur.The acidophilia iron-oxidizing bacterium that adopts can be the acidophilic microorganism that thiobacillus ferrooxidant, iron protoxide hook end spirobacteria etc. can red stone.Microorganism immobilization method can be methods such as known carrier absorption method, covalent attachment method, entrapping method.The activation culture method of immobilized cell is for to be linked into immobilized cell particle in the triangular flask that the 9k liquid nutrient medium is housed, the volume ratio 3:1 of immobilized cell particle and nutrient solution ~ 6:1, and 25-35 ℃ of shaking table cultivated, and treats Fe wherein
2+After number turnover reaches 80%, immobilized cell is linked in the new substratum, after repetitive operation 2-3 time, immobilized cell has just reached vigor preferably.
The invention has the beneficial effects as follows, at acidophilia iron-oxidizing bacterium and Fe
3+Under the catalysis system of forming, hydrogen sulfide and oxygen can be in successive reactions under the mild conditions, and catalysis system can move continuously; Compare with claus reaction; Greatly reduced energy consumption, working cost is low, and the elemental sulfur purity of generation is high; Reduce the investment of devices volume, avoided the secondary pollution that possibly cause.
Figure of description
Figure of description 1 is a technical matters schema of the present invention.Device main body is to be composed in series by bio-reactor and reaction apparatus two-stage reactor, built-in porous barrier of bio-reactor or employing internal recycle liquid bed.Reaction apparatus adopts the internal recycle liquid bed, and the waste gas shower nozzle adopts porous nozzle, about hole count >=20; Bore dia 0.02-1mm, for fear of the transition evaporation of inside reactor liquid, two kinds of gases all pass through the humidifier system before getting into reactor drum; A certain amount of water of the inner loading of humidifier; Bio-reactor is linked to each other by pipeline with reaction apparatus, and pipeline enclosure has acid proof recycle pump and valve, to control the circulation of liquid between two reactor drums.
Embodiment
Embodiment one
The agent set of technology is composed in series by bio-reactor and reaction apparatus two-stage reactor; Like Figure of description 1; What fill (voidage 30%) in the bio-reactor is immobilization thiobacillus ferrooxidant (Acidithiobacillus ferroxidans) particle after the activated cultivation; For preventing that particulate from overstocking built-in porous barrier of bio-reactor or employing internal recycle liquid bed.Reaction apparatus adopts the internal recycle liquid bed, and the waste gas shower nozzle adopts acidproof special teflon (tetrafluoroethylene) porous nozzle, hole count=20, and bore dia 0.02-1mm to reduce the diameter of waste gas bubble, increases vapour-liquid ratio.Simultaneously, for the evaporation of the circulation fluid that prevents to cause because of the gas that feeds, the gas that the biological and chemical two-stage reactor feeds is handled through humidification respectively.Two-stage reactor internal recycle liquid phase is made up of the 9K nutrient solution of bacterial growth, regulates initial pH1.0, and is the flow rate of liquid circulation of 0.1/h with the thinning ratio, and the Fe of 1g/L is arranged in the dichromate titration tracer liquid
2+, circulation fluid behind bio-reactor, the Fe in the solution
2+Change Fe into
3+, and flow into reaction apparatus and H
2The S reaction, Fe in reaction apparatus
3+Change Fe again into
2+, through equalizing tank to precipitate and separate after, flow into bio-reactor again, so that the energy of immobilized microorganism growth to be provided.Through follow the tracks of detecting the variation of various ionic concns in the equalizing tank, and according to the needs of immobilized microorganism, adjustment keeps the stability of nutrient concentrations in the bio-reactor.In entire reaction course, temperature remains on 25-35 ℃ in the bio-reactor.The reaction apparatus normal-temperature operation, bio-reactor air flow 20kgO
2/ m
3D, the hydrogen sulfide under above condition in the biogas of operate continuously and oxygen reaction can reach 16.2 kg/m
3D (with the bio-reactor volume calculation), reaction efficiency is more than 99%.
Embodiment two
Use the hydrogen sulfide in this technical finesse rubber industry tail gas; Used technique device such as Figure of description 1; Fill immobilization iron protoxide hook end spirobacteria (Leptospirillum ferrooxidans), thiobacillus ferrooxidant particle and the mixture of the two (1:1) after (voidage 30%) activated cultivation in the bio-reactor respectively, the fixed form of these bacterium all adopts entrapping method (referring to Chinese patent 2005102004915), and reaction apparatus adopts the internal recycle liquid bed; The waste gas shower nozzle adopts acidproof special teflon (tetrafluoroethylene) porous nozzle; Hole count=20, bore dia 0.02-1mm regulates initial pH1.8; And be the flow rate of liquid circulation of 1/h with the thinning ratio, Fe in the dichromate titration detection system
2+Concentration 15g/L, bio-reactor air flow 20kgO
2/ m
3D, hydraulic detention time (bio-reactor) 1.0h detects hydrogen sulfide tail gas content with the hydrogen sulfide detector tube, operate continuously under above condition, reaction efficiency is more than 99%.Hydrogen sulfide and oxygen reaction generate the experimental result such as the table 1 of elemental sulfur.
Table 1. hydrogen sulfide and oxygen reaction generate the experimental result of elemental sulfur
| Bacterial classification | Catalysis system temperature ℃ | Sulphur generation (with the bio-reactor volume calculation) |
| Iron protoxide hook end spirobacteria | 37.5 | 10.5 kg/m 3d |
| Thiobacillus ferrooxidant | 30 | 28.5kg/m 3d |
| Mixture | 32 | 15 kg/m 3d |
Embodiment three
Height overall 60cm bio-reactor and reaction apparatus two-stage reactor respectively is composed in series and quickens catalysis hydrogen sulfide reaction generates the system of elemental sulfur, employing free or immobilized thiobacillus ferrooxidant and Fe with oxygen
3+The liquid-phase catalysis system that forms; Hydrogen sulfide and oxygen mainly react under the inner normal temperature of reaction apparatus; Load thiobacillus ferrooxidant in the bio-reactor, internal temperature remains on about 31 ℃, regulates initial pH2.5; And be the flow rate of liquid circulation of 2/h with the thinning ratio, the Fe of 30g/L is arranged in the dichromate titration tracer liquid
2+, mikrobe is regenerated catalyst Fe rapidly
3+, the vigor of bacterium can be judged Fe in the dichromate titration detection system through analyzing its rate of oxidation to ferrous ion
2+The variation of concentration, reaction apparatus and bio-reactor be through pipe connection, and through realization response catalytic liquid phase systems such as recycle pumps between the two circulation.The H of question response
2S gas is from bottom to top through reaction apparatus, and reaction therein, and the air in the bio-reactor after the feeding degerming contains Fe
3+Reaction solution in total system, circulate.The top of the reaction solution that is overflowed by bio-reactor top through reaction apparatus flows into the H that contains of the inner and countercurrent flow of reaction apparatus
2The S gas reaction is flowed out by the reaction apparatus bottom afterwards.Can produce sulphur 28.5kg/m
3D.
Claims (9)
1. one kind is quickened the technology that the reaction of catalysis hydrogen sulfide and oxygen generates elemental sulfur; It is characterized in that; This technological system is composed in series by bio-reactor and reaction apparatus two-stage reactor; Hydrogen sulfide and oxygen react in reaction apparatus inside, and reaction apparatus and bio-reactor are through pipe connection, and the catalytic reaction liquid-phase system is in circulation between the two.
2. a kind of technology of quickening catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur according to claim 1 is characterized by this technical matters and adopts mikrobe and Fe
3+The catalysis system of forming, thus realized under mild conditions, quickened the reaction process that the reaction of hydrogen sulfide and oxygen produces sulphur.
3. a kind of technology of quickening catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur according to claim 1, it is characterized by the catalyzer that quickens catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur is Fe
3+
4. a kind of technology of quickening catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur according to claim 1; The action of microorganisms that it is characterized by in the catalysis system is rapid regenerated catalyst, and employed mikrobe can be that thiobacillus ferrooxidant, iron protoxide hook end spirobacteria etc. can make catalyst Fe
2+Change Fe into
3+Mikrobe or microbial population.
5. according to any described a kind of technology of quickening catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur in the claim 1 to 3, it is characterized by the initial pH1.0-2.5 of reaction solution, the content of catalyzer is 1-30g/L.
6. according to any described a kind of technology of quickening catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur in the claim 1 to 3, it is characterized by the H of question response
2S gas is from bottom to top through reaction apparatus, and reaction therein, and the air in the bio-reactor after the feeding degerming contains Fe
3+Reaction solution in total system, circulate.
7. according to any described a kind of technology of quickening catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur in the claim 1 and 4, it is characterized by used mikrobe can be free, also can be immobilized.
8. according to any described a kind of technology of quickening catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur in the claim 1 and 6, it is characterized by reaction solution and in total system, circulate, the thinning ratio of bio-reactor is controlled at 0.1-2.0/h.
9. according to any described a kind of technology of quickening catalysis hydrogen sulfide and oxygen reaction generation elemental sulfur in the claim 1,6 and 7, its characteristic is at the H that contains that flows into reaction apparatus inside and countercurrent flow for the reaction solution that is overflowed by bio-reactor top through the top of reaction apparatus
2The S gas reaction is flowed out by the reaction apparatus bottom afterwards.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254957A (en) * | 2013-05-06 | 2013-08-21 | 陕西科技大学 | Device and method for removing hydrogen sulfide out of methane by utilizing collagenous fiber/polyester composite material to load Fe(III) |
| CN106268291A (en) * | 2016-11-03 | 2017-01-04 | 南京工业大学 | Filter tower device and the method for biological desulphurization deodorization are dripped in a kind of biological desulphurization deodorization |
| CN111330425A (en) * | 2020-03-11 | 2020-06-26 | 唐山绿源环保科技有限公司 | Biological desulfurization system of desorption high concentration hydrogen sulfide |
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| CN1895747A (en) * | 2006-06-23 | 2007-01-17 | 兰州大学 | Hydrogen sulfide treatment of biological and chemical two-stage reactor |
| EP1572325B1 (en) * | 2002-12-20 | 2007-08-22 | ENI S.p.A. | Chemical-biological process for the removal of h2s from a gas |
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2010
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| EP1572325B1 (en) * | 2002-12-20 | 2007-08-22 | ENI S.p.A. | Chemical-biological process for the removal of h2s from a gas |
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Non-Patent Citations (1)
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103254957A (en) * | 2013-05-06 | 2013-08-21 | 陕西科技大学 | Device and method for removing hydrogen sulfide out of methane by utilizing collagenous fiber/polyester composite material to load Fe(III) |
| CN103254957B (en) * | 2013-05-06 | 2014-08-27 | 陕西科技大学 | Device and method for removing hydrogen sulfide out of methane by utilizing collagenous fiber/polyester composite material to load Fe(III) |
| CN106268291A (en) * | 2016-11-03 | 2017-01-04 | 南京工业大学 | Filter tower device and the method for biological desulphurization deodorization are dripped in a kind of biological desulphurization deodorization |
| CN111330425A (en) * | 2020-03-11 | 2020-06-26 | 唐山绿源环保科技有限公司 | Biological desulfurization system of desorption high concentration hydrogen sulfide |
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Application publication date: 20120516 |