CN101705249B - High-value utilization process for in-situ biogas desulfurization comprehensive treatment - Google Patents
High-value utilization process for in-situ biogas desulfurization comprehensive treatment Download PDFInfo
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- CN101705249B CN101705249B CN2009100127336A CN200910012733A CN101705249B CN 101705249 B CN101705249 B CN 101705249B CN 2009100127336 A CN2009100127336 A CN 2009100127336A CN 200910012733 A CN200910012733 A CN 200910012733A CN 101705249 B CN101705249 B CN 101705249B
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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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
Abstract
The invention discloses a high-value utilization process for in-situ biogas desulfurization comprehensive treatment, which solves the problems of short service cycle and frequent and inconvenient replacement of a desulfurizer, high running cost and the like in the conventional biogas desulfurization. The process comprises the following operating steps that: a coupling type long-acting desulfurizer is added into a biogas fermentation device through a dosing device to make desulfurization and raw material fermentation carried out synchronously; and the desulfurizer inhibits the activity of sulfureted hydrogen generating bacteria in the biogas fermentation device to reduce the generated sulfureted hydrogen in the in-situ biogas, and is also reacted with the sulfureted hydrogen generated in the fermentation process to generate water insoluble sulphide, and precipitate is discharged along with discharged materials, so that the in-situ biogas is comprehensively treated and desulfurized in the biogas fermentation device, and then is directly output and utilized. The process has the advantages of simple process flow, convenient operation, improvement of resource utilization values, obvious improvement of desulfurization efficiency, equipment cost conservation, low running cost and the like; and the service life of the biogas fermentation device and an output pipeline is prolonged.
Description
Technical field:
Patent of the present invention relates to a kind of in-situ biogas desulfurization comprehensive treating process high-value-use technology, is specially adapted to various fermentation concentration and is not more than 35% anaerobic ferment process (being TS≤35%).This technology can be used for the original position desulfurization of large, medium and small type anaerobic ferment devices and domestic methane tank.
Technical background:
Hydrogen sulfide is a kind of hypertoxic gas, the serious harm person poultry safety.Because popularizing of rat chow, sulphur content constantly increases in the feces of livestock and poultry, causes the hydrogen sulfide content in the biogas also general by 1 original～2g/m
3Rise to 3～4g/m
3, biogas desulfurization is more urgent.In China, no matter be big-and-middle-sized biogas engineering or rural area household biogas, biogas desulfurization is main with traditional dry desulfurization (sweetening agent is a red oxide of iron) still at present; There is the part biogas engineering to adopt biological desulphurization abroad.The red oxide of iron method is with a long history, technology maturation, relatively be suitable for hydrogen sulfide in methane content lower (≤1g/L); And desulfurization when biogas makings is relatively drier; The initial stage desulfuration efficiency all can reach more than 95%, but along with the reduction of Sulfur capacity, the later stage sweetening effectiveness is decay rapidly; Because of Sulfur capacity restriction cause life cycle short, change frequently and inconvenient, running cost is high, in actual use, many users feel trouble and sweetening agent are not regenerated or changes that desulfurizer performs practically no function, and causes high sulfur-bearing biogas by directly use.
In order to overcome the drawback of red oxide of iron desulfurization, some units are through improving the chemical desulfurization agent, add means such as catalyzer and improve sweetening agent both at home and abroad, with the cost that reduces sweetening agent, improve desulfuration efficiency, extend working time.Biogas desulfurization efficient etc. improves through adding flocculation agent in cu-zsm catalyzer, vannadate oxygenant, Germany like the Maria of U.S. development, and Hebaiyi Ecological Energy Sci., & Tech. Development Co., Ltd., Beijing has developed the multi-functional devulcanizer that peasant household uses.These measures can partly improve the deficiency of iron processes, but still can not effectively overcome the drawback of dry desulfurization.
In view of some drawbacks of materialization desulfurization, scientific research personnel both domestic and external is successively with the biological removal technology introduction biogas desulfurization of hydrogen sulfide.Because biological desulphurization has working pressure and temperature is low, running cost is low, level of automation is high, do not have advantage such as secondary pollution, thereby has obtained certain achievement, has market outlook preferably.
In recent years, utilize both at home and abroad the desulfurization mikrobe that from different habitats, is separated to carry out biogas desulfurization, and comprised photosynthetic sulfur bacteria, thiobacillus etc., the most sophisticated to represent bacterium be T.f bacterium (thiobacillus ferrooxidant).Carried out the mechanism research of microbial desulfurization simultaneously.Verified the metabolism principle of some bacterial strains at present, found out the gene of coding desulphurase, made up engineering strain, to improve desulfuration efficiency and range of application.It is reported that the dsz gene cluster successfully is cloned in many strains pseudomonas.Recombinant bacterial strain is than more effectively desulfurization of original strain.And the engineering bacteria of structure has wide industrial application and environment protection prospect.States such as Holland, Germany, Japan, the U.S. have obtained some successes aspect biological desulphurization; Reported in literature according to some biological desulphurization aspects; As 1) German patent is in " biogas biochemical doctor treatment " of DE102005025040, disclose with biogas with derive from photosynthetic oxygen rich gas and in biochemical desulfurizer, mix biochemical desulfurization afterwards; 2) the Japanese Patent patent No. is in " the methane bio-desulfurization system " of JP2004135579, discloses through nitrification liquid to contact with biogas is reverse hydrogen sulfide in absorption, the oxidation biogas; 3) Japanese Patent No. is in " sulfur method and the desulfurizer " of JP2003113386, disclose natural pond liquid is imported in the biological desulphurization tower, thereby and put into the hydrogen sulfide that carrier fixing sulfur bacterium is removed biogas; 4) Japanese Patent No. is in " bio-desulfurization device " of JP2003062421, discloses aerobic aeration mud is sprayed in the thionizer and the reverse contact desulfuriation of sulfurous gas, and desulfurization mud passes back into and carries out regeneration activating in the aeration tank; 5) at " ACTA Scientiae Circumstantiae " (2008; Vol.28; No.8:1542-1548) in " startup of piggery wastewater denitrogenation and marsh gas desulfurization coupling reactor drum " literary composition, the biogas desulfurization that Ministry of Agriculture's biogas studied and the contents such as linked reaction of denitrogenation of waste water are disclosed; 6) the Chinese patent notification number is in " a kind of methane bio-desulfurization equipment " of CN 2870960Y, discloses a kind of biological process sweetener of inventor's exploitation, promptly utilizes the immobilization thiobacterium to remove the bio-desulfurization device of the hydrogen sulfide in the biogas; 7) at " Harbin Institute of Technology's journal " (2005; Vol.37, " low-temperature biological is handled sulfur-bearing nitrogenous gas usefulness and mechanism research " No.2:167-197) is at " Techniques and Equipment for Environmental Pollution Control " (2006; Vol.7, " modified version bio-trickling filter processing H No.2:45-49)
2The righttest processing condition research of S foul smell " 8) inventor once delivered in " use with environmental organism journal " (2004, Vol.10, No.2:215～217) and had been entitled as that " the wood chip microbial film is handled H
2The S gas studies ", from different environment seed selection several plant heights imitate the desulfurization mikrobes, at H
2The S inlet gas concentration is 1107mg/m
3The time desulfurization degree reach 94%.This method successfully is applied to (daily output biogas 1500m in Tanzania's sisal hemp waste residue biogas engineering
3), desulfurization degree can reach more than 95%.
But biological desulfurizing technology is relatively more responsive to temperature, if will reach the clearance more than 90%, its temperature of reaction must be controlled at more than 25 ℃, is only limited to the biogas engineering desulfurization at present, and the stability of its desulfurization receives the influence of envrionment temperature bigger.And after running to certain phase, because of the desulfurization particle accumulates in the device, latch up phenomenon appears, need change filler to certain phase.
Existing sulfur method all is outside the pond or Chi Ding sets up a desulfurizer, utilizes chemical substance or mikrobe to deviate from the hydrogen sulfide in the biogas, all is after hydrogen sulfide produces, to carry out desulfurization again, belongs to desulfurization afterwards.Have drawbacks such as investment is higher, replacing is complicated, the extra occupation of land of needs.Do not see the report that in biogas fermentation device, carries out in-situ biogas comprehensive treating process desulfurization at present both at home and abroad.
Summary of the invention:
The purpose of this invention is to provide a kind of in-situ biogas desulfurization comprehensive treating process high-value-use technology, it has solved, and the sweetening agent life cycle of existing biogas desulfurization existence is short, replacing is frequent and inconvenient, problems such as running cost height.It is simple that it has technical process; Easy to operate; Improve the utilization of resources and be worth, significantly save advantages such as cost of equipment, working cost, raising desulfuration efficiency, can stablize the hydrogen sulfide that removes in the biogas; Fundamentally solve the problem of environmental pollution that hydrogen sulfide brings, prolonged the work-ing life of biogas fermentation device, export pipeline.
The technical scheme that the present invention adopted is: the concrete operations step of this in-situ biogas desulfurization comprehensive treating process high-value-use technology is following: through chemicals dosing plant coupling type long-acting desulfurizer is added in the biogas fermentation device; Desulfurization and fermenting raw materials are carried out synchronously; Said sweetening agent had both suppressed the activity of the hydrogen sulfide generation bacterium in the said biogas fermentation device; Reduce the generation of hydrogen sulfide in the in-situ biogas; Make again that hydrogen sulfide reacts in the said in-situ biogas that produces in itself and the fermenting process, generate water-fast sulfide, deposition is discharged with discharging; Carry out in-situ biogas comprehensive treating process desulfurization in the biogas fermentation device thereby be implemented in, no longer need extra desulfurizer can directly export utilization; Said sweetening agent comprises sulfate reduction bacteria inhibitor and hydrogen sulfide scavengers, and both mass ratioes are (1～4): (19～16); The consumption mass ratio of desulfurizer therefor and biogas fermentation raw material dry product is (1～35): 1000.
Said sulphate reducing bacteria suppressor factor comprises Sodium orthomolybdate, formaldehyde and qingfengmeisu qiong, and three's mass ratio is (10～88): (10～88): (1～2).
Said hydrogen sulfide scavengers is a molysite, is in Ferrox, iron protochloride, ferrous sulfate, Iron nitrate, iron protocarbonate, iron(ic)chloride, ferric sulfate, iron nitrate, all molysite of ironic citrate one or more.
Described coupling type long-acting desulfurizer adopts solid or liquid, is used for the various biogas engineerings of TS≤35% and the biogas fermentation device of methane-generating pit for farm household.
Said biogas fermentation raw material comprises one or more in feces of livestock and poultry, stalk, high concentrated organic wastewater and the various organic waste.
Advantage and positively effect that the present invention has are: owing to adopt chemicals dosing plant directly coupling type long-acting desulfurizer to be added in the biogas fermentation device in the method for the present invention; Institute and then removes the hydrogen sulfide that environment and equipment are worked the mischief so that desulfurization and fermenting raw materials are carried out synchronously from the source in firedamp gas equipment.Because of containing the suppressor factor that can suppress sulfate reducing bacteria activity in this sweetening agent component; Utilize biochemical technology in biogas fermentation device, a large amount of ions that can produce hydrogen sulfide to be restrained; So in the biogas generative process, just carry out desulfurization first; Reduce the generation of hydrogen sulfide in the in-situ biogas significantly, also just reduced the workload of follow-up desulfurization in a large number.Again because of also containing hydrogen sulfide scavengers in this sweetening agent component; Can make hydrogen sulfide in the in-situ biogas that itself and fermenting process produce that the reaction of on-gaseous sulfide takes place irreversibly to be converted into; So desulfurization again in the biogas generative process; Generate water-fast sulfide, post precipitation is discharged with discharging.Therefore, the present invention is readily embodied in the interior twice comprehensive treating process desulfurization to in-situ biogas of biogas fermentation device, stablizes to remove the hydrogen sulfide in the biogas, thereby need not to be provided with extraly desulfurizer.This both can directly export the biogas that produces; Carry out the high-value-use of biogas, can reduce the cost of high-value-use of volume and the biogas of necessary refining desulfurization device again significantly, fundamentally solved the problem of environmental pollution that hydrogen sulfide brings; The real construction investment that realizes that biogas desulfurization had economizes; Advantages such as technical process is simple, and is easy to operate, and running cost is low.In addition, also can reduce the corrosion of hydrogen sulfide, the work-ing life of significant prolongation export pipeline and biogas fermentation device, improve desulfuration efficiency and reduce cost output channel through in-situ biogas desulfurization.Prove through actual survey, directly in biogas fermentation device, add coupling type long-acting desulfurizer, in-situ biogas is carried out hydrogen sulfide stripping, clearance reaches as high as 99%.
In sum; The incomparable advantages of other sweetening agent such as the technology that in-situ biogas coupling type long-acting desulfurizer has is simple, economical and practical; Adopt biological and chemical coupled technology through it; In methane-generating pit, the hydrogen sulfide in the in-situ biogas is carried out comprehensive treating process and remove, will become the new trend of biogas desulfurization.
Embodiment:
Below in conjunction with embodiment the present invention is elaborated.The concrete operations step of this in-situ biogas desulfurization comprehensive treating process high-value-use technology is following: through chemicals dosing plant coupling type long-acting desulfurizer is added in the biogas fermentation device, desulfurization and fermenting raw materials are carried out synchronously.Coupling type long-acting desulfurizer can suppress the activity of sulphate reducing bacteria in the said biogas fermentation device; Reduce the generation of hydrogen sulfide in the in-situ biogas; Can make again that hydrogen sulfide reacts in the in-situ biogas that produces in itself and the fermenting process, generate water-fast sulfide, deposition is discharged with discharging; Carry out in-situ biogas comprehensive treating process desulfurization in the biogas fermentation device thereby be implemented in, no longer need extra desulfurizer can directly export utilization.The coupling type long-acting desulfurizer that is adopted comprises sulfate reduction bacteria inhibitor and hydrogen sulfide scavengers, and both mass ratioes can be in (1～4): select as required in the scope of (19～16).The consumption mass ratio of used sulfate reduction bacteria inhibitor and hydrogen sulfide scavengers and the biogas fermentation raw material dry product that adopts is (1～35): 1000.The sulfate reduction bacteria inhibitor has adopted Sodium orthomolybdate, formaldehyde and qingfengmeisu qiong in the present embodiment, and make this triangular mass ratio according to actual materials amount in (10～88): (10～88): in (1～2) scope the apolegamy.Hydrogen sulfide scavengers mainly adopts molysite; Can select a kind of in all molysite of Ferrox, iron protochloride, ferrous sulfate, Iron nitrate, iron protocarbonate, iron(ic)chloride, ferric sulfate, iron nitrate, ironic citrate for use, can select also that wherein two or more are used in combination for use.
Dosing method can adopt dosing pump quantitatively coupling type long-acting desulfurizer to be pumped into the biogas fermentation device from medicine storage device according to actual needs and (generally be applicable to various biogas engineering), also can adopt artificial with in an amount of coupling type long-acting desulfurizer input methane-generating pit (generally being applicable to methane-generating pit for farm household).Coupling type long-acting desulfurizer both can add by liquid form, can add by solid-state form again.But be more evenly distributed with the liquid form adding.The both large, medium and small anaerobic digestion device of fermentation unit, methane-generating pit for farm household again.The biogas fermentation raw material is to comprise in the various organic wastes such as feces of livestock and poultry, stalk, high concentrated organic wastewater one or more.
Embodiment one
The biogas engineering application example
First the 300kg sweetening agent is dissolved in the water, from opening for feed, add 450m
3Fermentor tank in (contain 13～25 tons of dry-matteies approximately, fermentation raw material is feces of livestock and poultry such as cow dung, chicken manure), stirred then 5 minutes, make sweetening agent uniform distribution in fermentor tank, make the H that produces in the fermentor tank
2S and reactive desulfurizing agent generate indissoluble FeS deposition, get rid of with the discharge of biogas residue and biogas liquid, thereby realize in-situ biogas desulfurization.After adding sweetening agent first, add sweetening agent 1～10kg/T raw material with raw material when adding raw material later at every turn, add when the biogas sulphur content is high, add less after a little while.
The sweetening agent prescription is: Sodium orthomolybdate 17.6g, formaldehyde 2g, qingfengmeisu qiong 0.4g, ferrous sulfate 80g.
Through a month desulfurization test, make H in the biogas
2S concentration is from 1200mg/m
3Drop to about 15mg/m
3, clearance reaches more than 98%.
Embodiment two
Application example continuously ferments
Fermentation unit volume 20L, fermentation raw material are pig manure, and total solid matters (TS) is 5%, 35 ℃ of mesophilic digestion, adds raw material 1.0～2.0L every day, first week feed supplement every day 1 time, and add 2 second every day in week, and add 4 the 3rd every day in week, and add 8 every day around the.An amount of coupling type long-acting desulfurizer is dissolved in the water, forms even liquid sweetening agent, when adding fermentation raw material, quantitatively add by micro pump, and under the whisking appliance effect in fermentation unit uniform distribution.
The 20L fermentation unit adds coupling type long-acting desulfurizer 0.25～1.5g every day.The coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 0.5g, formaldehyde 4.4g, qingfengmeisu qiong 0.1g, Ferrox 25g, iron(ic)chloride 25g, ferrous sulfate 25g, Iron nitrate 10g, iron protocarbonate 10g.
Test shows through in fermentation unit, adding coupling type long-acting desulfurizer can realize the original position desulfurization, and the concentration that makes hydrogen sulfide in methane is by 2000mg/m
3Drop to 50～100mg/m
3, clearance reaches more than 95%.The different sweetening effectivenesss that add frequency are more or less the same.
Embodiment three
Application example in batches ferments
In ten groups of 1.5L upper and lower opening filter flasks, add the 1L high concentrated organic wastewater respectively and carry out biogas fermentation; The methane inoculum is 20%; About 1～3% (TS=1～3%) of fermentation total solids, the disposable coupling type long-acting desulfurizer 0.5～2g that adds respectively when charging feedstock shakes up back 30 ℃ of fermentations.Blank fermentation group with not adding sweetening agent compares.
First group of coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 2.9g, formaldehyde 7g, qingfengmeisu qiong 0.1g, iron nitrate 90g.
Second group of coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 2.9g, formaldehyde 7g, qingfengmeisu qiong 0.1g, ironic citrate 90g.
The 3rd group of coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 2.9g, formaldehyde 7g, qingfengmeisu qiong 0.1g, iron protochloride 90g.
The 4th group of coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 2.9g, formaldehyde 7g, qingfengmeisu qiong 0.1g, ferric sulfate 90g.
The 5th group of coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 2.9g, formaldehyde 7g, qingfengmeisu qiong 0.1g, iron(ic)chloride 90g.
The 6th group of coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 2.9g, formaldehyde 7g, qingfengmeisu qiong 0.1g, Ferrox 90g.
The 7th group of coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 2.9g, formaldehyde 7g, qingfengmeisu qiong 0.1g, Iron nitrate 90g.
The 8th group of coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 2.9g, formaldehyde 7g, qingfengmeisu qiong 0.1g, iron protocarbonate 90g.
The 9th group of coupling type long-acting desulfurizer prescription is: Sodium orthomolybdate 2.9g, formaldehyde 7g, qingfengmeisu qiong 0.1g, ferric sulfate 20g, iron protochloride 20g, ironic citrate 20g, iron nitrate 20g, iron protocarbonate 10g.
The tenth group is blank, does not add sweetening agent.
Test group continues about 2 months of desulfurization, all can not remove hydrogen sulfide on the same group, but clearance becomes downtrending as time passes.Each is organized the hydrogen sulfide removal rate and all drops to 70%～80% of february gradually from initial about 95%.
Embodiment four
Do the fermentation application example
In big mouthful of vial of 2.5L, add the 200g stalk; Add an amount of inoculum and water; Make in the fermentation flask total solid concentration about 35%, about 20%, the 30 ℃ of fermentation of biogas inoculum; Disposable adding coupling type long-acting desulfurizer 2～6g when charging feedstock, the composition of coupling type long-acting desulfurizer is: Sodium orthomolybdate 1.82g, qingfengmeisu qiong 0.18g, formaldehyde 16g, Ferrox 30g, iron protochloride 25g, iron protocarbonate 17g, ironic citrate 10g.Add and fashionable coupling type long-acting desulfurizer and fermentation raw material etc. is mixed.
Actual survey shows, the sustainable desulfurization of coupling type long-acting desulfurizer 4～6 months.Make stalk fermentation produce hydrogen sulfide in methane concentration by 500～800mg/m
3Drop to 10～50mg/m
3
Embodiment five
The domestic methane tank application example
At different rural area 8m
3(fermentation raw material is organic mixtures such as pig manure, stalk, dish leaf in the domestic methane tank; Contain about 0.24～0.48 ton of dry-matter) respectively disposable input 2Kg, 4kg, 6kg sweetening agent; Sweetening agent can directly be sprinkled into from the methane-generating pit manhole by solid form; Stir with article such as clubs then and (from the opening for feed of domestic methane tank, add after also can dissolving in sweetening agent in the water; Utilize sludge pump that natural pond liquid is pumped into opening for feed from discharge port again, form liquid circulation, the sweetening agent of adding is evenly distributed in methane-generating pit).The sweetening agent prescription is: Sodium orthomolybdate 5g, formaldehyde 9.7g, qingfengmeisu qiong 0.3g, molysite 85g.
Test shows, drops into 2～5Kg sweetening agent, can make methane-generating pit continue desulfurization 3～6 months.Make H in the biogas
2S concentration is from 2000～3000mg/m
3Drop to 100～1000mg/m
3, clearance reaches as high as more than 95%.
The family is better at the interpolation initial stage with the sweetening effectiveness in pond, and the later stage desulfuration efficiency has certain decline, and then can promote desulfuration efficiency as carrying out suitably replenishing sweetening agent in the above described manner this moment.
Claims (2)
1. in-situ biogas desulfurization comprehensive treating process high-value-use technology; It is characterized in that the concrete operations step is following: coupling type long-acting desulfurizer is added in the biogas fermentation device through chemicals dosing plant; Desulfurization and fermenting raw materials are carried out synchronously; Said sweetening agent had both suppressed the activity of the sulphate reducing bacteria in the said biogas fermentation device, reduced the generation of hydrogen sulfide in the in-situ biogas, made again that hydrogen sulfide reacts in the said in-situ biogas that produces in itself and the fermenting process; Generate water-fast sulfide; Deposition is discharged with discharging, carries out in-situ biogas comprehensive treating process desulfurization in the biogas fermentation device thereby be implemented in, and no longer needs extra desulfurizer can directly export utilization; Said sweetening agent is made up of sulfate reduction bacteria inhibitor and hydrogen sulfide scavengers, and both mass ratioes are 1 ~ 4:19 ~ 16; The mass ratio of desulfurizer therefor and biogas fermentation raw material dry product consumption is 1 ~ 35 : 1000; Said sulfate reduction bacteria inhibitor is made up of Sodium orthomolybdate, formaldehyde and qingfengmeisu qiong, and three's mass ratio is 10 ~ 88:10 ~ 88:1 ~ 2; Said hydrogen sulfide scavengers is one or more in Ferrox, iron protochloride, ferrous sulfate, Iron nitrate, iron protocarbonate, iron(ic)chloride, ferric sulfate, iron nitrate, the ironic citrate.
2. in-situ biogas desulfurization comprehensive treating process high-value-use technology according to claim 1, it is characterized in that: said biogas fermentation raw material comprises one or more in feces of livestock and poultry, stalk, high concentrated organic wastewater and the various organic waste.
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| CN103539328B (en) * | 2013-10-12 | 2015-11-18 | 同济大学 | A kind of original position sulphur-fixing agent for anaerobic sludge digestion and its production and use |
| CN106554837B (en) * | 2016-11-17 | 2019-10-22 | 南京工业大学 | A kind of method of iron containing compounds and Acidithiobacillus caldus combined removal hydrogen sulfide in methane |
| CN107164415A (en) * | 2017-07-04 | 2017-09-15 | 合肥择浚电气设备有限公司 | A kind of technique of utilization fermenting crops straws biogas |
| CN113215413B (en) * | 2021-04-13 | 2022-04-22 | 华南理工大学 | Desulfurizing agent and method for preparing zero-carbon smelting precursor by removing sulfur in waste lead paste |
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| JP2004135579A (en) * | 2002-10-17 | 2004-05-13 | Mitsubishi Heavy Ind Ltd | Biodesulfurization system for biogas |
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