CN108579373B - Desulfurization system and desulfurization method for biogas containing high-concentration hydrogen sulfide - Google Patents
Desulfurization system and desulfurization method for biogas containing high-concentration hydrogen sulfide Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 104
- 230000023556 desulfurization Effects 0.000 title claims abstract description 104
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 49
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 47
- 230000008929 regeneration Effects 0.000 claims abstract description 47
- 238000011069 regeneration method Methods 0.000 claims abstract description 47
- 239000007921 spray Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007789 gas Substances 0.000 claims abstract description 25
- 230000008569 process Effects 0.000 claims abstract description 12
- 230000003009 desulfurizing effect Effects 0.000 claims description 52
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 31
- 239000011593 sulfur Substances 0.000 claims description 31
- 229910052717 sulfur Inorganic materials 0.000 claims description 31
- 239000003795 chemical substances by application Substances 0.000 claims description 30
- 239000003054 catalyst Substances 0.000 claims description 25
- 239000006260 foam Substances 0.000 claims description 22
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000002485 combustion reaction Methods 0.000 claims description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 14
- 230000001105 regulatory effect Effects 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 238000005276 aerator Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- 238000010521 absorption reaction Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 230000009977 dual effect Effects 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000011152 fibreglass Substances 0.000 claims description 2
- -1 meanwhile Substances 0.000 claims description 2
- 239000002356 single layer Substances 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims description 2
- 239000010935 stainless steel Substances 0.000 claims description 2
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims 1
- 239000006227 byproduct Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000005192 partition Methods 0.000 description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical group O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 150000004700 cobalt complex Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
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- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
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- 238000011084 recovery Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/75—Multi-step processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/30—Alkali metal compounds
- B01D2251/304—Alkali metal compounds of sodium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2251/602—Oxides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2251/60—Inorganic bases or salts
- B01D2251/606—Carbonates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
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- B01D2255/70—Non-metallic catalysts, additives or dopants
- B01D2255/705—Ligands for metal-organic catalysts
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2258/05—Biogas
Abstract
The invention relates to a desulfurization system for biogas containing high-concentration hydrogen sulfide, which comprises a biogas inlet, a biogas flowmeter, a biogas cabinet, a wet desulfurization tower, a gas-water separator, a plurality of dry desulfurization towers connected in series or in parallel, an outlet gas detector, a biogas fan and a biogas utilization pipeline which are sequentially communicated through biogas, wherein spray liquid treated by the wet desulfurization tower and liquid of the gas-water separator both enter a desulfurization liquid regeneration treatment device. The desulfurization system combines wet desulfurization and dry desulfurization processes, can reduce the concentration of hydrogen sulfide from 20000ppm to below 100ppm, and meets the requirement of biogas energy utilization. The operation cost is low, the methane can be utilized after treatment to generate economic benefits, and the generated by-products can be sold as goods, so that multiple purposes are achieved.
Description
Technical Field
The invention relates to a desulfurization system and a desulfurization method for high-concentration hydrogen sulfide-containing biogas, and belongs to the technical field of biogas desulfurization.
Background
Biogas is a combustible gas produced by the fermentation of various organic substances in the absence of air (reducing conditions) and at a suitable temperature and pH value by microorganisms. The biogas belongs to secondary energy and is renewable energy, the heat productivity of the biogas per cubic meter is about 20800-23600 kilojoules, which is equivalent to the heat provided by 0.7 kg of anthracite, so the biogas is a good energy source. The main components of the biogas comprise: 50% -80% methane (CH)4) 20% -40% of carbon dioxide (CO)2) 0% -5% nitrogen (N)2) Less than 1% hydrogen (H)2) Less than 0.4% oxygen (O2) and 0.1% -3% hydrogen sulfide (H)2S), and the like. At present, biogas generated in industrial production mostly comes from an anaerobic fermentation process, and the generated biogas is generally used for power generation, and is combusted by a biogas or a biogas boiler to generate steam or hot water for plant use.
Because the biogas contains a certain amount of hydrogen sulfide, the hydrogen sulfide has a strong corrosion effect, and if the hydrogen sulfide enters a biogas boiler or a generator, the inner wall of equipment is easily corroded, so that equipment damage or safety accidents are caused. Therefore, before the biogas is used, desulfurization treatment is required, and the content of hydrogen sulfide in the biogas is less than 100ppm generally before the biogas enters a biogas boiler or a generator.
However, most of high-concentration wastewater in pharmacy, chemical industry and the like contains sulfur-containing compounds, so that the content of hydrogen sulfide in methane generated by anaerobic treatment is high. The concentration of hydrogen sulfide in the biogas exceeds 5000ppm, and is even more than 30000 ppm. The removal of the hydrogen sulfide with the concentration is usually absorbed by a sodium hydroxide wet method, but the operation cost of the method is higher and is usually higher than the utilization cost of the methane, so most enterprises directly combust the part of the methane and then discharge the part of the methane. The mode not only causes energy waste, but also causes environmental pollution due to the combustion of hydrogen sulfide in the methane.
Disclosure of Invention
The invention provides a desulfurization system and a desulfurization method for biogas containing high-concentration hydrogen sulfide, and solves the problems of high operation cost, energy waste and the like in the conventional desulfurization process of the biogas containing high-concentration hydrogen sulfide.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a desulfurization system for biogas containing high-concentration hydrogen sulfide comprises a biogas inlet, a biogas flowmeter, a biogas cabinet, a wet desulfurization tower, a gas-water separator, a plurality of dry desulfurization towers connected in series or in parallel, an outlet gas detector, a biogas fan and a biogas utilization pipeline which are sequentially communicated through biogas, wherein spray liquid treated by the wet desulfurization tower and liquid of the gas-water separator enter a desulfurization liquid regeneration treatment device, the desulfurization liquid regeneration treatment device comprises a rich liquid tank, a regeneration tank and a barren liquid tank which are sequentially communicated, the barren liquid tank is communicated with the wet desulfurization tower through a wet tower spray pump, a jet ejector and an aerator are arranged in the regeneration tank, the regeneration tank is connected with a sulfur foam collector, the regeneration tank and the sulfur foam collector are communicated with a plate-and frame filter press through a plate-frame filter press lifting pump, and the plate-frame filter press is communicated with the barren liquid tank through a pipeline, the plate-and-frame filter press is provided with a sulfur discharge pipeline.
Further, a preferred embodiment of the present invention is: the desulfurization system further comprises a desulfurizer dosing device and a catalyst dosing device, and the desulfurizer dosing device and the catalyst dosing device are connected with the barren solution tank.
Further, a preferred embodiment of the present invention is: the desulfurization system further comprises a biogas combustion torch, and the biogas combustion torch is sequentially connected with the flame arrester and the biogas cabinet.
Further, a preferred embodiment of the present invention is: the wet desulfurization tower is a filler spray tower or an empty tower spray tower, the air speed of the empty tower of the wet tower is not more than 0.25m/s, the retention time in the tower is more than 60s, and the liquid-air ratio of the spray of the wet tower is 150L/m3-300L/m3。
Further, a preferred embodiment of the present invention is: the spray head in the wet desulphurization tower adopts a vortex spray head.
Further, a preferred embodiment of the present invention is: the dry desulfurization tower comprises a dry desulfurization tower main body and an online regeneration device, wherein a plurality of layers of desulfurizer supporting plates are arranged inside the dry desulfurization tower main body, the dry desulfurization tower main body is divided into a plurality of desulfurizer filling areas by the desulfurizer supporting plates, iron oxide desulfurizer is filled in the desulfurizer filling areas, a biogas inlet pipe is arranged at the bottom of the dry desulfurization tower main body, a biogas one-way valve and a second biogas flowmeter are sequentially arranged on the biogas inlet pipe, a biogas outlet and an exhaust port are arranged at the top of the dry desulfurization tower main body, and the biogas outlet is connected with an outlet gas detector; the on-line regeneration device comprises an air inlet pipe and an on-line thermometer, the air inlet pipe is communicated with the methane inlet pipe, the inlet end of the air inlet pipe is connected with an air compressor, an air flow meter, an electric regulating valve and an air one-way valve are sequentially arranged on the air inlet pipe, and the on-line thermometers are a plurality of and are arranged at different positions of a desulfurizer filling area.
Further, a preferred embodiment of the present invention is: the dry-type desulfurizing tower also comprises a dry-type desulfurizing tower base, a desulfurizing agent access hole and a water outlet.
Further, a preferred embodiment of the present invention is: the iron oxide desulfurizer is a yellow or brown yellow small cylinder, the diameter is 4-6mm, the length is 5-15mm, and the bulk density is 0.7-0.9 kg/L.
The invention also provides a desulfurization method of methane containing high-concentration hydrogen sulfide, which is characterized by comprising the following steps: the desulfurization system comprises the following steps:
(1) biogas generated by the anaerobic tank enters a biogas cabinet from a biogas inlet through a first biogas flowmeter, and enters the wet desulfurization tower after being temporarily stored in the biogas cabinet; in the tower, biogas runs from bottom to top, and reacts after contacting with a desulfurization spray liquid from top to bottom to remove 90-98% of hydrogen sulfide in the biogas, the biogas after the removal of the hydrogen sulfide enters a gas-water separator, the biogas and water are separated in the gas-water separator, the separated biogas enters a dry desulfurization tower, the content of the hydrogen sulfide in the biogas after dry desulfurization is reduced to be below 100ppm, and the biogas can enter a biogas utilization pipeline after being pressurized by a biogas fan to generate power or enter a biogas boiler for combustion and utilization;
(2) after the liquid separated by the spray liquid and the gas-water separator enters the pregnant solution tank for temporary storage, the liquid enters the regeneration tank through the ejector by utilizing the jet pump, under the dual action of a jet pump and an aerator, a desulfurizer is regenerated under the action of a catalyst, sulfur foam is separated out to a sulfur foam collector, the regenerated desulfurization solution automatically flows into a barren solution pool, the supernatant of the barren solution pool can enter a wet desulfurization tower through a wet tower spray pump for reaction, precipitates of the sulfur foam collector and the barren solution pool enter through a lifting pump of a plate and frame filter press for filter pressing in the plate and frame filter press, the sulfur foam generated after filter pressing is discharged through a sulfur discharge pipeline, the filtrate after filter pressing returns to the barren solution pool to continuously participate in the reaction, in the using process, the wet desulfurizer is added through the desulfurizer dosing device, the catalyst is added through the catalyst dosing device, and the two agents are dissolved and then added into the barren solution tank;
(3) an outlet gas detector is arranged on a pipeline before entering the biogas fan so as to determine the desulfurization effect;
(4) if the system for utilizing the biogas fails, the system can monitor signals through the pressure sensor, redundant biogas can be directly combusted through the biogas combustion torch, the system failure caused by overlarge pressure is avoided, and a flame arrester is arranged in front of the biogas combustion torch to prevent potential safety hazards caused by backfire.
The invention has the beneficial effects that:
the desulfurization system combines wet desulfurization and dry desulfurization processes, can reduce the concentration of hydrogen sulfide from 20000ppm to below 100ppm, and meets the requirement of biogas energy utilization. The operation cost is low, the methane can be utilized after treatment to generate economic benefits, and the generated by-products can be sold as goods, so that multiple purposes are achieved.
The wet desulphurization of the invention adopts a new wet catalytic oxidation technology, and utilizes a desulphurization catalyst to complete two processes of catalytic chemical absorption and catalytic oxidation regeneration of sulfide. In the desulfurization process, hydrogen sulfide in the biogas is absorbed by using a chemical agent sodium carbonate, and the catalyst has a stronger desulfurization function than common chemical absorption due to the addition of the catalyst; in the oxidation regeneration process, the catalyst can simultaneously catalyze and oxidize inorganic sulfur and organic sulfur compounds, so that the regeneration of the sodium carbonate absorbent is realized.
The basic reaction is as follows:
Na2CO3+2H2S→NaHS+NaHCO3
the dry desulfurization device adopts a dry desulfurizer capable of being regenerated on line, the main component of a desulfurizer is ferric oxide, the service life of the desulfurizer can be prolonged by 3-4 times through on-line regeneration, the cost of the desulfurizer is saved, meanwhile, the on-line regeneration can realize automatic operation, the safety risk caused by improper operation is avoided, and a guarantee is added for the utilization of methane.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of one embodiment of the present invention;
FIG. 2 is a schematic view of the waste liquid recovery and treatment apparatus shown in FIG. 1;
FIG. 3 is a schematic structural view of the dry desulfurization tower of FIG. 1;
FIG. 4 is a front view of the vortex nozzle of the present invention;
FIG. 5 is a left side view of the vortex nozzle of the present invention;
in the figure, 1, a methane inlet; 2. a biogas flow meter; 3. a methane cabinet; 4. a flame arrestor; 5. a wet desulfurization tower; 6. a gas-water separator; 7. 1# dry desulfurization tower; 8. 2# dry desulfurization tower; 9. an outlet gas detector; 10. a biogas fan; 11. a biogas utilization pipeline; 12. a rich liquor pool; 13. a jet pump; 14. an ejector; 15. a regeneration tank; 16. an aerator; 17. a sulfur foam collector; 18. a plate-and-frame filter press lift pump; 19. a barren liquor pool; 20. a wet tower spray pump; 21. a desulfurizer dosing device; 22. a catalyst dosing device; 23. a plate-and-frame filter press; 24. a sulfur discharge pipe; 25. a biogas combustion torch; 26. an exhaust gas treatment pipe; 27. a vortex nozzle; 7-1, a biogas inlet pipeline; 7-2, a methane one-way valve; 7-4, an air compressor; 7-5, an air flow meter; 7-6, electric control valve; 7-7, an air inlet pipeline; 7-8, an air check valve; 7-9, a dry desulfurizing tower base; 7-10 parts of desulfurizer supporting partition plates; 7-11 parts of desulfurizer overhaul holes; 7-12 parts of desulfurizer filling area; 7-13, a dry desulfurizing tower main body; 7-14, electronic thermometer; 7-15, a biogas outlet; 7-16 parts of air outlet; 7-17 and a water outlet.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
As shown in fig. 1-5, a desulfurization system for biogas containing high concentration hydrogen sulfide comprises a biogas inlet 1, a biogas flowmeter 2, a biogas cabinet 3, a wet desulfurization tower, a gas-water separator 6, a plurality of dry desulfurization towers connected in series or in parallel, outlet gas detectors 7-17, a biogas blower 10 and a biogas utilization pipeline 11 which are sequentially communicated with each other through biogas, wherein spray liquid treated by the wet desulfurization tower 5 and liquid of the gas-water separator 6 enter a desulfurization liquid regeneration treatment device, the desulfurization liquid regeneration treatment device comprises a rich liquid tank 12, a regeneration tank 1915 and a lean liquid tank 19 which are sequentially communicated with each other, the lean liquid tank 19 is communicated with the wet desulfurization tower 5 through a wet tower spray pump 20, a jet pump 13, a jet ejector 14 and an aerator 16 are arranged in the regeneration tank 15, the regeneration tank 1915 is connected with a sulfur foam collector 17, the regeneration tank 15 and the sulfur foam collector 17 are connected with a plate-and frame filter press 18 through a plate-frame 23 lifting pump 18 23, the plate and frame filter press 23 is communicated with the barren liquor pool 19 through a pipeline, and the plate and frame filter press 23 is provided with a sulfur discharge pipeline 24.
The two dry desulfurization towers in the embodiment are a 1# dry desulfurization tower 7 and a 2# dry desulfurization tower 8, and the two dry desulfurization towers can be connected in parallel or in series through different pipelines and valves.
In the using process, the wet desulfurizing agent (sodium carbonate) and the catalyst (the high-efficiency desulfurizing agent taking the bispolyphthalocyanine cobalt complex as the main component) are partially lost, so the desulfurizing system also comprises a desulfurizing agent dosing device 21 and a catalyst dosing device 22, and the desulfurizing agent dosing device 21 and the catalyst dosing device 22 are connected with the barren solution pool 19.
The desulfurization system also comprises a biogas combustion torch 25, and the biogas combustion torch 25 is sequentially connected with the flame arrester 4 and the biogas cabinet 3. If the biogas utilization system fails, the system can monitor signals through the pressure sensor, and redundant biogas can be directly combusted through the biogas combustion torch 25, so that system failure caused by overlarge pressure is avoided. The flame arrester 4 is arranged in front of the biogas combustion torch 25 to prevent potential safety hazards caused by tempering.
The wet desulfurization tower is a filler spray tower or an empty tower spray tower, the air speed of the empty tower of the wet tower is not more than 0.25m/s, the retention time in the tower is more than 60s, and the liquid-air ratio of the spray of the wet tower is selected to be 150L/m3-300L/m 3. If a packed column is used, the residence time in the packing region is not less than 15 s.
The spray head in the wet desulphurization tower adopts the vortex spray head 27, and the vortex spray head 27 can prevent blockage, increase the gas-liquid contact area and improve the reaction efficiency.
The residence time of the rich liquid pool 12 is not more than 30min, the residence time of the regeneration pool 15 is designed to be 3-5h, and the residence time of the barren liquid pool 19 is designed to be 1-2 h.
The rich liquid pool 12 is matched with a liquid level meter for controlling the start and stop of the jet pump 13;
the regeneration tank 15 is matched with an ejector 14 and an aerator, and a large amount of air enters the regeneration tank 15 under the action of the aerator 16 and the ejector 14 and reacts with NaHS, NaHCO3 and the like generated by desulfurization under the left and right of a catalyst to form sodium hydroxide and the like to continuously participate in the reaction. The regeneration tank 15 is designed with a scraper which can scrape and collect the surface sulfur foam into the sulfur foam collector 17 because the sulfur foam can float on the water surface.
The barren liquor tank 19 is designed in the form of a sedimentation tank to facilitate the discharge of impurities.
The dry desulfurization tower comprises a dry desulfurization tower main body 7-13 and an online regeneration device, wherein a plurality of layers of desulfurizer supporting plates are arranged inside the dry desulfurization tower main body 7-13, the dry desulfurization tower main body 7-13 is divided into a plurality of desulfurizer filling areas 7-12 by the desulfurizer supporting plates, iron oxide desulfurizer is filled in the desulfurizer filling areas 7-12, a biogas inlet pipe is arranged at the bottom of the dry desulfurization tower main body 7-13, a biogas one-way valve 7-2 is arranged on the biogas inlet pipe, a biogas outlet 7-15 and an exhaust port 7-16 are arranged at the top of the dry desulfurization tower main body 7-13, and the biogas outlet 7-15 is connected with an outlet gas detector 9; the on-line regeneration device comprises an air inlet pipe and on-line thermometers 7-14, the air inlet pipe is communicated with the biogas inlet pipe, the inlet end of the air inlet pipe is connected with an air compressor 7-4, an air flow meter 7-5, an electric regulating valve 7-6 and air one-way valves 7-8 are sequentially arranged on the air inlet pipe, and the on-line thermometers 7-14 are arranged at different positions of a desulfurizer filling area 7-12.
In the embodiment, the number of the desulfurizer support partition plates 7-10 is two, the main body 7-13 of the dry desulfurization tower is divided into two desulfurizer filling areas 7-12 by the desulfurizer support partition plates 7-10, and the number of the online thermometers 7-14 is two, and the two thermometers are arranged at the upper part of the desulfurizer filling areas 7-12.
The dry-type desulfurizing tower also comprises a dry-type desulfurizing tower base 7-9, a desulfurizing agent access hole 7-11 and a water outlet 7-17.
The ferric oxide desulfurizer is a yellow or brown yellow small cylinder with the diameter of 4-6mm, the length of 5-15mm and the bulk density of 0.7-0.9 kg/L.
The main bodies 7-13 of the dry-type desulfurizing tower are made of glass fiber reinforced plastics or stainless steel which can resist the temperature of more than 70 ℃.
The empty linear velocity of the main body 7-13 of the dry desulfurizing tower is 0.2-0.4m/s, and the stacking height of the single-layer desulfurizing agent is 0.3-0.8 m.
The purpose of the biogas check valve 7-2 is to prevent gas return and the biogas flow meter 2 is used to monitor the intake air flow to calculate the intake air flow. After the methane enters the main tower. The desulfurizer supporting partition plates 7-10 have the functions of supporting the filling of the desulfurizer to fix the desulfurizer, and also have the function of uniformly distributing the biogas to avoid local short flow; the desulfurizer filling area 7-12 is mainly filled with an iron oxide desulfurizer which is a yellow or brown yellow small cylinder, the diameter of the iron oxide desulfurizer is about 4-6mm, the length of the iron oxide desulfurizer is 5-15mm, the stacking density of the iron oxide desulfurizer is 0.7-0.9kg/L, and the filling amount and the filling area are determined according to the designed biogas air intake amount and the hydrogen sulfide removal amount. The dry-type desulfurizing tower base 7-9 is aimed at ensuring the structural stability of the desulfurizing tower, and reinforcing columns and the like can be added according to the structural requirements during design. The desulfurizer manhole aims at filling desulfurizer and performing overhaul setting in the tower, and the diameter of the desulfurizer is generally designed to be 600 mm. The exhaust ports 7-16 should be in a long-term closed position. The gas detector is used for measuring the concentration of outlet hydrogen sulfide and the concentration of oxygen, and when the outlet hydrogen sulfide content is higher than 100ppm continuously for 1 hour, the desulfurizing agent is basically saturated and needs to start on-line regeneration. .
The dry desulfurizing tower also comprises a dry desulfurizing tower base 7-9, a desulfurizing agent access hole and a water outlet 7-17.
The ferric oxide desulfurizer is a yellow or brown yellow small cylinder with the diameter of 4-6mm, the length of 5-15mm and the bulk density of 0.7-0.9 kg/L.
In the implementation, the two dry desulfurization towers share a gas detector and an air compressor 7-4.
Example 2
A desulfurization method of biogas containing high concentration of hydrogen sulfide, using the desulfurization system of example 1, comprising the steps of:
(1) biogas generated by the anaerobic tank enters a biogas cabinet from a biogas inlet through a first biogas flowmeter, and enters the wet desulfurization tower after being temporarily stored in the biogas cabinet; in the tower, biogas runs from bottom to top, and reacts after contacting with a desulfurization spray liquid from top to bottom to remove 90-98% of hydrogen sulfide in the biogas, the biogas after the removal of the hydrogen sulfide enters a gas-water separator, the biogas and water are separated in the gas-water separator, the separated biogas enters a dry desulfurization tower, the content of the hydrogen sulfide in the biogas after dry desulfurization is reduced to be below 100ppm, and the biogas can enter a biogas utilization pipeline after being pressurized by a biogas fan to generate power or enter a biogas boiler for combustion and utilization; an outlet gas detector is arranged on a pipeline before entering the biogas fan so as to determine the desulfurization effect.
(2) After entering a pregnant solution tank for temporary storage, liquid separated by spray liquid and a gas-water separator enters a regeneration tank through a jet device by using a jet pump, under the dual actions of the jet pump and an aerator, a desulfurizer is regenerated under the action of a catalyst, meanwhile, sulfur foam is separated out to a sulfur foam collector, the regenerated desulfurization liquid automatically flows into a barren solution tank, supernatant of the barren solution tank can enter a wet desulfurization tower for reaction through a wet tower spray pump, precipitates of the sulfur foam collector and the barren solution tank enter a plate and frame filter press for filter pressing through a plate and frame filter press lifting pump, sulfur foam generated after filter pressing is discharged through a sulfur discharge pipeline, and filtrate after filter pressing returns to the barren solution tank to continuously participate in reaction;
(3) an outlet gas detector is arranged on a pipeline before entering the biogas fan so as to determine the desulfurization effect;
(4) if the system for utilizing the biogas fails, the system can monitor signals through the pressure sensor, redundant biogas can be directly combusted through the biogas combustion torch, the system failure caused by overlarge pressure is avoided, and a flame arrester is arranged in front of the biogas combustion torch to prevent potential safety hazards caused by tempering;
(5) in the using process, the wet desulfurizer is added through the desulfurizer dosing device, the catalyst is added through the catalyst dosing device, and the two agents are dissolved and then added into the barren solution tank.
The dry desulfurization process comprises the following steps:
(1) the biogas separated by the gas-liquid separator enters a main body 7-13 of the dry-type desulfurizing tower through a biogas inlet pipeline 7-1, the biogas enters the main body tower and then passes through a desulfurizing agent supporting partition plate 7-10 and a desulfurizing agent filling area 7-12 in sequence and then is discharged through a biogas outlet 7-15, a gas detector measures the concentration of hydrogen sulfide and oxygen at the outlet, when the content of the hydrogen sulfide at the outlet is higher than 100ppm continuously for 1 hour, the desulfurizing agent is basically saturated, online regeneration is started, and the water discharged from the dry-type desulfurizing tower is discharged through a water outlet 7-17;
(2) injecting air through an air inlet pipeline 7-7 by an air compressor 7-4, regenerating the reacted desulfurizer by using oxygen in the air, wherein an air flow meter 7-5 is used for metering air inflow, an electric regulating valve 7-6 is used for regulating the air inflow, an online thermometer 7-14 is used for measuring the temperature of the tower wall, when the temperature is higher than 50 ℃, a temperature sensor prepared by the online thermometer 7-14 sends a 4-20mA signal and transmits the signal to a valve of the electric regulating valve 7-6 to be closed, the air inflow is reduced, the regeneration speed is delayed, when the temperature is lower, the opening degree of the valve of the electric regulating valve 7-6 is increased, the regeneration speed is accelerated, the temperature can be set according to the field condition, and the discharged gas is introduced into sodium carbonate absorption liquid to be absorbed;
(3) in the regeneration process, the opening of the electric regulating valve 7-6 is controlled by temperature, when the electric regulating valve is opened for the first time, the opening degree of the electric regulating valve is controlled according to a methane flow meter and is represented by air flow, the air flow is generally the methane flow multiplied by the hydrogen sulfide concentration multiplied by 4/oxygen concentration, the numerical value of the air flow meter 7-5 is smaller than the numerical value whenever, the oxygen concentration detected by an outlet gas detector is smaller than 1%, and if the oxygen concentration is larger than 1%, the opening degree of the electromagnetic valve is reduced.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (1)
1. A desulfurization method of methane containing high-concentration hydrogen sulfide is characterized by comprising the following steps: the desulfurization method adopts a desulfurization system aiming at the methane containing high-concentration hydrogen sulfide;
the desulfurization system comprises a biogas inlet (1), a biogas flowmeter (2), a biogas cabinet (3), a wet desulfurization tower (5), a gas-water separator (6), a plurality of dry desulfurization towers connected in series, an outlet gas detector (9), a biogas fan (10) and a biogas utilization pipeline (11) which are sequentially communicated through biogas;
the spray liquid treated by the wet desulphurization tower (5) and the liquid of the gas-water separator (6) both enter a desulphurization liquid regeneration treatment device, the desulfurization solution regeneration treatment device comprises a rich solution pool (12), a regeneration pool (15) and a lean solution pool (19) which are communicated in sequence, the barren liquor pool (19) is communicated with the wet desulphurization tower (5) through a wet tower spray pump (20), a jet pump (13), a jet device (14) and an aerator (16) are arranged in the regeneration tank (15), the regeneration pool (15) is connected with a sulfur foam collector (17), the regeneration pool (15) and the sulfur foam collector (17) are communicated with a plate and frame filter press (23) through a plate and frame filter press lifting pump (18), the plate-and-frame filter press (23) is communicated with the barren liquor pool (19) through a pipeline, the plate-and-frame filter press (23) is provided with a sulfur discharge pipeline (24);
the wet desulphurization tower (5) is a filler spray tower or an empty tower spray tower; the spray head in the wet desulphurization tower (5) adopts a vortex spray head (27);
the dry desulfurizing tower comprises a dry desulfurizing tower main body (7-13) and an online regenerating device, wherein a plurality of layers of desulfurizing agent supporting plates (7-10) are arranged inside the dry desulfurizing tower main body (7-13), the dry desulfurizing tower main body (7-13) is divided into a plurality of desulfurizing agent filling areas (7-12) by the desulfurizing agent supporting plates (7-10), iron oxide desulfurizing agents are filled in the desulfurizing agent filling areas (7-12), a biogas inlet pipe (7-1) is arranged at the bottom of the dry desulfurizing tower main body (7-13), a biogas one-way valve (7-2) and a second biogas flowmeter are sequentially arranged on the biogas inlet pipe (7-1), a biogas outlet (7-15) and an exhaust port (7-16) are arranged at the top of the dry desulfurizing tower main body (7-13), the methane outlets (7-15) are connected with an outlet gas detector (9); the online regeneration device comprises an air inlet pipe (7-7) and an online thermometer (7-14), wherein the air inlet pipe (7-1) is communicated with the methane inlet pipe, the inlet end of the air inlet pipe is connected with an air compressor (7-4), the air inlet pipe is sequentially provided with an air flow meter (7-5), an electric regulating valve (7-6) and an air one-way valve (7-8), the online thermometers (7-14) are arranged at different positions of a desulfurizer filling area (7-12); the dry-type desulfurizing tower also comprises a dry-type desulfurizing tower base (7-9), a desulfurizing agent access hole (7-11) and a water outlet (7-17); the iron oxide desulfurizer is a yellow or brown yellow small cylinder, the diameter is 4-6mm, the length is 5-15mm, and the bulk density is 0.7-0.9 kg/L; the main body (7-13) of the dry-type desulfurizing tower is made of glass fiber reinforced plastics or stainless steel which can resist the temperature of more than 70 ℃, the empty linear velocity of the main body (7-13) of the dry-type desulfurizing tower is 0.2-0.4m/s, and the stacking height of a single-layer desulfurizing agent is 0.3-0.8 m;
the desulfurization system also comprises a desulfurizer dosing device (21) and a catalyst dosing device (22), and the desulfurizer dosing device and the catalyst dosing device are connected with the barren liquor pool (19); the desulfurization system also comprises a biogas combustion torch (25), wherein the biogas combustion torch (25) is sequentially connected with the flame arrester (4) and the biogas cabinet (3) through biogas pipelines;
the desulfurization method comprises the following steps:
s1, enabling biogas generated by the anaerobic tank to enter a biogas cabinet (3) from a biogas inlet (1) through a first biogas flowmeter, temporarily storing in the biogas cabinet (3), and then entering a wet desulfurization tower (5); in the tower, the biogas runs from bottom to top and reacts after contacting with the desulfurization spray liquid from top to bottom so as to remove 90-98% of hydrogen sulfide in the biogas;
in a wet desulfurization tower (5), the wet desulfurizing agent is sodium carbonate, the wet desulfurizing agent is added through a desulfurizing agent dosing device, the catalyst is a dimeric phthalocyanine cobalt complex, the catalyst is added through a catalyst dosing device, and the two agents are dissolved and then added into a barren liquor pool (19);
when the wet desulphurization tower (5) is an empty tower spray tower, the gas velocity is not more than 0.25m/s, the retention time in the tower is more than 60s, and the liquid-gas ratio of the spray of the wet desulphurization tower (5) is selected to be 150L/m3-300L/m3；
When the wet desulphurization tower (5) is a filler spray tower, the retention time of a filler area is not less than 15 s;
the residence time of the rich liquid pool (12) is not more than 30min, the residence time of the regeneration pool (15) is designed to be 3-5h, and the residence time of the poor liquid pool (19) is designed to be 1-2 h;
the biogas without hydrogen sulfide enters a gas-water separator (6), the biogas and water are separated in the gas-water separator (6), the separated biogas enters a dry-type desulfurizing tower main body (7-13) tower, passes through a desulfurizing agent supporting plate (7-10) and a desulfurizing agent filling area (7-12) in sequence and then is discharged through a biogas outlet (7-15), an outlet gas detector (9) detects the concentration of hydrogen sulfide and the concentration of oxygen at an outlet, when the content of hydrogen sulfide at the outlet is continuously higher than 100ppm for 1 hour, the desulfurizing agent is basically saturated, online regeneration is started, and the water discharged from the dry-type desulfurizing tower is discharged through a water outlet (7-17);
injecting air from an air compressor (7-4) through an air inlet pipeline (7-7), regenerating the reacted desulfurizer by using oxygen in the air, metering air inflow by using an air flow meter (7-5), adjusting the air inflow by using an electric control valve (7-6), measuring the temperature of the tower wall by using an online thermometer (7-14), sending a 4-20mA signal by a temperature sensor configured on the online thermometer (7-14) when the temperature is higher than 50 ℃, closing a valve of the electric control valve (7-6), reducing the air inflow, delaying the regeneration speed, increasing the opening degree of the valve of the electric control valve (7-6) when the temperature is lower, accelerating the regeneration speed, setting the temperature according to the field condition, and introducing the discharged gas into a sodium carbonate absorption liquid for absorption treatment;
in the regeneration process, the opening of the electric regulating valve (7-6) is controlled by temperature, when the electric regulating valve is opened for the first time, the opening degree of the electric regulating valve (7-6) is controlled according to the methane flowmeter (2) and is represented by air flow, the common air flow is the methane flow multiplied by the hydrogen sulfide concentration multiplied by 4/oxygen concentration, the air flow counting value is always smaller than the common air flow value, the oxygen concentration detected by the outlet gas detector (9) is smaller than 1%, and if the oxygen concentration is larger than 1%, the opening degree of the electric regulating valve (7-6) is reduced;
the content of hydrogen sulfide in the biogas after dry desulfurization is reduced to be below 100ppm, and the biogas can enter a biogas utilization pipeline (11) after being pressurized by a biogas fan (10) to generate power or enter a biogas boiler for combustion and utilization;
s2, after the liquid separated by the spray liquid and the gas-water separator (6) enters a rich liquid pool (12) for temporary storage, a jet pump (13) enters a regeneration pool (15) through a jet device (14), under the dual action of the jet pump (13) and an aerator (16), a desulfurizer is regenerated under the action of a catalyst, meanwhile, sulfur foam is separated out to a sulfur foam collector (17), the regenerated desulfurization liquid automatically flows into a poor liquid pool (19), the supernatant of the poor liquid pool (19) can enter a wet desulfurization tower (5) for reaction through a wet tower spray pump (20), the precipitates of the sulfur foam collector (17) and the poor liquid pool (19) enter a plate-and-frame filter press (23) through a plate-and-frame filter press lifting pump (18) for filter pressing, the sulfur foam generated after filter pressing is discharged through a sulfur discharge pipeline (24), and the filtrate returns to the poor liquid pool (19) for continuous reaction after filter pressing, adding wet desulfurizer through a desulfurizer dosing device (21), adding catalyst through a catalyst dosing device (22), dissolving both agents, and adding the dissolved agents into a barren liquor pool (19);
s3, arranging an outlet gas detector (9) on a pipeline before entering the biogas fan (10) to determine the desulfurization effect;
s4, if the biogas utilization system fails, the system can monitor signals through the pressure sensor, redundant biogas can be directly combusted through the biogas combustion torch (25), the system failure caused by overlarge pressure is avoided, and a flame arrester (4) is arranged in front of the biogas combustion torch (25) to prevent potential safety hazards caused by backfire.
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| CN111948332A (en) * | 2019-05-17 | 2020-11-17 | 福建福源凯美特气体有限公司 | Device for detecting and calculating sulfur capacity of desulfurizer |
| CN110115930A (en) * | 2019-05-23 | 2019-08-13 | 无锡格林嘉科技有限公司 | A kind of gas desulfurization system between bioanalysis and wet process |
| CN110756004A (en) * | 2019-10-30 | 2020-02-07 | 中国石油化工股份有限公司 | Combined process for deeply purifying hydrogen sulfide and organic sulfur |
| CN112881606B (en) * | 2021-01-16 | 2023-11-10 | 佰利天控制设备(北京)股份有限公司 | Gas fine desulfurization reactant detection experimental device |
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| CN102895866A (en) * | 2012-09-27 | 2013-01-30 | 开封黄河空分集团有限公司 | Dry-method desulfuration technology for methane |
| CN102989289A (en) * | 2012-10-10 | 2013-03-27 | 贵州泰然环境科技有限责任公司 | Methane wet desulphurization device capable of recycling sulphur |
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Denomination of invention: A desulfurization system and desulfurization method for biogas containing high concentration hydrogen sulfide Effective date of registration: 20221226 Granted publication date: 20201211 Pledgee: Bank of China Zhengzhou branch of Limited by Share Ltd. culture Pledgor: Huaxia Bishui Environmental Protection Technology Co.,Ltd. Registration number: Y2022980028978 |
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