CN110756004A - Combined process for deeply purifying hydrogen sulfide and organic sulfur - Google Patents
Combined process for deeply purifying hydrogen sulfide and organic sulfur Download PDFInfo
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- CN110756004A CN110756004A CN201911042000.7A CN201911042000A CN110756004A CN 110756004 A CN110756004 A CN 110756004A CN 201911042000 A CN201911042000 A CN 201911042000A CN 110756004 A CN110756004 A CN 110756004A
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- 238000000034 method Methods 0.000 title claims abstract description 111
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 81
- 125000001741 organic sulfur group Chemical group 0.000 title claims abstract description 31
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 97
- 230000023556 desulfurization Effects 0.000 claims abstract description 97
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 60
- 239000011593 sulfur Substances 0.000 claims abstract description 60
- 239000007789 gas Substances 0.000 claims abstract description 58
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000746 purification Methods 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 230000008929 regeneration Effects 0.000 claims abstract description 22
- 238000011069 regeneration method Methods 0.000 claims abstract description 22
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- 238000011084 recovery Methods 0.000 claims abstract description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 15
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 239000006260 foam Substances 0.000 claims description 11
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000003009 desulfurizing effect Effects 0.000 claims description 8
- 239000011787 zinc oxide Substances 0.000 claims description 8
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000009279 wet oxidation reaction Methods 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 238000005553 drilling Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000005984 hydrogenation reaction Methods 0.000 claims description 4
- 235000018553 tannin Nutrition 0.000 claims description 4
- 229920001864 tannin Polymers 0.000 claims description 4
- 239000001648 tannin Substances 0.000 claims description 4
- 150000003568 thioethers Chemical class 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims description 3
- 239000011964 heteropoly acid Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000013589 supplement Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- QGJOPFRUJISHPQ-UHFFFAOYSA-N carbon disulfide Substances S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 17
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000003345 natural gas Substances 0.000 description 5
- 230000009469 supplementation Effects 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- -1 hydrogen sulfide Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012954 risk control Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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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
- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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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
- B01D53/14—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 by absorption
- B01D53/1418—Recovery of products
-
- 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
- B01D53/14—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 by absorption
- B01D53/1425—Regeneration of liquid absorbents
-
- 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
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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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—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
- B01D53/75—Multi-step processes
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- 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
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
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- B01D2257/306—Organic sulfur compounds, e.g. mercaptans
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Abstract
The invention relates to a combined process for deeply purifying hydrogen sulfide and organic sulfur.A wet desulphurization section and a dry desulphurization section are connected with the input end of a gas-liquid separator; the output ends of the wet desulphurization section and the dry desulphurization section are both connected with the input end of the purification gas separator; the output end of the wet desulphurization section is connected with the input end of the dry desulphurization section; the output end of the purification gas separator outputs purification gas; the wet desulphurization section comprises a wet desulphurization tower; the dry desulfurization section comprises a dry desulfurization tower; also comprises a desulfurization solution regeneration section and a sulfur recovery section. The desulfurization solution absorbing the hydrogen sulfide enters the regeneration tank from the bottom of the wet desulfurization tower, and then is oxidized with air self-absorbed in the regeneration tank to realize regeneration, the generated liquid is a solution recovering the desulfurization performance, and the solution recovering the desulfurization performance enters the barren solution tank and then is pumped into the wet desulfurization tower by a pump to realize circulating absorption of the hydrogen sulfide. The invention has the advantages of simple process flow, less investment, stable operation, convenient management, simple operation and high desulfurization precision.
Description
Technical Field
The invention relates to a flue gas desulfurization system and a desulfurization method, in particular to a combined process for deeply purifying hydrogen sulfide and organic sulfur.
Background
With the enactment of national energy saving law and the strictness of environmental protection laws and regulations, the problem of sulfur pollution, especially the pollution of hydrogen sulfide, not only brings serious threats to safety production and resident safety, but also causes corrosion to equipment and pipelines, brings serious potential safety hazards, and has attracted general attention of people.
In the chemical industry using coal, petroleum, natural gas and the like as raw materials, process gas in the production process often contains some sulfides, particularly hydrogen sulfide, has strong corrosivity and strong toxicity, and is one of main objects of risk control in the production process. For this purpose, the sulfur-containing gas must be subjected to desulfurization treatment.
At present, the domestic and foreign desulfurization processes are many, and are mainly divided into wet desulfurization, dry desulfurization and the like. The wet desulphurization can be divided into physical desulphurization and chemical desulphurization, the flow of the two methods is similar, both methods adopt an absorption and regeneration mode, an absorbent absorbs or reacts with a sulfur-containing component, and a pregnant solution generates the absorbent and is recycled; however, the method needs to continuously supplement the desulfurizer, has more devices and equipment, high energy consumption and complex flow, the waste liquid of the desulfurizer generated in the production process needs to be treated, the wet desulphurization precision is generally not high due to the influence of factors such as mass transfer, gas and liquid absorption balance, fluctuation of production working conditions and the like, the requirement of various catalysts on the content of sulfide in the production process cannot be met, particularly, the method has limited removal of organic sulfur, and the method is suitable for sulfur containing with large treatment capacity, high gas sulfur content and low desulphurization precision requirement. The dry desulfurization is mainly realized by utilizing the chemical adsorption and reaction of the solid desulfurizer on the sulfide, not only can remove inorganic sulfur, but also can remove organic sulfur, and can well solve the problem that the sulfide is difficult to remove due to the complex composition of the sulfide in the wet desulfurization. Therefore, the task of fine desulfurization of gas is mostly accomplished by a dry process. The dry desulfurization has high precision, generally adopts a three-tower or two-tower series-parallel process, has less investment on a desulfurization device, less equipment, simple flow, convenient operation and low energy consumption, and does not produce waste liquid and waste gas in the production process. Is suitable for treating sulfur-containing gas with small gas amount and low sulfur content.
In many sulfur-containing gas removal processes, the single use of wet oxidation desulfurization has not been able to satisfy the desulfurization precision of inorganic sulfur and organic sulfur, while dry desulfurization has not been able to achieve as high a sulfur capacity as wet desulfurization, but has high desulfurization precision and simple operation. The method combines the advantages of a wet desulfurization mode and a dry desulfurization mode, develops a purification process technology suitable for the characteristics of the low-sulfur-containing gas, optimizes a process method suitable for treating the low-sulfur-containing natural gas, and has positive significance for improving the effective sulfur capacity of the device and realizing the safe, stable and economic operation of the desulfurization device.
The prior art application number is: 201711232685.2, the name of the invention is: a wet method and dry method unite the desulfurized system of the flue gas and desulfurization method, disclose a desulfurized system of the flue gas and its desulfurization method, the said desulfurized system includes the pressurized system of dust removal, wet method desulfurized system and dry method desulfurized system; the outlet end of the dedusting and pressurizing system is respectively connected with the inlet ends of the wet desulphurization system and the dry desulphurization system; the outlet end of the wet desulphurization system is connected with the inlet end of the dry desulphurization system, so that the environmental problem caused by the emission of a wet chimney is fundamentally solved. But has the following problems that (1) the equipment is more, the occupied area is large, the flow is more complex, and the operation difficulty is increased; (2) the desulfurization absorption liquid is not reproducible, the consumption is large, and the byproducts are more. Therefore, a device which can regenerate and circularly absorb the absorption liquid and has few side reaction products is needed.
Disclosure of Invention
1. The technical problem to be solved is as follows:
aiming at the technical problems, the invention provides a combined process for deeply purifying hydrogen sulfide and organic sulfur, which combines the advantages of a wet desulfurization mode and a dry desulfurization mode, develops a purification process technology suitable for the characteristics of low-sulfur-containing gas, particularly organic sulfur, and optimizes a process method suitable for treating the low-sulfur-containing natural gas.
2. The technical scheme is as follows:
a combined process for deeply purifying hydrogen sulfide and organic sulfur comprises a wet desulphurization section and a dry desulphurization section; the raw gas containing hydrogen sulfide flows into the input end of a gas-liquid separator, and the input ends of the wet desulphurization section and the dry desulphurization section are both connected with the output end of the gas-liquid separator; the output ends of the wet desulphurization section and the dry desulphurization section are both connected with the input end of the purification gas separator; the output end of the wet desulphurization section is connected with the input end of the dry desulphurization section; the output end of the purification gas separator outputs purification gas; the method is characterized in that: the wet desulphurization section comprises a wet desulphurization tower; the dry desulfurization section comprises a dry desulfurization tower; also comprises a desulfurization solution regeneration section and a sulfur recovery section.
The desulfurization solution regeneration section comprises the following concrete steps: and the generated liquid is a solution for recovering the desulfurization performance, and the solution for recovering the desulfurization performance is pumped into the wet desulphurization tower by a pump after entering a barren solution tank to realize the cyclic absorption of the hydrogen sulfide.
The sulfur recovery section specifically comprises: sulfur foam separated out from the regeneration tank in the desulfurization solution regeneration section overflows into a sulfur foam collecting tank and is conveyed to a sulfur filtering system by a sulfur foam pump for sulfur recovery.
Furthermore, valves are arranged on connecting pipelines among the gas-liquid separator, the wet desulphurization section, the dry desulphurization section and the purification gas separator.
Furthermore, the wet desulphurization section and the dry desulphurization section are connected in series by adjusting the opening and closing of the valve.
Furthermore, the wet desulphurization section and the dry desulphurization section are connected in parallel by adjusting the on-off state of a valve.
Further, the wet desulphurization section is wet oxidation desulphurization; the wet oxidation desulfurization is one of a modified ADA process, a tannin extract process, a PDS process, an MSQ process, a complex iron process, a heteropoly acid process and a DDS process.
Further, the dry desulfurization section is used for desulfurization by a solid desulfurizer; the solid desulfurizer is one of an activated carbon method, an iron oxide method, a zinc oxide method, a molybdenum-drilling hydrogenation tandem zinc oxide method and a molecular sieve method.
Further, the desulfurization tower in the dry desulfurization comprises oxygen supplementation, and the oxygen supplementation amount is below 0.05%.
Further, the operation temperature of the desulfurizing tower in the dry desulfurization is 20-100 ℃.
Further, the organic sulfur in the raw material gas contains one or more of carbon disulfide, carbon oxysulfide, mercaptan and thioether and thiophene.
Furthermore, the removal rate of the wet desulphurization section on hydrogen sulfide is not lower than 99%, and the dry desulphurization section mainly carries out fine removal treatment on hydrogen sulfide and organic sulfur.
3. Has the advantages that:
the invention combines the advantages of wet desulphurization and dry desulphurization, develops a purification process technology which is suitable for the characteristics of low-sulfur-containing gas, particularly organic sulfur, optimizes a process method suitable for treating the low-sulfur-containing natural gas, and has positive significance for improving the effective sulfur capacity of a device and realizing the safe, stable and economic operation of a desulphurization device. The process flow is simple, the investment is less, the operation is stable, the management is convenient, the operation is simple, and the desulfurization precision is high. Can treat the removal of hydrogen sulfide and organic sulfur in the prior medium-low potential sulfur content, and is particularly suitable for the purification treatment of sulfur-containing natural gas in distributed and dispersed low-potential sulfur content and densely populated oil and gas wells and gas collection stations. The deep purification of the hydrogen sulfide and the organic sulfur meets the current increasingly severe requirements on safety and environmental protection, and has wide application prospect.
Drawings
FIG. 1 is a flow diagram of a desulfurization process of the present invention.
Detailed Description
A combined process for deeply purifying hydrogen sulfide and organic sulfur comprises a wet desulphurization section and a dry desulphurization section; the raw gas containing hydrogen sulfide flows into the input end of a gas-liquid separator, and the input ends of the wet desulphurization section and the dry desulphurization section are both connected with the output end of the gas-liquid separator; the output ends of the wet desulphurization section and the dry desulphurization section are both connected with the input end of the purification gas separator; the output end of the wet desulphurization section is connected with the input end of the dry desulphurization section; the output end of the purification gas separator outputs purification gas; the method is characterized in that: the wet desulphurization section comprises a wet desulphurization tower; the dry desulfurization section comprises a dry desulfurization tower; also comprises a desulfurization solution regeneration section and a sulfur recovery section.
The desulfurization solution regeneration section comprises the following concrete steps: and the generated liquid is a solution for recovering the desulfurization performance, and the solution for recovering the desulfurization performance is pumped into the wet desulphurization tower by a pump after entering a barren solution tank to realize the cyclic absorption of the hydrogen sulfide.
The sulfur recovery section specifically comprises: sulfur foam separated out from the regeneration tank in the desulfurization solution regeneration section overflows into a sulfur foam collecting tank and is conveyed to a sulfur filtering system by a sulfur foam pump for sulfur recovery.
Furthermore, valves are arranged on connecting pipelines among the gas-liquid separator, the wet desulphurization section, the dry desulphurization section and the purification gas separator.
Furthermore, the wet desulphurization section and the dry desulphurization section are connected in series by adjusting the opening and closing of the valve.
Furthermore, the wet desulphurization section and the dry desulphurization section are connected in parallel by adjusting the on-off state of a valve.
Further, the wet desulphurization section is wet oxidation desulphurization; the wet oxidation desulfurization is one of a modified ADA process, a tannin extract process, a PDS process, an MSQ process, a complex iron process, a heteropoly acid process and a DDS process.
Further, the dry desulfurization section is used for desulfurization by a solid desulfurizer; the solid desulfurizer is one of an activated carbon method, an iron oxide method, a zinc oxide method, a molybdenum-drilling hydrogenation tandem zinc oxide method and a molecular sieve method.
Further, the desulfurization tower in the dry desulfurization comprises oxygen supplementation, and the oxygen supplementation amount is below 0.05%.
Further, the operation temperature of the desulfurizing tower in the dry desulfurization is 20-100 ℃.
Further, the organic sulfur in the raw material gas contains one or more of carbon disulfide, carbon oxysulfide, mercaptan and thioether and thiophene.
Furthermore, the removal rate of the wet desulphurization section on hydrogen sulfide is not lower than 99%, and the dry desulphurization section mainly carries out fine removal treatment on hydrogen sulfide and organic sulfur.
The process of the invention is shown as the attached figure 1: the raw material gas containing hydrogen sulfide enters a raw material gas-liquid separator 1 and then enters a wet desulphurization tower 3 to be in gas-liquid contact with desulphurization liquid to carry out the rough desulphurization of the hydrogen sulfide; the sulfur-containing gas after the coarse removal enters a dry-method desulfurization tower 4 for fine removal of hydrogen sulfide and organic sulfur, and the purified gas enters an external discharge pipeline after passing through a purification gas separator 2; the desulfurization solution absorbing the hydrogen sulfide enters a regeneration tank 5 from the bottom of a wet desulfurization tower 3, is oxidized and regenerated with air which is self-absorbed, the solution recovering the desulfurization performance enters a barren solution tank 6, and is pumped into the wet desulfurization tower 3 by a barren solution pump 9 to circularly absorb the hydrogen sulfide; the sulfur separated out from the regeneration tank 5 enters a sulfur foam collecting tank 7 and is sent to a sulfur filtering system by a sulfur foam pump 8 for sulfur recovery.
The specific embodiment is as follows:
example 1: the content of sulfureted hydrogen in the sulfur-containing gas is 5g/m3The content of sulfur-oxidized Carbon (COS) is 22mg/m3。
Wherein the wet desulphurization section adopts an improved ADA method, the dry desulphurization section adopts special functional active carbon, and the process is series absorption.
The hydrogen sulfide content of the gas containing hydrogen sulfide is less than or equal to 35mg/m after wet desulphurization3COS content of 20mg/m3(ii) a The hydrogen sulfide is not detected after the dry desulfurization, and the content of COS is less than or equal to 1mg/m3And (5) after purification treatment.
Example 2: the content of sulfureted hydrogen in the sulfur-containing gas is 3g/m3The content of mercaptan (RSH) is 15mg/m3。
The wet desulfurization section adopts a matching iron method, the dry desulfurization section adopts a functional iron oxide method, and the process is series absorption.
The hydrogen sulfide content of the gas containing hydrogen sulfide is less than or equal to 25mg/m after wet desulphurization3The content of RSH is 15mg/m3(ii) a Hydrogen sulfide is not detected after dry desulfurization, and the content of RSH is less than or equal to 0.5mg/m3And (5) after purification treatment.
Example 3: the content of sulfureted hydrogen in the sulfur-containing gas is 6g/m3Thioether (RSR) content of 23mg/m3。
The wet desulfurizing section adopts tannin extract process, the dry desulfurizing section adopts iron oxide process, and the process is series absorption.
The hydrogen sulfide content of the gas containing the hydrogen sulfide is less than or equal to 38mg/m after wet desulphurization3RSR content of 20mg/m3(ii) a Hydrogen sulfide is not detected after dry desulfurization, and the RSR content is less than or equal to 1mg/m3And (5) after purification treatment.
Example 4: the content of sulfureted hydrogen in the sulfur-containing gas is 5g/m3Thiophene (CHS) content of-15 mg/m3。
Wherein the wet desulphurization section adopts a PDS method, the dry desulphurization section adopts a zinc oxide method, and the process is series absorption.
The hydrogen sulfide content of the gas containing hydrogen sulfide is less than or equal to 25mg/m after wet desulphurization3CHS content of 15mg/m3(ii) a Hydrogen sulfide is not detected after dry desulfurization, and CHS content is less than or equal to 0.5mg/m3And (5) after purification treatment.
Example 5: the content of sulfureted hydrogen in the sulfur-containing gas is 6g/m3Carbon disulfide (CS) content of 15mg/m3The content of sulfur-oxidized Carbon (COS) is 7mg/m3。
Wherein the wet desulphurization section adopts an improved ADA method, the dry desulphurization section adopts special functional active carbon, and the process is series absorption.
The hydrogen sulfide content of the gas containing hydrogen sulfide is less than or equal to 35mg/m after wet desulphurization3CS content of 15mg/m3，COS content is 7mg/m3(ii) a Hydrogen sulfide is not detected after dry desulfurization, and the content of CS is less than or equal to 1mg/m3After purification treatment, the content of COS is less than or equal to 1mg/m3And (5) after purification treatment.
Example 6: the content of sulfureted hydrogen in the sulfur-containing gas is 4g/m3The content of carbon disulfide (CS) is 22mg/m3The content of sulfur-oxidized Carbon (COS) is 15mg/m3The content of mercaptan (RSH) is 15mg/m3。
The wet desulfurization section adopts a matching iron method, the dry desulfurization section adopts a functional iron oxide method, and the process is series absorption.
The hydrogen sulfide content of the gas containing hydrogen sulfide is less than or equal to 25mg/m after wet desulphurization3CS content of 22mg/m3、COS content of 15mg/m3RSH content of 15mg/m3(ii) a Hydrogen sulfide is not detected after dry desulfurization, and the CS content is 0.5mg/m3、COS content of 0.6mg/m3The content of RSH is less than or equal to 0.5mg/m3And (5) after purification treatment.
Example 7: the content of sulfureted hydrogen in the sulfur-containing gas is 8g/m3The content of sulfur-oxidized Carbon (COS) is 22mg/m3The content of mercaptan (RSH) is 22mg/m3。
Wherein the wet desulphurization section adopts an improved ADA method, the dry desulphurization section adopts special functional active carbon, and the process is series absorption.
The hydrogen sulfide content of the gas containing hydrogen sulfide is less than or equal to 45mg/m after wet desulphurization3COS content of 22mg/m3The content of RSH is 22mg/m3(ii) a After dry desulfurization, the hydrogen sulfide is not detected, and the content of COS is 0.2mg/m3RSH content of 0.32mg/m3(ii) a And (5) after purification treatment.
Example 8: the content of sulfureted hydrogen in the sulfur-containing gas is 3g/m3Thioether (RSR) content of 15mg/m3And thiophene (CHS) content of 15mg/m3。
Wherein the wet desulphurization section adopts an MSQ method, the dry desulphurization section adopts a functional iron oxide method, and the process is series absorption.
The hydrogen sulfide content of the gas containing hydrogen sulfide is less than or equal to 25mg/m after wet desulphurization3RSR content of-15 mg/m3CHS content of 15mg/m3(ii) a Hydrogen sulfide is not detected after dry desulfurization, and the content of RSH is less than or equal to 0.5mg/m3CHS content is less than or equal to 0.4mg/m3And (5) after purification treatment.
Example 9: the content of sulfureted hydrogen in the sulfur-containing gas is 5g/m3The content of mercaptan (RSH) is 20mg/m3The content of thioether (RSR) is 20mg/m3。
Wherein the wet desulphurization section adopts a PDS method, the dry desulphurization section adopts special functional active carbon, and the process is series absorption.
The hydrogen sulfide content of the gas containing hydrogen sulfide is less than or equal to 35mg/m after wet desulphurization3The content of RSH is 20mg/m3RSR content of 20mg/m3(ii) a Hydrogen sulfide is not detected after dry desulfurization, and the content of RSH is less than or equal to 1mg/m3The RSR content is less than or equal to 1mg/m3And (5) after purification treatment.
Example 10: the content of sulfureted hydrogen in the sulfur-containing gas is 3g/m3The content of sulfur-oxidized Carbon (COS) is 25mg/m3。
The wet desulfurization section adopts a matched iron method, the dry desulfurization section adopts a drilling molybdenum hydrogenation tandem zinc oxide method, and the process is parallel absorption.
The hydrogen sulfide content of the gas containing hydrogen sulfide is less than or equal to 15mg/m after wet desulphurization3COS content of 15mg/m3(ii) a The hydrogen sulfide is not detected after the dry desulfurization, and the content of COS is less than or equal to 0.5mg/m3And (5) after purification treatment.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (10)
1. A combined process for deeply purifying hydrogen sulfide and organic sulfur comprises a wet desulphurization section and a dry desulphurization section; the raw gas containing hydrogen sulfide flows into the input end of a gas-liquid separator, and the input ends of the wet desulphurization section and the dry desulphurization section are both connected with the output end of the gas-liquid separator; the output ends of the wet desulphurization section and the dry desulphurization section are both connected with the input end of the purification gas separator; the output end of the wet desulphurization section is connected with the input end of the dry desulphurization section; the output end of the purification gas separator outputs purification gas; the method is characterized in that: the wet desulphurization section comprises a wet desulphurization tower; the dry desulfurization section comprises a dry desulfurization tower; also comprises a desulfurization solution regeneration section and a sulfur recovery section;
the desulfurization solution regeneration section comprises the following concrete steps: the desulfurization solution absorbing hydrogen sulfide in the wet desulfurization section enters a regeneration tank from the bottom of the wet desulfurization section, and then is oxidized with air self-absorbed in the regeneration tank to realize regeneration, the generated liquid is a solution recovering desulfurization performance, and the solution recovering desulfurization performance enters a barren solution tank and then is pumped into the wet desulfurization tower by a pump to realize cyclic absorption of hydrogen sulfide;
the sulfur recovery section specifically comprises: sulfur foam separated out from the regeneration tank in the desulfurization solution regeneration section overflows into a sulfur foam collecting tank and is conveyed to a sulfur filtering system by a sulfur foam pump for sulfur recovery.
2. The integrated process for the deep purification of hydrogen sulfide and organic sulfur according to claim 1, wherein: and valves are arranged on connecting pipelines among the gas-liquid separator, the wet desulphurization section, the dry desulphurization section and the purification gas separator.
3. The integrated process for the deep purification of hydrogen sulfide and organic sulfur according to claim 2, wherein: the wet desulphurization section and the dry desulphurization section are connected in series by adjusting the opening and closing of the valve.
4. The integrated process for the deep purification of hydrogen sulfide and organic sulfur according to claim 2, wherein: the wet desulphurization section and the dry desulphurization section are connected in parallel by adjusting the on-off of a valve.
5. The integrated process for the deep purification of hydrogen sulfide and organic sulfur according to claim 1, wherein: the wet desulphurization section is used for desulphurization by a wet oxidation method; the wet oxidation desulfurization is one of a modified ADA process, a tannin extract process, a PDS process, an MSQ process, a complex iron process, a heteropoly acid process and a DDS process.
6. The integrated process for the deep purification of hydrogen sulfide and organic sulfur according to claim 1, wherein: the dry desulfurization section is used for desulfurizing by a solid desulfurizing agent; the solid desulfurizer is one of an activated carbon method, an iron oxide method, a zinc oxide method, a molybdenum-drilling hydrogenation tandem zinc oxide method and a molecular sieve method.
7. The integrated process for the deep purification of hydrogen sulfide and organic sulfur according to claim 1, wherein: the desulfurizing tower in the dry desulfurization comprises oxygen supplement, and the supplement amount of the oxygen is below 0.05%.
8. The integrated process for the deep purification of hydrogen sulfide and organic sulfur according to claim 1, wherein: the operation temperature of the desulfurizing tower in the dry desulfurization is 20-100 ℃.
9. The integrated process for the deep purification of hydrogen sulfide and organic sulfur according to claim 1, wherein: the organic sulfur in the raw material gas contains one or more of carbon disulfide, carbon oxysulfide, mercaptan and thioether and thiophene.
10. The integrated process for the deep purification of hydrogen sulfide and organic sulfur according to claim 1, wherein: the wet desulphurization section has a removal rate of hydrogen sulfide of not less than 99%, and the dry desulphurization section is mainly used for fine removal treatment of hydrogen sulfide and organic sulfur.
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