CN117942739A - Hydrogen sulfide-containing gas treatment system and hydrogen sulfide-containing gas treatment method - Google Patents
Hydrogen sulfide-containing gas treatment system and hydrogen sulfide-containing gas treatment method Download PDFInfo
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- 239000007789 gas Substances 0.000 title claims abstract description 467
- 238000000034 method Methods 0.000 title claims abstract description 81
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910000037 hydrogen sulfide Inorganic materials 0.000 title claims abstract description 78
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 229
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 207
- 239000011593 sulfur Substances 0.000 claims abstract description 205
- 238000001179 sorption measurement Methods 0.000 claims abstract description 202
- 239000003463 adsorbent Substances 0.000 claims abstract description 190
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 185
- 239000001257 hydrogen Substances 0.000 claims abstract description 176
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 150
- 230000008929 regeneration Effects 0.000 claims abstract description 73
- 238000011069 regeneration method Methods 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- 238000010521 absorption reaction Methods 0.000 claims abstract description 51
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 30
- 238000000746 purification Methods 0.000 claims abstract description 29
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 192
- 238000001816 cooling Methods 0.000 claims description 128
- 238000005984 hydrogenation reaction Methods 0.000 claims description 53
- 238000003860 storage Methods 0.000 claims description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 15
- 238000010791 quenching Methods 0.000 claims description 15
- 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 15
- 230000000171 quenching effect Effects 0.000 claims description 14
- 239000002918 waste heat Substances 0.000 claims description 14
- 229910044991 metal oxide Inorganic materials 0.000 claims description 6
- 150000004706 metal oxides Chemical class 0.000 claims description 6
- 239000006096 absorbing agent Substances 0.000 claims description 5
- 239000000571 coke Substances 0.000 claims description 5
- 238000011084 recovery Methods 0.000 abstract description 53
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 35
- 239000003546 flue gas Substances 0.000 abstract description 35
- 208000012839 conversion disease Diseases 0.000 description 61
- 239000003054 catalyst Substances 0.000 description 53
- 239000007795 chemical reaction product Substances 0.000 description 45
- 239000007788 liquid Substances 0.000 description 40
- 238000010438 heat treatment Methods 0.000 description 37
- 150000002431 hydrogen Chemical class 0.000 description 26
- 238000009833 condensation Methods 0.000 description 23
- 230000005494 condensation Effects 0.000 description 23
- 238000004064 recycling Methods 0.000 description 17
- 238000006477 desulfuration reaction Methods 0.000 description 16
- 230000023556 desulfurization Effects 0.000 description 16
- 238000002955 isolation Methods 0.000 description 16
- 230000000630 rising effect Effects 0.000 description 13
- 239000002250 absorbent Substances 0.000 description 10
- 230000002745 absorbent Effects 0.000 description 10
- 238000007599 discharging Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 4
- -1 O 2 Chemical compound 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910000431 copper oxide Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000003345 natural gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007809 chemical reaction catalyst Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 description 2
- 229940043276 diisopropanolamine Drugs 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
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
- B01D53/005—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 heat treatment
-
- 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
- B01D53/04—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 with stationary adsorbents
-
- 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
- B01D53/343—Heat recovery
-
- 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
- B01D53/86—Catalytic 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
- B01D53/74—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23J—REMOVAL OR TREATMENT OF COMBUSTION PRODUCTS OR COMBUSTION RESIDUES; FLUES
- F23J15/00—Arrangements of devices for treating smoke or fumes
- F23J15/02—Arrangements of devices for treating smoke or fumes of purifiers, e.g. for removing noxious material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/30—Sulfur compounds
- B01D2257/302—Sulfur oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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- Engineering & Computer Science (AREA)
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- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention relates to the technical field of sulfur-containing flue gas treatment, and discloses a treatment system and a treatment method for hydrogen sulfide-containing gas. The system comprises a thermal reaction unit (1), a catalytic reaction unit (2), a tail gas purification unit (3) and an adsorption unit (4) which are connected in sequence; the adsorption unit (4) comprises a connected moving adsorbent bed (41) loaded with adsorbent and a regenerator (42). The system adopts the movable adsorption bed to carry out SO 2 adsorption on the incineration tail gas, can realize near zero emission of the sulfur device flue gas SO 2 with the emission concentration less than or equal to 10mg/m 3, and adopts the hydrogen-containing hydrogen sulfide removal tail gas from the absorption tower as a regeneration gas source of the adsorbent, SO that the use loss of the adsorbent can be reduced. The treatment method of the gas containing hydrogen sulfide based on the system can realize the closed cycle of sulfur resources in the treatment process, and the total sulfur recovery rate is obviously improved.
Description
Technical Field
The invention relates to the technical field of sulfur-containing flue gas treatment, in particular to a treatment system and a treatment method for hydrogen sulfide-containing gas.
Background
Sulfur dioxide is widely regarded as a main atmospheric pollutant, and the control of pollution and the reduction of sulfur dioxide emission are important tasks for realizing sustainable development of society. The requirements in emission standards for pollutants for the oil refining industry (GB 31570-2015) published on 4 months and 16 days of 2015 are as follows: the limit value of the emission concentration of the sulfur dioxide in the flue gas of the sulfur device is generally lower than 400mg/Nm 3, and the limit value of the emission concentration of the sulfur dioxide in the flue gas of the sulfur device is lower than 100mg/Nm 3.
The existing sulfur device 300 in China is the rest, and the sulfur recovery device is used as the final checkpoint, not only a set of production devices, but also a set of environment protection devices. At present, two types of processes are mainly adopted for domestic sulfur recovery, namely LS-DeGAS complete technology for reducing sulfur dioxide emission of a sulfur recovery device, which is formed by researching and developing a catalyst by China and petrochemical company, and the technology can be used for reducing the concentration of the sulfur dioxide emission of the flue gas of the sulfur recovery device to below 100mg/Nm 3. However, the process cannot ensure the long-term stable standard emission of the sulfur recovery device due to factors such as the scale of the device, the composition of the acid gas, the process route and the like. Another kind of process is alkali liquor absorption method, which mainly uses alkaline solution as absorbent to absorb and remove sulfur dioxide in flue gas to generate sodium sulfite, and then generates sodium sulfate through oxidation. The main defects of the process are that the high-concentration salt-containing wastewater produced by the process has strong corrosiveness, so that the device cannot normally operate for a long time, the produced salt-containing wastewater cannot be directly discharged, the treatment difficulty is high, the investment is high, secondary pollution is generated, and the like.
The existing sulfur technology has difficulty in meeting the stricter low-sulfur emission requirements. Therefore, the novel process which can realize low sulfur emission of the sulfur recovery device and can stably run for a long time is provided, and has important significance for the development of the refining and coal chemical industry.
Disclosure of Invention
Aiming at the problems that the emission concentration of flue gas SO 2 in the prior sulfur recovery process is still higher and the device is difficult to stably operate for a long time, the invention provides a treatment system and a treatment method for hydrogen sulfide-containing gas.
In order to achieve the above object, a first aspect of the present invention provides a treatment system for a hydrogen sulfide-containing gas, the system comprising a thermal reaction unit 1, a catalytic reaction unit 2, an exhaust gas purification unit 3, and an adsorption unit 4, which are connected in this order;
the thermal reaction unit 1 is used for carrying out thermal reaction on the gas containing hydrogen sulfide to obtain sulfur and process gas;
The catalytic reaction unit 2 is used for carrying out a claus conversion reaction on the process gas to obtain sulfur and claus tail gas;
the tail gas purifying unit 3 is used for sequentially carrying out hydrotreatment and dehydrosulfuration on the claus tail gas to obtain hydrogen-containing dehydrosulfuration tail gas, wherein the hydrogen-containing dehydrosulfuration tail gas is divided into two streams of hydrogen-containing dehydrosulfuration tail gas-I and hydrogen-containing dehydrosulfuration tail gas-II, and the hydrogen-containing dehydrosulfuration tail gas-I is subjected to incineration treatment to obtain the incineration tail gas containing sulfur dioxide;
The adsorption unit 4 comprises a movable adsorption bed 41 and a regenerator 42 which are connected and loaded with an adsorbent, and is used for carrying out adsorption and sulfur dioxide removal treatment on the incineration tail gas by using the adsorbent to obtain purified gas; and performing thermal regeneration treatment on the adsorbent to be regenerated obtained after adsorption and sulfur dioxide removal treatment by using at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II as regeneration gas to obtain a regenerated adsorbent and regeneration gas containing sulfur dioxide;
Wherein the regenerated adsorbent is circulated back to the moving adsorbent bed 41, and the regenerated gas containing sulfur dioxide is returned to at least one of the thermal reaction unit 1, the catalytic reaction unit 2, and the exhaust gas purifying unit 3.
The second aspect of the present invention provides a method for treating a hydrogen sulfide-containing gas, comprising:
(1) Carrying out thermal reaction on the gas containing hydrogen sulfide to obtain sulfur and process gas;
(2) Carrying out a Claus conversion reaction on the process gas to obtain sulfur and Claus tail gas;
(3) The Claus tail gas is subjected to hydrotreatment and dehydrosulfurization in sequence to obtain hydrogen-containing dehydrosulfurization tail gas, wherein the hydrogen-containing dehydrosulfurization tail gas is divided into hydrogen-containing dehydrosulfurization tail gas-I and hydrogen-containing dehydrosulfurization tail gas-II, and the hydrogen-containing dehydrosulfurization tail gas-I is subjected to incineration treatment to obtain sulfur dioxide-containing incineration tail gas;
(4) Absorbing and removing sulfur dioxide from the incineration tail gas by using an adsorbent to obtain purified gas; and performing thermal regeneration treatment on the adsorbent to be regenerated obtained after adsorption and sulfur dioxide removal treatment by using at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II as regeneration gas to obtain a regenerated adsorbent and regeneration gas containing sulfur dioxide;
Wherein the regenerated adsorbent is recycled back to the adsorption sulfur dioxide removal treatment; the sulfur dioxide-containing regeneration gas is recycled back to at least one of the thermal reaction, the claus conversion reaction, and the hydrotreatment.
Through the technical scheme, the invention can obtain the following beneficial effects:
(1) The system provided by the invention fully utilizes the existing conditions of the sulfur device, adopts the movable adsorption bed to carry out SO 2 adsorption on the incineration tail gas, can realize near zero emission of the flue gas SO 2 emission concentration of less than or equal to 10mg/m 3 of the sulfur device, and preferably reaches the emission concentration of less than or equal to 5mg/m 3 of SO 2;
(2) The hydrogen sulfide-removed tail gas containing hydrogen from the absorption tower is used as a regeneration gas source of the adsorbent, so that the use loss of the adsorbent can be reduced, and the loss of the adsorbent is less than or equal to 1wt%/1000h;
(3) The closed cycle of sulfur resources can be realized, the regenerated gas containing sulfur dioxide generated after the adsorbent regeneration can be returned to a sulfur recovery device of the system to continuously recover the sulfur resources, and the total sulfur recovery rate of the system is close to 100%;
(4) The waste heat of devices in the system is fully utilized for heat exchange, so that the operation energy consumption of the system can be effectively reduced;
(5) The process flow is simple, the equipment in the adsorption unit is less, the operation and control are easy, the investment is low, and no secondary pollution is caused.
Drawings
FIG. 1 is a schematic view of a treatment system for a hydrogen sulfide containing gas according to one embodiment of the present invention.
Description of the reference numerals
1-Thermal reaction unit 2-catalytic reaction unit 3-tail gas purifying unit
4-Adsorption unit 11-sulfur-producing furnace 12-first cooling device
21-Primary converter 22-secondary converter 23-second cooling device
24-Third cooling device 31-hydrogenation device 32-fourth cooling device
33-Quench tower 34-absorber tower 35-incinerator
36-Claus tail gas heater 41-moving adsorbent bed 411-reservoir
412-Adsorption layer 413-discharge layer 42-regenerator
43 Lifting device 44 waste heat boiler 45 first heat exchanger
46-Second heat exchanger 47-auxiliary heater 48-chimney
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The first aspect of the present invention provides a treatment system for a hydrogen sulfide-containing gas, as shown in fig. 1, the system comprising a thermal reaction unit 1, a catalytic reaction unit 2, an exhaust gas purification unit 3, and an adsorption unit 4, which are connected in sequence;
the thermal reaction unit 1 is used for carrying out thermal reaction on the gas containing hydrogen sulfide to obtain sulfur and process gas;
The catalytic reaction unit 2 is used for carrying out a claus conversion reaction on the process gas to obtain sulfur and claus tail gas;
the tail gas purifying unit 3 is used for sequentially carrying out hydrotreatment and dehydrosulfuration on the claus tail gas to obtain hydrogen-containing dehydrosulfuration tail gas, wherein the hydrogen-containing dehydrosulfuration tail gas is divided into two streams of hydrogen-containing dehydrosulfuration tail gas-I and hydrogen-containing dehydrosulfuration tail gas-II, and the hydrogen-containing dehydrosulfuration tail gas-I is subjected to incineration treatment to obtain the incineration tail gas containing sulfur dioxide;
The adsorption unit 4 comprises a movable adsorption bed 41 and a regenerator 42 which are connected and loaded with an adsorbent, and is used for carrying out adsorption and sulfur dioxide removal treatment on the incineration tail gas by using the adsorbent to obtain purified gas; and performing thermal regeneration treatment on the adsorbent to be regenerated obtained after adsorption and sulfur dioxide removal treatment by using at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II as regeneration gas to obtain a regenerated adsorbent and regeneration gas containing sulfur dioxide;
Wherein the regenerated adsorbent is circulated back to the moving adsorbent bed 41, and the regenerated gas containing sulfur dioxide is returned to at least one of the thermal reaction unit 1, the catalytic reaction unit 2, and the exhaust gas purifying unit 3.
According to the invention, the hydrogen sulfide-containing gas refers to H 2 S-containing gas generated in the fields of natural gas purification, refining and coal chemical industry, and the components of the hydrogen sulfide-containing gas comprise H 2S、CO2、H2O、NH3, hydrocarbons and the like. Preferably, the content of H 2 S in the hydrogen sulfide-containing gas is 30-90% by volume, preferably 50-85% by volume.
According to the invention, the thermal reaction unit 1 comprises a sulfur producer 11 and a first cooling device 12 connected in sequence. In the invention, the gas containing hydrogen sulfide enters the thermal reaction unit 1, is firstly mixed with air in the sulfur producing furnace 11 and combusted to obtain a thermal reaction product gas containing S, H 2S、SO2, COS and CS 2; the hot reaction product gas is then introduced into the first cooling means 12 for condensation, wherein S is condensed and separated as elemental sulfur, preferably into a liquid sulfur pool outside the boundary zone. The hot reaction product gas after separation of elemental sulphur, i.e. the process gas, leaves the first cooling device 12 and enters the catalytic reaction unit 2.
In the present invention, the sulfur producing furnace 11 may be a conventional sulfur producing combustion furnace in the art, and the present invention is not particularly limited.
According to the invention, the content of H 2 S in the process gas is 3-10v%; the content of SO 2 is 1.5-5% by volume; the COS content is 0.2-1v%.
According to the present invention, the catalytic reaction unit 2 includes a primary converter 21 and a secondary converter 22 connected in sequence; wherein the primary converter 21 is connected to the first cooling device 12.
In the present invention, the process gas enters the catalytic reaction unit 2, and sequentially enters a multistage converter to perform a claus conversion reaction, preferably two-stage conversion. Specifically, the process gas enters a primary converter 21, the primary converter 21 carries a first sulfur recovery catalyst, under the existence of the first sulfur recovery catalyst, H 2 S in the process gas and SO 2 undergo a Claus reaction to generate elemental sulfur, COS and CS 2 undergo a hydrolysis reaction to generate H 2 S, and a sulfur-containing primary conversion reaction product is obtained; the primary conversion reaction product is sulfur separated before entering the secondary converter 22; the secondary converter 22 carries a second sulfur recovery catalyst, in the presence of the second sulfur recovery catalyst, the H 2 S in the primary conversion reaction product and the SO 2 continue to undergo claus reaction to generate elemental sulfur, SO as to obtain a sulfur-containing secondary conversion reaction product, and the sulfur is separated to obtain claus tail gas, and the claus tail gas enters the tail gas purification unit 3. The claus tail gas contains H 2S、SO2、COS、CS2 and trace amounts of S. Preferably, the content of H 2 S in the Claus tail gas is 0.5-2% by volume; the content of SO 2 is 0.3-1% v; the COS content is 0.01-0.05v%.
In the present invention, the first sulfur recovery catalyst and the second sulfur recovery catalyst may be claus conversion reaction catalysts conventional in the art, and may each be independently selected from at least one of a oxygen-leaking type sulfur recovery catalyst, a titanium oxide-based sulfur recovery catalyst, and an alumina-based sulfur recovery catalyst.
According to the invention, the catalytic reaction unit 2 further comprises second cooling means 23 and third cooling means 24; wherein the second cooling device 23 is connected to the primary converter 21 and the secondary converter 22, respectively; the third cooling device 24 is connected to the secondary converter 22. In the present invention, the second cooling device 23 is used for condensing the primary conversion reaction product, and the S in the primary conversion reaction product is separated out in the form of elemental sulfur after condensation, and is preferably discharged into a liquid sulfur pool outside the boundary region; the third cooling device 24 is used for condensing the secondary conversion reaction product, and S in the secondary conversion reaction product is separated out in the form of elemental sulfur after condensation, and is preferably discharged into a liquid sulfur pool outside the boundary region.
In the present invention, the first cooling device 12, the second cooling device 23 and the third cooling device 24 may employ cooling separation devices which are conventional in the art, and the present invention is not particularly limited thereto.
According to the present invention, the exhaust gas purifying unit 3 includes a hydrogenation apparatus 31, an absorption tower 34, and an incinerator 35, which are sequentially connected; wherein the hydrogenation unit 31 is connected to the third cooling unit 24.
In the invention, the claus tail gas enters a tail gas purifying unit 3, firstly enters a hydrogenation device 31, and is subjected to hydrogenation reaction under the action of a hydrogenation catalyst, SO 2、COS、CS2, S and the like in the claus tail gas are converted into H 2 S, and hydrogenated tail gas containing H 2 S is obtained; introducing the hydrogenated tail gas containing H 2 S from the lower part of the absorption tower 34, enabling gas to be in countercurrent contact with a desulfurization absorbent in the absorption tower 34 in the ascending process, absorbing H 2 S in the gas by the desulfurization absorbent, and finally obtaining hydrogen-containing dehydrosulfide tail gas at the top of the absorption tower 34; the hydrogen-containing hydrogen sulfide removal tail gas is divided into two parts, namely hydrogen-containing hydrogen sulfide removal tail gas-I and hydrogen-containing hydrogen sulfide removal tail gas-II, and the hydrogen-containing hydrogen sulfide removal tail gas-I enters the incinerator 35 for incineration treatment to obtain the incineration tail gas containing sulfur dioxide. The hydrogen sulfide-removed tail gas-II and the incineration tail gas containing hydrogen enter the adsorption unit 4 from different lines.
In the present invention, the hydrogen-containing dehydrosulfidation tail gas contains H 2, a small amount of remaining H 2 S, and COS. Preferably, the content of H 2 in the hydrogen-containing hydrogen sulfide removal tail gas is 2-8% by volume, preferably 3-5% by volume; h 2 S content is 5-200ppm; the COS content is 2-100ppm.
In the present invention, the incineration tail gas contains water vapor, O 2、SO2、N2、CO2, CO, and the like. Preferably, the content of SO 2 in the incineration tail gas is 50-1000mg/m 3, preferably 50-500mg/m 3.
According to the present invention, the exhaust gas purifying unit 3 further includes a quenching tower 33, and the quenching tower 33 is connected to the hydrogenation apparatus 31 and the absorption tower 34, respectively. In the present invention, the quenching tower 33 is used for cooling the hydrogenated tail gas containing H 2 S from the hydrogenation device 31. Preferably, a fourth cooling device 32 is arranged before the quenching tower 33, that is, the hydrogenated tail gas containing H 2 S sequentially passes through the fourth cooling device 32 and the quenching tower 33, and enters the absorption tower 34 after being cooled.
According to the present invention, in the exhaust gas purifying unit 3, a claus exhaust gas heater 36 is preferably provided in the connection line between the third cooling device 24 and the hydrogenation device 31 for preheating the claus exhaust gas before the hydrotreating.
In the present invention, the hydrogenation unit 31, the fourth cooling unit 32, the quenching tower 33, the absorption tower 34, the incinerator 35, and the claus tail gas heater 36 may be selected by using conventional means in the art, and the present invention is not particularly limited.
According to the invention, the adsorption unit 4 further comprises a waste heat boiler 44, a first heat exchanger 45 and a second heat exchanger 46, which are connected in sequence. Wherein the waste heat boiler 44 is connected to the incinerator 35; the first heat exchanger 45 is connected to the absorber 34 and the regenerator 42, respectively; the second heat exchanger 46 is connected to the moving adsorbent bed 41.
According to the present invention, for the connection mode of the first heat exchanger 45 and the absorption tower 34, specifically, the first heat exchanger 45 is connected to the product gas outlet at the top of the absorption tower 34.
According to the present invention, the moving adsorbent bed 41 includes a storage layer 411, an adsorption layer 412 and a discharge layer 413 sequentially disposed from top to bottom. In the moving adsorbent bed 41, the storage layer 411, the adsorption layer 412 and the discharge layer 413 are separated by using openable isolation baffles, so as to form a storage functional area, an adsorption functional area and a discharge functional area respectively. Specifically, the storage layer 411 is configured to store fresh adsorbent or regenerated adsorbent, an adsorbent inlet is provided at the upper portion of the storage layer 411, and a separation baffle between the bottom and the adsorption layer 412 can be opened and closed, so as to discharge the adsorbent stored in the storage layer 411 to the adsorption layer 412; the adsorption layer 412 is used for performing adsorption sulfur dioxide removal treatment by contacting incineration tail gas with an adsorbent, the adsorption layer 412 is provided with an air inlet and an air outlet, the air inlet is positioned at the lower part of the adsorption layer 412, the air outlet is positioned at the upper part of the adsorption layer 412, and an isolation baffle between the bottom of the adsorption layer 412 and the discharge layer 413 can be opened and closed to realize discharge of the adsorbent to be regenerated generated by the adsorption layer 412 to the discharge layer 413; the discharging layer 413 is used for storing the adsorbent to be regenerated, which is saturated by adsorption of sulfur dioxide from the adsorption layer 412.
According to the present invention, the regenerator 42 is provided with an adsorbent regeneration chamber, an adsorbent inlet to be regenerated and a regenerated adsorbent outlet; the regenerator 42 is provided with a heating coil, and the adsorbent can be regenerated by supplying heat to the adsorbent to be regenerated and raising the temperature through introducing a heat medium into the heating coil.
According to the invention, the reservoir 411 is connected to the regenerator 42; the adsorption layer 412 is connected to the second heat exchanger 46; the discharge layer 413 is connected to the regenerator 42.
According to the present invention, for the connection of the storage layer 411 to the regenerator 42, specifically, the storage layer 411 is connected to the regenerated adsorbent outlet of the regenerator 42 through a lifting device 43.
According to the present invention, for the connection mode of the adsorption layer 412 and the second heat exchanger 46, specifically, the air inlet and the air outlet of the adsorption layer 412 are connected to the second heat exchanger 46, respectively.
According to the invention, for the way in which the discharge layer 413 is connected to the regenerator 42, in particular, the discharge layer 413 is connected to the adsorbent inlet of the regenerator 42 to be regenerated.
According to the invention, the SO 2 content of the purified gas obtained by the adsorption sulfur dioxide removal treatment by the movable adsorption bed 41 is less than or equal to 10mg/m 3, preferably less than or equal to 5mg/m 3.
According to the invention, the adsorption unit 4 further comprises an auxiliary heater 47, the auxiliary heater 47 being connected to the regenerator 42 and the first heat exchanger 45, respectively. Wherein, for the connection mode of the auxiliary heater 47 and the regenerator 42, specifically, the auxiliary heater 47 is connected with at least the heating coil air inlet of the regenerator 42.
According to the present invention, for the connection of the auxiliary heater 47 and the regenerator 42, it is preferable that the auxiliary heater 47 is connected to the heating coil inlet of the regenerator 42 and the adsorbent regeneration chamber, respectively.
According to the invention, the regenerator 42 may also be connected to the first heat exchanger 45 by means of a circulating heating line. Wherein, for the connection mode of the circulation heating line and the regenerator 42, specifically, the circulation heating line is connected with the heating coil air outlet of the regenerator 42.
According to the present invention, the regenerator 42 is connected to at least one of the sulfur producing furnace 11, the primary converter 21, the secondary converter 22, and the hydrogenation apparatus 31.
According to the present invention, the adsorbent is at least one selected from the group consisting of activated carbon, activated coke, metal oxide and molecular sieve, preferably activated carbon.
In the present invention, the metal oxide that can be used as the adsorbent includes, but is not limited to, copper oxide, iron oxide, zinc oxide, or the like, and copper oxide is preferable.
In the present invention, the molecular sieve which can be used as the adsorbent includes, but is not limited to, an X-type molecular sieve, a Y-type molecular sieve, a NaY molecular sieve, etc., preferably a NaY molecular sieve.
According to the invention, the adsorbent preferably has an initial sulfur capacity of 100-250g sulfur per 1000g adsorbent.
In the present invention, the operation of the adsorption unit 4 is described as follows:
1. desulfurization adsorption of incineration tail gas
The incineration tail gas from the incinerator 35 and the hydrogen-containing hydrogen sulfide removal tail gas-II from the top of the absorption tower 34 enter an adsorption unit 4, the incineration tail gas firstly passes through the waste heat boiler 44 for heat exchange and cooling, then exchanges heat and cools with the hydrogen-containing hydrogen sulfide removal tail gas-II in the first heat exchanger 45, continuously exchanges heat and cools with the purified gas from the gas outlet of the adsorption layer 412 of the movable adsorption bed 41 in the second heat exchanger 46, and finally enters the adsorption layer from the gas inlet at the lower part of the adsorption layer 412 of the movable adsorption bed 41; the cooled incineration tail gas moves in the adsorption layer 412 from bottom to top, contacts with an adsorbent to perform multistage adsorption, SO 2 contained in the incineration tail gas is removed to obtain purified gas and is led out from an air outlet of the adsorption layer 412, then the purified gas exchanges heat with the incineration tail gas in the second heat exchanger 46 to raise the temperature, and finally the standard emission is realized through a chimney 48;
In the process of absorbing and removing sulfur dioxide from the incineration tail gas, preferably, the purifying effect is monitored by an online analyzer of purified flue gas, and when the content of SO 2 in the purified gas is stable and has no obvious rising trend, the content of sulfur in the adsorbent in the adsorption layer 412 is larger, SO that the adsorption can be continued. When the SO 2 content in the purified gas is gradually increased and the upward trend is obvious, the residual sulfur capacity of the adsorbent is smaller, and the adsorbent needs to be regenerated and the fresh adsorbent is replenished. At this time, the isolation barrier between the adsorption layer 412 and the discharge layer 413 is opened, the adsorbent is discharged to the discharge layer 413, and at the same time, the isolation barrier between the storage layer 411 and the adsorption layer 412 is opened, and fresh adsorbent is replenished to the adsorption layer 412 to continue to adsorb SO 2.
2. Recycling regeneration of adsorbents
The adsorbent to be regenerated enters the regenerator 42 from the discharging layer 413, the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34 exchanges heat with the incineration flue gas in the first heat exchanger 45 to raise the temperature, and preferably is heated and raised by the auxiliary heater 47, and enters the regenerator 42 to serve as a regeneration heat source of the adsorbent to be regenerated, the regenerated adsorbent is subjected to heat regeneration treatment, the obtained regenerated adsorbent is sent to the storage layer 411 through the lifting device 43 to be recycled, and the obtained regenerated gas containing high-concentration sulfur dioxide is introduced into at least one of the sulfur making furnace 11, the primary converter 21, the secondary converter 22 and the hydrogenation device 31 to repeatedly recycle sulfur.
Preferably, the hydrogen-containing hydrogen sulfide removal tail gas-II is divided into two lines and enters the regenerator 42, one line enters a heating coil of the regenerator 42 to heat the regenerator 42 for heating and thermally regenerating the adsorbent, and then is led out from the heating coil, enters a circulating heating line, and enters the heating coil for recycling after being heated in sequence by the first heat exchanger 45 and the auxiliary heater 47; the other path enters the adsorbent regeneration chamber for carrying the SO 2 gas desorbed by the thermal regeneration into at least one of the sulfur making furnace 11, the primary converter 21, the secondary converter 22 and the hydrogenation device 31.
Preferably, the regenerated gas containing sulfur dioxide is returned to the primary converter 21, so that the recovery utilization rate of sulfur resources can be effectively increased, and the influence on the normal operation of the sulfur device can be reduced.
Preferably, the regenerated sorbent is cooled down using a portion of the hydrogen-containing hydrogen sulfide depleted tail gas-II from the top of absorber 34 before sending the cooled regenerated sorbent to storage layer 411.
The treatment system for the hydrogen sulfide-containing gas fully utilizes the existing conditions of a sulfur device, adopts the movable adsorption bed to carry out SO 2 adsorption on incineration tail gas, can realize near zero emission of flue gas SO 2 emission concentration less than or equal to 10mg/m 3 of the sulfur device, and preferably reaches SO 2 emission concentration less than or equal to 5mg/m 3. The system can reasonably adjust the regeneration period of the adsorbent through the content of sulfur dioxide in the purified gas, the adsorbent regeneration process can be continuously carried out or intermittently carried out, and the system can be flexibly controlled according to the actual condition of the adsorption process, so that the energy consumption increase and the adsorbent abrasion consumption caused by long-term continuous regeneration are avoided. The system adopts the hydrogen-containing hydrogen sulfide removal tail gas from the absorption tower as a regeneration gas source of the adsorbent, fully utilizes a heat source in the system to heat the regeneration gas source, effectively reduces the regeneration energy consumption, can effectively reduce the use loss of the adsorbent by a specific regeneration gas source, has the loss of the adsorbent less than or equal to 1wt%/1000h, and is beneficial to long-period stable operation of the system. The system can realize the closed cycle of sulfur resources in the process of treating the gas containing hydrogen sulfide, and the regenerated gas containing sulfur dioxide can return to the sulfur recovery device to continuously recover the sulfur resources, so that the total sulfur recovery rate of the system is close to 100%.
In addition, the treatment system for the hydrogen sulfide-containing gas provided by the invention not only can realize near zero emission of the device flue gas SO 2 during normal operation of a sulfur device, but also can realize standard emission of the device flue gas SO 2 during shutdown of the device. For the shutdown stage of the device, the regenerated gas cannot be recycled, three bed layers in the movable adsorption bed can be used for treating the regenerated gas, the regenerated gas sequentially passes through the unloading layer, the adsorption layer and the storage layer from bottom to top, the normal adsorption process is carried out, the adsorption effect of SO 2 can be ensured by the storage of the adsorbent in the movable adsorption bed, the regeneration is not needed, and the standard emission of SO 2 is realized.
The second aspect of the present invention provides a method for treating a hydrogen sulfide-containing gas, comprising:
(1) Carrying out thermal reaction on the gas containing hydrogen sulfide to obtain sulfur and process gas;
(2) Carrying out a Claus conversion reaction on the process gas to obtain sulfur and Claus tail gas;
(3) The Claus tail gas is subjected to hydrotreatment and dehydrosulfurization in sequence to obtain hydrogen-containing dehydrosulfurization tail gas, wherein the hydrogen-containing dehydrosulfurization tail gas is divided into hydrogen-containing dehydrosulfurization tail gas-I and hydrogen-containing dehydrosulfurization tail gas-II, and the hydrogen-containing dehydrosulfurization tail gas-I is subjected to incineration treatment to obtain sulfur dioxide-containing incineration tail gas;
(4) Absorbing and removing sulfur dioxide from the incineration tail gas by using an adsorbent to obtain purified gas; and performing thermal regeneration treatment on the adsorbent to be regenerated obtained after adsorption and sulfur dioxide removal treatment by using at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II as regeneration gas to obtain a regenerated adsorbent and regeneration gas containing sulfur dioxide;
Wherein the regenerated adsorbent is recycled back to the adsorption sulfur dioxide removal treatment; the sulfur dioxide-containing regeneration gas is recycled back to at least one of the thermal reaction, the claus conversion reaction, and the hydrotreatment.
According to the invention, in the step (1), the hydrogen sulfide-containing gas refers to H 2 S-containing gas generated in the fields of natural gas purification, refining and coal chemical industry, and the components thereof include H 2S、CO2、H2O、NH3, hydrocarbons and the like. Preferably, the content of H 2 S in the hydrogen sulfide-containing gas is 30-90% by volume, preferably 50-85% by volume.
According to the invention, in the step (1), the thermal reaction comprises mixing the hydrogen sulfide-containing gas with air and burning to obtain a thermal reaction product gas containing S, H 2S、SO2, COS and CS 2, and then condensing the thermal reaction product gas, wherein S is separated out in the form of elemental sulfur after condensation, and the thermal reaction product gas after separation of the elemental sulfur is the process gas.
According to the invention, the content of H 2 S in the process gas is 3-10v%; the content of SO 2 is 1.5-5% by volume; the COS content is 0.2-1v%.
According to the present invention, the thermal reaction may employ thermal reaction devices and parameters conventional in the art. Preferably, the conditions of the thermal reaction include: the temperature is 950-1350 ℃; the airspeed is 800-1200h -1. Herein, space velocity refers to the space velocity of the mixed feed gas comprising hydrogen sulfide gas and air.
According to the present invention, preferably, the thermal reaction is performed in a sulfur producing furnace.
According to the invention, in step (2), the claus conversion reaction may be carried out in multiple stages, preferably with two stages. Specifically, in the presence of a first sulfur recovery catalyst, carrying out a primary conversion reaction on the process gas to obtain a primary conversion reaction product containing sulfur, and carrying out sulfur separation on the primary conversion reaction product; and then carrying out secondary conversion reaction on the primary conversion reaction product from which sulfur is separated in the presence of a second sulfur recovery catalyst to obtain a secondary conversion reaction product containing sulfur, and obtaining the Claus tail gas after sulfur separation.
In the present invention, the first sulfur recovery catalyst and the second sulfur recovery catalyst may be claus conversion reaction catalysts conventional in the art, and may each be independently selected from at least one of a oxygen-leaking type sulfur recovery catalyst, a titanium oxide-based sulfur recovery catalyst, and an alumina-based sulfur recovery catalyst. Preferably, the oxygen-leaking-type sulfur catalyst contains ferric oxide and aluminum oxide components; the titanium oxide-based sulfur recovery catalyst contains aluminum oxide and titanium oxide components; the alumina-based sulfur recovery catalyst contains an alumina component. In the invention, the first sulfur recovery catalyst and the second sulfur recovery catalyst can be obtained by adopting conventional commercial brand products or by adopting a conventional method.
According to the present invention, in step (2), preferably, the conditions of the primary conversion reaction include: the temperature is 280-330 ℃; the airspeed is 800-1200h -1. Space velocity herein refers to the space velocity of the process gas.
According to the present invention, in step (2), preferably, the conditions of the secondary conversion reaction include: the temperature is 230-260 ℃; the airspeed is 800-1200h -1. Space velocity herein refers to the space velocity of the first conversion reaction product from which sulfur is separated.
According to the invention, in step (2), the sulfur separation of the primary conversion reaction product and the secondary conversion reaction product may be carried out in a conventional manner, such as condensation separation.
According to the invention, the claus tail gas contains H 2S、SO2、COS、CS2 and trace amounts of S. Preferably, the content of H 2 S in the Claus tail gas is 0.5-2% by volume; the content of SO 2 is 0.3-1% v; the COS content is 0.01-0.05v%.
According to the invention, in the step (3), the claus tail gas is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst, SO 2、COS、CS2, S and the like in the claus tail gas are subjected to hydrogenation conversion into H 2 S, and hydrogenated tail gas containing H 2 S is obtained.
According to the present invention, the hydrogenation catalyst may be a conventional hydrogenation catalyst in the art. Preferably, the hydrogenation catalyst comprises alumina, cobalt oxide and molybdenum oxide components. In the invention, the hydrogenation catalyst can be obtained by adopting a conventional commercial brand product or adopting a conventional method for self-making.
According to the present invention, preferably, the hydrogenation reaction conditions include: the temperature is 260-320 ℃; the airspeed is 800-1200h -1. The space velocity herein refers to the space velocity of the mixed feed gas of the claus tail gas and hydrogen.
According to the invention, in step (3), the claus tail gas is preferably preheated, preferably to 200-300 ℃, prior to the hydrotreatment.
According to the invention, in the step (3), the hydrotreated tail gas containing H 2 S obtained by the hydrotreatment is continuously subjected to dehydrosulfidation. In the present invention, the limitation of the dehydrosulfuration treatment is wide, and it is preferable to use a desulfurization absorber absorption method.
In the present invention, the desulfurization absorbent is limited in a wide range, and an amine liquid is preferably used, and for example, at least one selected from the group consisting of ethanolamine (MEA), diethanolamine (DEA), diisopropanolamine (DIPA) and N-Methyldiethanolamine (MDEA) may be used.
The hydrogen sulfide removal treatment of the H 2 S-containing hydrogenated tail gas with an amine solution according to the present invention may be carried out in a conventional manner and under conventional conditions, and is not particularly limited.
According to the invention, in step (3), the hydrogenated tail gas comprising H 2 S is preferably cooled, preferably to 25-42 ℃, prior to the dehydrosulphide treatment.
According to the invention, the hydrogen-containing dehydrosulphide tail gas contains H 2, a small amount of remaining H 2 S and COS. Preferably, the content of H 2 in the hydrogen-containing hydrogen sulfide removal tail gas is 2-8% by volume, preferably 3-5% by volume; h 2 S content is 5-200ppm; the COS content is 2-100ppm.
In the present invention, in the step (3), H 2 contained in the hydrogen-containing dehydrosulfided tail gas comes from the hydrotreating process of the claus tail gas, and the content of H 2 in the hydrogen-containing dehydrosulfided tail gas can be adjusted to the above range by controlling the amount of the raw material hydrogen in the hydrotreating process.
According to the invention, in step (3), the hydrogen-containing hydrogen sulfide removal tail gas-I: the volume ratio of the hydrogen sulfide removal tail gas-II containing hydrogen is (20-50): 1, preferably (30-45): 1.
According to the invention, in step (3), the incineration treatment may employ devices and parameters conventional in the art. Preferably, the incineration treatment conditions include: the temperature is 550-750 ℃; the airspeed is 800-1200h -1. The space velocity herein refers to the space velocity of the mixed feed gas of the hydrogen-containing hydrogen sulfide removal tail gas-I and air.
According to the present invention, preferably, the incineration treatment is performed in an incinerator.
According to the invention, the incineration tail gas contains water vapor, O 2、SO2、N2、CO2, CO and the like. Preferably, the content of SO 2 in the incineration tail gas is 50-1000mg/m 3, preferably 50-500mg/m 3.
According to the present invention, in the step (4), the adsorbent is selected from at least one of activated carbon, activated coke, metal oxide and molecular sieve, preferably activated carbon.
In the present invention, the metal oxide that can be used as the adsorbent includes, but is not limited to, copper oxide, iron oxide, zinc oxide, or the like, and copper oxide is preferable.
In the present invention, the molecular sieve which can be used as the adsorbent includes, but is not limited to, an X-type molecular sieve, a Y-type molecular sieve, a NaY molecular sieve, etc., preferably a NaY molecular sieve.
According to the invention, the adsorbent preferably has an initial sulfur capacity of 100-250g sulfur per 1000g adsorbent.
According to the invention, in step (4), the adsorption sulfur dioxide removal treatment is performed by contacting the incineration tail gas with an adsorbent. Preferably, the conditions for the adsorption sulfur dioxide removal treatment include: the temperature is 30-120deg.C, preferably 60-110deg.C; the space velocity of the incineration gas is 800-1500h -1, preferably 1000-1250h -1.
According to the invention, the SO 2 content in the purified gas obtained by the adsorption sulfur dioxide removal treatment is less than or equal to 10mg/m 3, preferably less than or equal to 5mg/m 3.
According to the invention, the incineration tail gas has higher temperature (500-650 ℃) to fully utilize heat, and in the step (4), preferably, the incineration tail gas is subjected to multistage heat exchange and temperature reduction before the adsorption sulfur dioxide removal treatment. In a preferred embodiment of the invention, the incineration tail gas is introduced into a waste heat boiler to perform primary heat exchange cooling (cooling to 240-270 ℃), then the incineration tail gas and the hydrogen-containing hydrogen sulfide removal tail gas-II are subjected to secondary heat exchange cooling (cooling to 180-220 ℃), the incineration tail gas and the purified gas obtained by adsorption sulfur dioxide removal treatment are continuously subjected to tertiary heat exchange cooling (cooling to 30-120 ℃), and then the incineration tail gas and the adsorbent are contacted to perform adsorption sulfur dioxide removal treatment.
According to the invention, in the step (4), in the adsorption sulfur dioxide removal treatment, when the adsorbent reaches adsorption saturation or the adsorption effect cannot meet the content requirement of SO 2 in the purified gas, regeneration is needed for recycling. The inventors of the present invention found that the use loss of the adsorbent can be reduced by using at least part of the hydrogen-containing hydrogen sulfide-removed tail gas-II as a regeneration gas of the adsorbent to be regenerated. Preferably, the hydrogen sulfide removal tail gas-II containing hydrogen is heated to 150-180 ℃ in the secondary heat exchange cooling process of the incineration tail gas, and then is heated to 300-450 ℃ by auxiliary heating so as to achieve high enough temperature for carrying out heat regeneration treatment on the adsorbent to be regenerated.
According to the present invention, the conditions of the thermal regeneration treatment include: the temperature of the hydrogen-containing hydrogen sulfide removal tail gas-II is 300-450 ℃.
According to the invention, at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II is used as regeneration gas of the adsorbent to be regenerated, so that the use loss of the adsorbent is less than or equal to 1wt%/1000h, namely the use loss of the adsorbent in 1000h is less than or equal to 1wt%.
According to a preferred embodiment of the invention, at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II is divided into two branches to participate in the thermal regeneration treatment, wherein one branch is used for heating and regenerating the adsorbent to be regenerated, and after the gas is used, the gas can participate in the heating and regenerating through heating and circulation; another stream of SO 2 gas for carrying the thermal regeneration and desorption is returned to at least one of the thermal reaction, claus conversion reaction and hydrotreatment for repeated recovery of sulfur.
According to the invention, preferably, part of the hydrogen-containing hydrogen sulfide removal tail gas-II is adopted to cool down the regenerated adsorbent, and the cooled regenerated adsorbent is returned to the adsorption sulfur dioxide removal treatment.
According to the invention, preferably, the regenerated gas containing sulfur dioxide is returned to the primary conversion reaction, so that the recycling rate of sulfur resources can be effectively increased, and the influence on the normal operation of the sulfur device is reduced.
In the present invention, the component content of the gas is measured using an infrared flue gas analyzer.
In the present invention, the loss (wt%) of the adsorbent= (1-weight of adsorbent after a certain time of use/initial loading weight of adsorbent) ×100%.
The following describes a method for treating a hydrogen sulfide-containing gas by using the system provided by the present invention with reference to fig. 1:
In the thermal reaction unit 1, hydrogen sulfide-containing gas (the content of H 2 S is 30-90% by volume) is mixed with air in a sulfur making furnace 11 and burnt (the temperature is 950-1350 ℃ and the airspeed is 800-1200H -1), the obtained thermal reaction product gas enters a first cooling device 12 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; process gas (3-10 v% H 2 S, 1.5-5v% SO 2, 0.2-1v% COS) is obtained at the outlet of the first cooling device 12;
In the catalytic reaction unit 2, the process gas from the thermal reaction unit 1 enters a primary converter 21, a primary conversion reaction is carried out in the presence of a oxygen-removing and sulfur-leaking type recovery catalyst and a titanium oxide-based sulfur recovery catalyst (the reaction temperature is 280-330 ℃ and the airspeed is 800-1200h -1), the obtained sulfur-containing primary conversion reaction product enters a second cooling device 23 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; the first-stage conversion reaction product separated out of sulfur enters a second-stage converter 22, a second-stage conversion reaction is carried out in the presence of an alumina-based sulfur recovery catalyst (the reaction temperature is 230-260 ℃, the airspeed is 800-1200H -1), the obtained second-stage conversion reaction product containing sulfur enters a third cooling device 24 for condensation, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region after cooling to obtain liquid sulfur, and claus tail gas (the content of H 2 S is 0.5-2v%, the content of SO 2 is 0.3-1v%, and the content of COS is 0.01-0.05 v%) is obtained at the outlet of the third cooling device 24;
In the tail gas purifying unit 3, the Claus tail gas from the catalytic reaction unit 2 is preheated to 200-300 ℃ by a Claus tail gas heater 36, then enters a hydrogenation device 31, and is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst (the reaction temperature is 260-320 ℃ and the space velocity is 800-1200H -1) to obtain hydrogenation tail gas containing H 2 S; the hydrogenated tail gas containing H 2 S is cooled to 25-42 ℃ through a fourth cooling device 32 and a quenching tower 33 in sequence, then enters an absorption tower 34, and is in countercurrent contact with a desulfurization absorbent, so that the hydrogen-containing dehydrosulfurated tail gas (the content of H 2 is 2-8v percent; the content of H 2 S is 5-200ppm; the content of COS is 2-100 ppm) is obtained at the top of the absorption tower 34; dividing the hydrogen-containing dehydrosulfide tail gas into two parts, namely hydrogen-containing dehydrosulfide tail gas-I and hydrogen-containing dehydrosulfide tail gas-II (the volume ratio of the hydrogen-containing dehydrosulfide tail gas-I to the hydrogen-containing dehydrosulfide tail gas-II is 20-50:1), wherein the hydrogen-containing dehydrosulfide tail gas-I enters an incinerator 35 for incineration treatment (the temperature is 550-750 ℃ and the airspeed is 800-1200h -1) to generate incineration tail gas containing sulfur dioxide (the content of SO 2 is 50-1000mg/m 3);
the hydrogen sulfide-removing tail gas-II containing hydrogen and the incineration tail gas enter an adsorption unit 4 from different lines;
In the adsorption unit 4, the incineration tail gas firstly undergoes heat exchange and cooling (cooling to 240-270 ℃) through the waste heat boiler 44, then undergoes heat exchange and cooling (cooling to 180-220 ℃) with the hydrogen-containing hydrogen sulfide removal tail gas-II in the first heat exchanger 45, and then undergoes heat exchange and cooling (cooling to 30-120 ℃) with the purified gas from the gas outlet of the adsorption layer 412 of the movable adsorption bed 41 in the second heat exchanger 46, and finally enters the adsorption layer through the gas inlet at the lower part of the adsorption layer 412 of the movable adsorption bed 41; the incineration tail gas entering the adsorption layer 412 moves from bottom to top, contacts with an adsorbent (at least one of active carbon, active coke, metal oxide and molecular sieve, and has an initial sulfur capacity of 100-250g sulfur/1000 g adsorbent) to perform adsorption sulfur dioxide removal treatment (the adsorption temperature is 30-120 ℃ and the airspeed is 800-1500h -1), SO 2 contained in the incineration tail gas is removed, and purified gas (the content of SO 2 is less than or equal to 10mg/m 3) is obtained at the gas outlet of the adsorption layer 412; the purified gas enters a second heat exchanger 46 to exchange heat with incineration tail gas to raise temperature, and finally is discharged through a chimney 48;
in the process of adsorption and sulfur dioxide removal, the purification effect is monitored by an online purification flue gas analyzer, and when the content of SO 2 in the purification flue gas is stable and has no obvious rising trend, the adsorption can be continued; when the content of SO 2 in the purified gas gradually rises and the rising trend is obvious, the adsorbent needs to be regenerated, at the moment, the isolation baffle between the adsorption layer 412 and the discharge layer 413 is opened, the adsorbent to be regenerated is discharged to the discharge layer 413, and meanwhile, the isolation baffle between the storage layer 411 and the adsorption layer 412 is opened, and fresh adsorbent is supplemented to the adsorption layer 412 to continuously adsorb and remove sulfur dioxide;
The adsorbent to be regenerated is conveyed to the regenerator 42 through the discharging layer 413, the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34 exchanges heat with incineration flue gas in the first heat exchanger 45 to raise the temperature to 150-180 ℃, then is heated to 300-450 ℃ through the auxiliary heater 47, enters the regenerator 42 and is used as a regeneration heat source of the adsorbent to be regenerated, the adsorbent to be regenerated is subjected to thermal regeneration treatment (the thermal regeneration temperature is 300-450 ℃), the obtained regenerated adsorbent is conveyed to the storage layer 411 through the lifting device 43 to be recycled, and the obtained regenerated gas containing high-concentration sulfur dioxide is introduced into at least one of the sulfur making furnace 11, the primary converter 21, the secondary converter 22 and the hydrogenation device 31 to repeatedly recycle sulfur.
The present invention will be described in detail by way of examples, which are provided below and comparative examples,
Hydrogen sulfide-containing gas: h 2S 80v％、CO2 10v％、H2O 5v％、NH3 4v% and hydrocarbons 1v%, produced by a natural gas purification process;
First sulfur recovery catalyst: the oxygen leakage-free sulfur recovery catalyst (with the trademark of LS-971, purchased from Shandong Ji Luke chemical industry institute of GmbH) and the titanium oxide-based sulfur recovery catalyst (with the trademark of LS-981G, purchased from Shandong Ji Luke chemical industry institute of GmbH) are mixed according to the volume ratio of 1:2, compounding to obtain the compound;
First sulfur recovery catalyst: alumina-based sulfur recovery catalyst, brand LS-02, available from Shandong Qilu chemical industry institute of GmbH;
Hydrogenation catalyst: the brand LSH-03A is purchased from Shandong Ji Luke institute of chemical industry, inc.
Example 1
(1) In the thermal reaction unit 1, hydrogen sulfide-containing gas is mixed with air in a sulfur production furnace 11 and combusted (the temperature is 1300 ℃ and the airspeed is 1000h -1), the obtained thermal reaction product gas enters a first cooling device 12 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; process gas (6.39 v% H 2 S; 3.26v% SO 2; 0.39v% COS) is obtained at the outlet of the first cooling unit 12;
(2) In the catalytic reaction unit 2, the process gas from the thermal reaction unit 1 enters a primary converter 21, primary conversion reaction is carried out in the presence of a first sulfur recovery catalyst (the reaction temperature is 315 ℃, the space velocity is 1000h -1), the obtained sulfur-containing primary conversion reaction product enters a second cooling device 23 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; the first-stage conversion reaction product separated out of sulfur enters a second-stage converter 22, a second-stage conversion reaction is carried out in the presence of a second sulfur recovery catalyst (the reaction temperature is 250 ℃, the space velocity is 1000H -1), the obtained second-stage conversion reaction product containing sulfur enters a third cooling device 24 for condensation, after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur, and claus tail gas (the content of H 2 S is 1.12v%, the content of SO 2 is 0.58v%, and the content of COS is 0.04 v%);
(3) In the tail gas purifying unit 3, the claus tail gas from the catalytic reaction unit 2 is preheated to 250 ℃ by a claus tail gas heater 36, then enters a hydrogenation device 31, and is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst (the reaction temperature is 280 ℃, the space velocity is 1000H -1) to obtain hydrogenation tail gas containing H 2 S; the hydrogenated tail gas containing H 2 S is cooled to 38 ℃ through a fourth cooling device 32 and a quenching tower 33 in sequence, then enters an absorption tower 34, and is in countercurrent contact with a desulfurization absorbent MDEA (the concentration is 45 wt%) (the absorption temperature is 36 ℃), and hydrogen-containing dehydrosulfide tail gas (the content of H 2 is 4.5v%; the content of H 2 S is 68ppm and the content of COS is 16 ppm) is obtained at the top of the absorption tower 34; dividing the hydrogen-containing dehydrosulfide tail gas into two parts, namely hydrogen-containing dehydrosulfide tail gas-I and hydrogen-containing dehydrosulfide tail gas-II (the volume ratio of the hydrogen-containing dehydrosulfide tail gas-I to the hydrogen-containing dehydrosulfide tail gas-II is 35:1), wherein the hydrogen-containing dehydrosulfide tail gas-I enters an incinerator 35 for incineration treatment (the temperature is 680 ℃ and the airspeed is 1000h -1) to generate incineration tail gas containing sulfur dioxide (the content of SO 2 is 238mg/m 3);
the hydrogen sulfide-removing tail gas-II containing hydrogen and the incineration tail gas enter an adsorption unit 4 from different lines;
(4-1) desulfurization adsorption of incineration exhaust gas
In the adsorption unit 4, the incineration tail gas firstly passes through the waste heat boiler 44 for heat exchange and cooling (cooling to 250 ℃), then carries out heat exchange and cooling (cooling to 200 ℃) with the hydrogen-containing dehydrosulfuration tail gas-II in the first heat exchanger 45, continuously carries out heat exchange and cooling (cooling to 100 ℃) with the purified gas from the gas outlet of the adsorption layer 412 of the movable adsorption bed 41 in the second heat exchanger 46, finally enters the adsorption layer from the gas inlet at the lower part of the adsorption layer 412 of the movable adsorption bed 41, and the incineration tail gas entering the adsorption layer 412 moves from bottom to top, contacts with the activated carbon adsorbent (the initial sulfur capacity is 160g sulfur/1000 g adsorbent) for adsorption and sulfur removal treatment (the adsorption temperature is 100 ℃, the airspeed of the incineration tail gas is 1000h -1), SO 2 contained in the incineration tail gas is removed, and the purified gas is obtained at the gas outlet of the adsorption layer 412; the purified gas enters a second heat exchanger 46 to exchange heat with incineration tail gas to raise temperature, and finally is discharged through a chimney 48;
in the process of adsorption and sulfur dioxide removal, the purification effect is monitored by an online purification flue gas analyzer, and when the content of SO 2 in the purification flue gas is stable and has no obvious rising trend, the adsorption can be continued; when the content of SO 2 in the purified gas gradually rises and the rising trend is obvious, the adsorbent needs to be regenerated, at the moment, the isolation baffle between the adsorption layer 412 and the discharge layer 413 is opened, the adsorbent to be regenerated is discharged to the discharge layer 413, and meanwhile, the isolation baffle between the storage layer 411 and the adsorption layer 412 is opened, and fresh adsorbent is supplemented to the adsorption layer 412 to continuously adsorb and remove sulfur dioxide;
(4-2) Recycling of adsorbent
The adsorbent to be regenerated is conveyed to a regenerator 42 by a discharging layer 413, the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34 is subjected to heat exchange with incineration flue gas in a first heat exchanger 45 to be heated to 380 ℃ by an auxiliary heater 47, then is divided into two circuits to enter the regenerator 42, one circuit enters a heating coil of the regenerator 42 to heat the adsorbent for thermal regeneration (the temperature of thermal regeneration is 375 ℃, the airspeed is 800h -1), and the gas enters a circulation heating line to be heated after exiting the heating coil and is sequentially heated by the first heat exchanger 45 and the auxiliary heater 47, and then enters the heating coil for recycling; the other path of the regenerated gas enters an adsorbent regeneration chamber for carrying regenerated gas containing high-concentration sulfur dioxide into a primary converter 21 to repeatedly recover sulfur;
The regenerated adsorbent obtained is cooled by cooling the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34, and then sent to the storage layer 411 for recycling through the lifting device 43.
The concentration of SO 2 in the purified gas is 0mg/m 3 during the period from the start-up of the system to the operation for 40 hours; after the system is operated for 46 hours, the concentration of SO 2 in the purified gas reaches 3mg/m 3, and at the moment, the adsorbent is continuously regenerated in the adsorption unit 4, and the total continuous operation of the system is maintained for 1000 hours from the starting.
In this example, the SO 2 content of the purified gas, the loss of the adsorbent, and the regeneration cycle of the adsorbent are shown in Table 1.
Example 2
(1) In the thermal reaction unit 1, hydrogen sulfide-containing gas is mixed with air in a sulfur production furnace 11 and combusted (the temperature is 1285 ℃, the airspeed is 800h -1), the obtained thermal reaction product gas enters a first cooling device 12 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; process gas (6.65 v% H 2 S; 3.26v% SO 2; 0.52v% COS) is obtained at the outlet of the first cooling unit 12;
(2) In the catalytic reaction unit 2, the process gas from the thermal reaction unit 1 enters a primary converter 21, primary conversion reaction is carried out in the presence of a first sulfur recovery catalyst (the reaction temperature is 310 ℃, the space velocity is 800h -1), the obtained sulfur-containing primary conversion reaction product enters a second cooling device 23 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; the first-stage conversion reaction product separated out of sulfur enters a second-stage converter 22, a second-stage conversion reaction is carried out in the presence of a second sulfur recovery catalyst (the reaction temperature is 245 ℃, the space velocity is 800H -1), the obtained second-stage conversion reaction product containing sulfur enters a third cooling device 24 for condensation, after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur, and claus tail gas (the content of H 2 S is 1.15v%, the content of SO 2 is 0.51v%, and the content of COS is 0.05 v%);
(3) In the tail gas purifying unit 3, the claus tail gas from the catalytic reaction unit 2 is preheated to 235 ℃ by a claus tail gas heater 36, then enters a hydrogenation device 31, and is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst (the reaction temperature is 270 ℃ C.; the space velocity is 800H -1) to obtain hydrogenation tail gas containing H 2 S; the hydrogenated tail gas containing H 2 S is cooled to 36 ℃ through a fourth cooling device 32 and a quenching tower 33 in sequence, then enters an absorption tower 34, and is in countercurrent contact with a desulfurization absorbent MDEA (the concentration is 42 wt%) (the absorption temperature is 38 ℃), and hydrogen-containing dehydrosulfide tail gas (the content of H 2 is 3.5v%; the content of H 2 S is 75ppm and the content of COS is 18 ppm) is obtained at the top of the absorption tower 34; dividing the hydrogen-containing dehydrosulfide tail gas into two parts, namely hydrogen-containing dehydrosulfide tail gas-I and hydrogen-containing dehydrosulfide tail gas-II (the volume ratio of the hydrogen-containing dehydrosulfide tail gas-I to the hydrogen-containing dehydrosulfide tail gas-II is 35:1), wherein the hydrogen-containing dehydrosulfide tail gas-I enters an incinerator 35 for incineration treatment (the temperature is 700 ℃ and the airspeed is 800h -1) to generate incineration tail gas containing sulfur dioxide (the content of SO 2 is 256mg/m 3);
the hydrogen sulfide-removing tail gas-II containing hydrogen and the incineration tail gas enter an adsorption unit 4 from different lines;
(4-1) desulfurization adsorption of incineration exhaust gas
In the adsorption unit 4, the incineration tail gas firstly passes through the waste heat boiler 44 for heat exchange and cooling (cooling to 260 ℃), then carries out heat exchange and cooling (cooling to 210 ℃) with the hydrogen-containing dehydrosulfuration tail gas-II in the first heat exchanger 45, continuously carries out heat exchange and cooling (cooling to 105 ℃) with the purified gas from the gas outlet of the adsorption layer 412 of the movable adsorption bed 41 in the second heat exchanger 46, finally enters the adsorption layer from the gas inlet at the lower part of the adsorption layer 412 of the movable adsorption bed 41, and the incineration tail gas entering the adsorption layer 412 moves from bottom to top, contacts with the activated carbon adsorbent (the initial sulfur capacity is 200g sulfur/1000 g adsorbent) for adsorption and sulfur removal treatment (the adsorption temperature is 110 ℃, the airspeed of the incineration tail gas is 1250h -1), SO 2 contained in the incineration tail gas is removed, and the purified gas is obtained at the gas outlet of the adsorption layer 412; the purified gas enters a second heat exchanger 46 to exchange heat with incineration tail gas to raise temperature, and finally is discharged through a chimney 48;
in the process of adsorption and sulfur dioxide removal, the purification effect is monitored by an online purification flue gas analyzer, and when the content of SO 2 in the purification flue gas is stable and has no obvious rising trend, the adsorption can be continued; when the content of SO 2 in the purified gas gradually rises and the rising trend is obvious, the adsorbent needs to be regenerated, at the moment, the isolation baffle between the adsorption layer 412 and the discharge layer 413 is opened, the adsorbent to be regenerated is discharged to the discharge layer 413, and meanwhile, the isolation baffle between the storage layer 411 and the adsorption layer 412 is opened, and fresh adsorbent is supplemented to the adsorption layer 412 to continuously adsorb and remove sulfur dioxide;
(4-2) Recycling of adsorbent
The adsorbent to be regenerated is conveyed to a regenerator 42 by a discharging layer 413, the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34 is subjected to heat exchange with incineration flue gas in a first heat exchanger 45 to be heated to 410 ℃ by an auxiliary heater 47, then is divided into two circuits to enter the regenerator 42, one circuit enters a heating coil of the regenerator 42 to heat the adsorbent for thermal regeneration (the temperature of thermal regeneration is 400 ℃ and the airspeed is 1000h -1), and the gas enters a circulation heating line to be heated after exiting the heating coil and is sequentially heated by the first heat exchanger 45 and the auxiliary heater 47 and then enters the heating coil for recycling; the other path of the regenerated gas enters an adsorbent regeneration chamber for carrying the regenerated gas containing high-concentration sulfur dioxide into a primary converter 21 for repeatedly recycling sulfur;
The regenerated adsorbent obtained is cooled by cooling the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34, and then sent to the storage layer 411 for recycling through the lifting device 43.
The concentration of SO 2 in the purified gas is 0mg/m 3 during 48 hours from system start-up to operation; after the system is operated for 52 hours, the concentration of SO 2 in the purified gas reaches 4mg/m 3, and at the moment, the adsorbent is continuously regenerated in the adsorption unit 4, and the total continuous operation of the system is maintained for 1000 hours from the starting.
In this example, the SO 2 content of the purified gas, the loss of the adsorbent, and the regeneration cycle of the adsorbent are shown in Table 1.
Example 3
(1) In the thermal reaction unit 1, hydrogen sulfide-containing gas is mixed with air in a sulfur production furnace 11 and combusted (the temperature is 1270 ℃ and the airspeed is 1100h -1), the obtained thermal reaction product gas enters a first cooling device 12 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; process gas (6.82 v% H 2 S; 3.40v% SO 2; 0.48v% COS) is obtained at the outlet of the first cooling unit 12;
(2) In the catalytic reaction unit 2, the process gas from the thermal reaction unit 1 enters a primary converter 21, primary conversion reaction is carried out in the presence of a first sulfur recovery catalyst (the reaction temperature is 320 ℃, the space velocity is 900h -1), the obtained sulfur-containing primary conversion reaction product enters a second cooling device 23 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; the first-stage conversion reaction product separated out of sulfur enters a second-stage converter 22, a second-stage conversion reaction is carried out in the presence of a second sulfur recovery catalyst (the reaction temperature is 248 ℃, the space velocity is 900H -1), the obtained second-stage conversion reaction product containing sulfur enters a third cooling device 24 for condensation, after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur, and claus tail gas (the content of H 2 S is 1.21v%, the content of SO 2 is 0.57v%, and the content of COS is 0.05 v%);
(3) In the tail gas purifying unit 3, the claus tail gas from the catalytic reaction unit 2 is preheated to 245 ℃ by a claus tail gas heater 36, then enters a hydrogenation device 31, and is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst (the reaction temperature is 290 ℃ C.; the space velocity is 900H -1) to obtain hydrogenation tail gas containing H 2 S; the hydrogenated tail gas containing H 2 S is cooled to 36 ℃ through a fourth cooling device 32 and a quenching tower 33 in sequence, then enters an absorption tower 34, and is in countercurrent contact with a desulfurization absorbent MDEA (the concentration is 40 wt%) (the absorption temperature is 40 ℃), and hydrogen-containing dehydrosulfide tail gas (the content of H 2 is 4v%; the content of H 2 S is 135ppm; the content of COS is 15 ppm) is obtained at the top of the absorption tower 34; dividing the hydrogen-containing dehydrosulfide tail gas into two parts, namely hydrogen-containing dehydrosulfide tail gas-I and hydrogen-containing dehydrosulfide tail gas-II (the volume ratio of the hydrogen-containing dehydrosulfide tail gas-I to the hydrogen-containing dehydrosulfide tail gas-II is 40:1), wherein the hydrogen-containing dehydrosulfide tail gas-I enters an incinerator 35 for incineration treatment (the temperature is 650 ℃, the airspeed is 900h -1) to generate incineration tail gas containing sulfur dioxide (the content of SO 2 is 318mg/m 3);
the hydrogen sulfide-removing tail gas-II containing hydrogen and the incineration tail gas enter an adsorption unit 4 from different lines;
(4-1) desulfurization adsorption of incineration exhaust gas
In the adsorption unit 4, the incineration tail gas firstly passes through the waste heat boiler 44 for heat exchange and cooling (cooling to 245 ℃), then carries out heat exchange and cooling (cooling to 200 ℃) with the hydrogen-containing dehydrosulfuration tail gas-II in the first heat exchanger 45, continuously carries out heat exchange and cooling (cooling to 75 ℃) with the purified gas from the gas outlet of the adsorption layer 412 of the movable adsorption bed 41 in the second heat exchanger 46, finally enters the adsorption layer from the gas inlet at the lower part of the adsorption layer 412 of the movable adsorption bed 41, and the incineration tail gas entering the adsorption layer 412 moves from bottom to top, contacts with the activated carbon adsorbent (the initial sulfur capacity is 150g sulfur/1000 g adsorbent) for adsorption and sulfur removal treatment (the adsorption temperature is 80 ℃, the airspeed of the incineration tail gas is 1100h -1), SO 2 contained in the incineration tail gas is removed, and the purified gas is obtained at the gas outlet of the adsorption layer 412; the purified gas enters a second heat exchanger 46 to exchange heat with incineration tail gas to raise temperature, and finally is discharged through a chimney 48;
in the process of adsorption and sulfur dioxide removal, the purification effect is monitored by an online purification flue gas analyzer, and when the content of SO 2 in the purification flue gas is stable and has no obvious rising trend, the adsorption can be continued; when the content of SO 2 in the purified gas gradually rises and the rising trend is obvious, the adsorbent needs to be regenerated, at the moment, the isolation baffle between the adsorption layer 412 and the discharge layer 413 is opened, the adsorbent to be regenerated is discharged to the discharge layer 413, and meanwhile, the isolation baffle between the storage layer 411 and the adsorption layer 412 is opened, and fresh adsorbent is supplemented to the adsorption layer 412 to continuously adsorb and remove sulfur dioxide;
(4-2) Recycling of adsorbent
The adsorbent to be regenerated is conveyed to the regenerator 42 by the discharging layer 413, the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34 is subjected to heat exchange with incineration flue gas in the first heat exchanger 45 to be heated to 430 ℃ by the auxiliary heater 47, then is divided into two lines to enter the regenerator 42, one line enters a heating coil of the regenerator 42 to heat the adsorbent for thermal regeneration (the temperature of thermal regeneration is 420 ℃ and the space velocity is 900h -1), and the gas enters a circulation heating line to be heated after exiting the heating coil and is sequentially heated by the first heat exchanger 45 and the auxiliary heater 47 and then enters the heating coil for circulation use; the other path of the regenerated gas enters an adsorbent regeneration chamber for carrying regenerated gas containing high-concentration sulfur dioxide into a primary converter 21 to repeatedly recover sulfur;
The regenerated adsorbent obtained is cooled by cooling the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34, and then sent to the storage layer 411 for recycling through the lifting device 43.
The concentration of SO 2 in the purified gas is 0mg/m 3 during the period from the start-up of the system to the operation for 28 hours; after the system is operated for 32 hours, the concentration of SO 2 in the purified gas reaches 5mg/m 3, and at the moment, the adsorbent is continuously regenerated in the adsorption unit 4, and the total continuous operation of the system is maintained for 1000 hours from the starting.
In this example, the SO 2 content of the purified gas, the loss of the adsorbent, and the regeneration cycle of the adsorbent are shown in Table 1.
Example 4
(1) In the thermal reaction unit 1, hydrogen sulfide-containing gas is mixed with air in a sulfur producer 11 and combusted (the temperature is 1260 ℃ and the airspeed is 800h -1), the obtained thermal reaction product gas enters a first cooling device 12 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; process gas (6.86 v% H 2 S; 3.42v% SO 2; 0.55v% COS) is obtained at the outlet of the first cooling unit 12;
(2) In the catalytic reaction unit 2, the process gas from the thermal reaction unit 1 enters a primary converter 21, primary conversion reaction is carried out in the presence of a first sulfur recovery catalyst (the reaction temperature is 310 ℃, the space velocity is 800h -1), the obtained sulfur-containing primary conversion reaction product enters a second cooling device 23 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; the first-stage conversion reaction product separated out of sulfur enters a second-stage converter 22, a second-stage conversion reaction is carried out in the presence of a second sulfur recovery catalyst (the reaction temperature is 250 ℃, the space velocity is 800H -1), the obtained second-stage conversion reaction product containing sulfur enters a third cooling device 24 for condensation, after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur, and claus tail gas (the content of H 2 S is 1.18v%, the content of SO 2 is 0.61v%, and the content of COS is 0.04 v%);
(3) In the tail gas purifying unit 3, the claus tail gas from the catalytic reaction unit 2 is preheated to 240 ℃ by a claus tail gas heater 36, then enters a hydrogenation device 31, and is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst (the reaction temperature is 280 ℃, the space velocity is 800H -1) to obtain hydrogenation tail gas containing H 2 S; the hydrogenated tail gas containing H 2 S is cooled to 36 ℃ through a fourth cooling device 32 and a quenching tower 33 in sequence, then enters an absorption tower 34, and is in countercurrent contact with a desulfurization absorbent MDEA (the concentration is 25 wt%) (the absorption temperature is 45 ℃) to obtain hydrogen-containing dehydrosulfide tail gas (the content of H 2 is 2.5v%; the content of H 2 S is 180ppm and the content of COS is 82 ppm) at the top of the absorption tower 34; dividing the hydrogen-containing dehydrosulfide tail gas into two parts, namely a hydrogen-containing dehydrosulfide tail gas-I and a hydrogen-containing dehydrosulfide tail gas-II (the volume ratio of the hydrogen-containing dehydrosulfide tail gas-I to the hydrogen-containing dehydrosulfide tail gas-II is 25:1), wherein the hydrogen-containing dehydrosulfide tail gas-I enters an incinerator 35 for incineration treatment (the temperature is 620 ℃ and the airspeed is 800h -1) to generate an incineration tail gas containing sulfur dioxide (the content of SO 2 is 656mg/m 3);
the hydrogen sulfide-removing tail gas-II containing hydrogen and the incineration tail gas enter an adsorption unit 4 from different lines;
(4-1) desulfurization adsorption of incineration exhaust gas
In the adsorption unit 4, the incineration tail gas firstly passes through a waste heat boiler 44 for heat exchange and cooling (cooling to 240 ℃), then passes through a first heat exchanger 45 for heat exchange and cooling (cooling to 180 ℃) with hydrogen-containing dehydrosulfuration tail gas-II, and then passes through a second heat exchanger 46 for heat exchange and cooling (cooling to 38 ℃) with purified gas from the gas outlet of an adsorption layer 412 of a movable adsorption bed 41, finally enters the adsorption layer from the gas inlet at the lower part of the adsorption layer 412 of the movable adsorption bed 41, the incineration tail gas entering the adsorption layer 412 moves from bottom to top, contacts with a NaY molecular sieve adsorbent (the initial sulfur capacity is 150g sulfur/1000 g adsorbent) for adsorption and sulfur dioxide removal treatment (the adsorption temperature is 40 ℃, the airspeed of the incineration tail gas is 1350h -1), SO 2 contained in the incineration tail gas is removed, and purified gas is obtained at the gas outlet of the adsorption layer 412; the purified gas enters a second heat exchanger 46 to exchange heat with incineration tail gas to raise temperature, and finally is discharged through a chimney 48;
in the process of adsorption and sulfur dioxide removal, the purification effect is monitored by an online purification flue gas analyzer, and when the content of SO 2 in the purification flue gas is stable and has no obvious rising trend, the adsorption can be continued; when the content of SO 2 in the purified gas gradually rises and the rising trend is obvious, the adsorbent needs to be regenerated, at the moment, the isolation baffle between the adsorption layer 412 and the discharge layer 413 is opened, the adsorbent to be regenerated is discharged to the discharge layer 413, and meanwhile, the isolation baffle between the storage layer 411 and the adsorption layer 412 is opened, and fresh adsorbent is supplemented to the adsorption layer 412 to continuously adsorb and remove sulfur dioxide;
(4-2) Recycling of adsorbent
The adsorbent to be regenerated is conveyed to a regenerator 42 by a discharging layer 413, the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34 is subjected to heat exchange with incineration flue gas in a first heat exchanger 45 to raise the temperature, then is heated to 390 ℃ by an auxiliary heater 47, is divided into two circuits and enters the regenerator 42, one circuit enters a heating coil of the regenerator 42 to carry out thermal regeneration (the temperature of thermal regeneration is 380 ℃ for 1000h -1), and the circuit gas enters a circulation heating line to raise the temperature after exiting the heating coil and is sequentially heated by the first heat exchanger 45 and the auxiliary heater 47 and then enters the heating coil again to be recycled; the other path of the regenerated gas enters an adsorbent regeneration chamber for carrying regenerated gas containing high-concentration sulfur dioxide into a primary converter 21 to repeatedly recover sulfur;
The regenerated adsorbent obtained is cooled by cooling the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34, and then sent to the storage layer 411 for recycling through the lifting device 43.
The concentration of SO 2 in the purified gas is 0mg/m 3 during the period from the start-up of the system to the operation for 20 hours; after the system is operated for 25 hours, the concentration of SO 2 in the purified gas reaches 6mg/m 3, and at the moment, the adsorbent is continuously regenerated in the adsorption unit 4, and the total continuous operation of the system is maintained for 1000 hours from the starting.
In this example, the SO 2 content of the purified gas, the loss of the adsorbent, and the regeneration cycle of the adsorbent are shown in Table 1.
Example 5
(1) In the thermal reaction unit 1, hydrogen sulfide-containing gas is mixed with air in a sulfur producer 11 and combusted (the temperature is 1250 ℃, the airspeed is 800h -1), the obtained thermal reaction product gas enters a first cooling device 12 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; process gas (7.06 v% H 2 S; 3.52v% SO 2; 0.75v% COS) is obtained at the outlet of the first cooling unit 12;
(2) In the catalytic reaction unit 2, the process gas from the thermal reaction unit 1 enters a primary converter 21, primary conversion reaction is carried out in the presence of a first sulfur recovery catalyst (the reaction temperature is 310 ℃, the space velocity is 800h -1), the obtained sulfur-containing primary conversion reaction product enters a second cooling device 23 for condensation, and after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur; the first-stage conversion reaction product separated out of sulfur enters a second-stage converter 22, a second-stage conversion reaction is carried out in the presence of a second sulfur recovery catalyst (the reaction temperature is 250 ℃, the space velocity is 800H -1), the obtained second-stage conversion reaction product containing sulfur enters a third cooling device 24 for condensation, after cooling, elemental sulfur is discharged into a liquid sulfur pool outside a boundary region to obtain liquid sulfur, and claus tail gas (the content of H 2 S is 1.22v%, the content of SO 2 is 0.62v%, and the content of COS is 0.05 v%);
(3) In the tail gas purifying unit 3, the claus tail gas from the catalytic reaction unit 2 is preheated to 245 ℃ by a claus tail gas heater 36, then enters a hydrogenation device 31, and is subjected to hydrogenation reaction in the presence of a hydrogenation catalyst (the reaction temperature is 280 ℃, the space velocity is 800H -1) to obtain hydrogenation tail gas containing H 2 S; the hydrogenated tail gas containing H 2 S is cooled to 36 ℃ through a fourth cooling device 32 and a quenching tower 33 in sequence, then enters an absorption tower 34, and is in countercurrent contact with a desulfurization absorbent MDEA (the concentration is 28 wt%) (the absorption temperature is 42 ℃), and hydrogen-containing dehydrosulfide tail gas (the content of H 2 is 8v%; the content of H 2 S is 195ppm and the content of COS is 76 ppm) is obtained at the top of the absorption tower 34; dividing the hydrogen-containing dehydrosulfide tail gas into two parts, namely hydrogen-containing dehydrosulfide tail gas-I and hydrogen-containing dehydrosulfide tail gas-II (the volume ratio of the hydrogen-containing dehydrosulfide tail gas-I to the hydrogen-containing dehydrosulfide tail gas-II is 50:1), wherein the hydrogen-containing dehydrosulfide tail gas-I enters an incinerator 35 for incineration treatment (the temperature is 650 ℃, the airspeed is 800h -1) to generate incineration tail gas containing sulfur dioxide (the content of SO 2 is 626mg/m 3);
the hydrogen sulfide-removing tail gas-II containing hydrogen and the incineration tail gas enter an adsorption unit 4 from different lines;
(4-1) desulfurization adsorption of incineration exhaust gas
In the adsorption unit 4, the incineration tail gas firstly passes through the waste heat boiler 44 for heat exchange and cooling (cooling to 265 ℃), then passes through the first heat exchanger 45 for heat exchange and cooling (cooling to 220 ℃) with the hydrogen-containing dehydrosulfuration tail gas-II, and then passes through the second heat exchanger 46 for heat exchange and cooling (cooling to 115 ℃) with the purified gas from the gas outlet of the adsorption layer 412 of the movable adsorption bed 41, finally enters the adsorption layer from the gas inlet at the lower part of the adsorption layer 412 of the movable adsorption bed 41, the incineration tail gas entering the adsorption layer 412 moves from bottom to top, contacts with the active coke adsorbent (the initial sulfur capacity is 180g sulfur/1000 g adsorbent) for adsorption and sulfur removal treatment (the adsorption temperature is 120 ℃, the airspeed of the incineration tail gas is 800h -1), SO 2 contained in the incineration tail gas is removed, and the purified gas is obtained at the gas outlet of the adsorption layer 412; the purified gas enters a second heat exchanger 46 to exchange heat with incineration tail gas to raise temperature, and finally is discharged through a chimney 48;
in the process of adsorption and sulfur dioxide removal, the purification effect is monitored by an online purification flue gas analyzer, and when the content of SO 2 in the purification flue gas is stable and has no obvious rising trend, the adsorption can be continued; when the content of SO 2 in the purified gas gradually rises and the rising trend is obvious, the adsorbent needs to be regenerated, at the moment, the isolation baffle between the adsorption layer 412 and the discharge layer 413 is opened, the adsorbent to be regenerated is discharged to the discharge layer 413, and meanwhile, the isolation baffle between the storage layer 411 and the adsorption layer 412 is opened, and fresh adsorbent is supplemented to the adsorption layer 412 to continuously adsorb and remove sulfur dioxide;
(4-2) Recycling of adsorbent
The adsorbent to be regenerated is conveyed to the regenerator 42 by the discharging layer 413, the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34 exchanges heat with incineration flue gas in the first heat exchanger 45 and heats up, then is heated to 360 ℃ by the auxiliary heater 47, and then is divided into two lines to enter the regenerator 42, one line enters a heating coil of the regenerator 42 to heat up the adsorbent for thermal regeneration (the thermal regeneration temperature is 350 ℃, 700h -1), and the line gas enters a circulation heating line to heat up after exiting the heating coil and is sequentially heated up by the first heat exchanger 45 and the auxiliary heater 47, and then enters the heating coil again for circulation use; the other path of the regenerated gas enters an adsorbent regeneration chamber for carrying regenerated gas containing high-concentration sulfur dioxide into a hydrogenation device 31 to repeatedly recycle sulfur;
The regenerated adsorbent obtained is cooled by cooling the hydrogen-containing hydrogen sulfide-removed tail gas-II from the top of the absorption tower 34, and then sent to the storage layer 411 for recycling through the lifting device 43.
The concentration of SO 2 in the purified gas is 0mg/m 3 during the period from the start-up to the operation of the system for 22 hours; after the system is operated for 24 hours, the concentration of SO 2 in the purified gas reaches 8mg/m 3, and at the moment, the adsorbent is continuously regenerated in the adsorption unit 4, and the total continuous operation of the system is maintained for 1000 hours from the starting.
In this example, the SO 2 content of the purified gas, the loss of the adsorbent, and the regeneration cycle of the adsorbent are shown in Table 1.
Example 6
Step (1) -step (3) were performed according to the method and parameters of example 3, wherein in step (3), the feed amount of H 2 for hydrogenation reaction was adjusted to obtain a hydrogen-containing hydrogen sulfide-removed tail gas (1.2 v% of H 2; 143ppm of H 2 S; 25ppm of COS) at the top of the absorption column 34; dividing the hydrogen-containing dehydrosulfide tail gas into two parts, namely hydrogen-containing dehydrosulfide tail gas-I and hydrogen-containing dehydrosulfide tail gas-II (the volume ratio of the hydrogen-containing dehydrosulfide tail gas-I to the hydrogen-containing dehydrosulfide tail gas-II is 40:1), wherein the hydrogen-containing dehydrosulfide tail gas-I enters an incinerator 35 for incineration treatment (the temperature is 650 ℃, the airspeed is 900h -1) to generate incineration tail gas containing sulfur dioxide (the content of SO 2 is 382mg/m 3);
The hydrogen sulfide free tail gas-II containing hydrogen and the incineration tail gas were subjected to steps (4-1) -step (4-2) according to the method and parameters of example 1.
The concentration of SO 2 in the purified gas is 0mg/m 3 during the period from the start-up to the operation of the system for 16 hours; after the system is operated for 18 hours, the concentration of SO 2 in the purified gas reaches 9.5mg/m 3, and at the moment, the adsorbent is continuously regenerated in the adsorption unit 4, and the total continuous operation of the system is maintained for 1000 hours from the starting.
In this example, the SO 2 content of the purified gas, the loss of the adsorbent, and the regeneration cycle of the adsorbent are shown in Table 1.
Comparative example 1
Based on the system of example 1, no adsorption unit was used, and only the thermal reaction unit, the catalytic reaction unit and the exhaust gas purification unit were maintained.
The method according to example 1 was conducted except that only steps (1) to (3) were conducted, in which in step (3), a hydrogen-containing hydrogen sulfide-removed tail gas (content of H 2: 4.5v%, content of H 2 S: 68ppm; content of COS: 16 ppm) was obtained at the top of the absorption column 34, and the entire hydrogen-containing hydrogen sulfide-removed tail gas was fed into the incinerator 35 to be incinerated (temperature: 680 ℃ C.; space velocity: 1000H -1), and an incineration tail gas containing sulfur dioxide was produced as a purge gas (content of SO 2: 238mg/m 3) to be discharged through a chimney. Other conditions were the same as in example 1.
In this comparative example, the content of SO 2 in the obtained purge gas is shown in Table 1.
Comparative example 2
The adsorption unit in the system of example 1 was replaced with a caustic scrubber.
Steps (1) to (3) were performed according to the method and parameters of example 1, wherein in step (3), a hydrogen-containing hydrogen sulfide-removed tail gas (content of H 2: 4.5v%, content of H 2 S: 68ppm; content of COS: 16 ppm) was obtained at the top of the absorption column 34, and the entire hydrogen-containing hydrogen sulfide-removed tail gas was fed into the incinerator 35 to be incinerated (temperature: 680 ℃ C.; space velocity: 1000H -1), yielding an incinerated tail gas containing sulfur dioxide (content of SO 2: 238mg/m 3);
And (3) conveying the incineration tail gas containing the sulfur dioxide to an alkaline washing tower (adopting NaOH solution with the concentration of 10 wt%) and removing SO 2 in the incineration tail gas under the absorption action of alkali liquor (the absorption temperature is 35 ℃ and the pressure is 0.1 MPa), SO as to obtain purified gas, and discharging the purified gas from the alkaline washing tower through a chimney.
In this comparative example, the content of SO 2 in the obtained purge gas is shown in Table 1.
The system can be operated for a long time to generate serious corrosion phenomenon, so that the device cannot be operated normally, the generated salt-containing wastewater is difficult to treat, and the reprocessing investment is huge.
Comparative example 3
Step (1) -step (3) were performed according to the method and parameters of example 3, wherein, in step (3), the resulting hydrogen-containing hydrogen sulfide free tail gas-II did not enter the adsorption unit 4; in the step (4-1), the hydrogen sulfide removal tail gas-II is replaced by nitrogen; in the step (4-2), the hydrogen sulfide removal tail gas-II is replaced by nitrogen which is subjected to heat exchange with the incineration tail gas and is heated in the step (4-1), and the nitrogen is heated to 380 ℃ when entering the regenerator 42. Other conditions were the same as in example 1.
The concentration of SO 2 in the purified gas is 0mg/m 3 during the period from the system start to the operation for 10 hours; after the system is operated for 13 hours, the concentration of SO 2 in the purified gas reaches 12mg/m 3, and at the moment, the adsorbent is continuously regenerated in the adsorption unit 4, and the total continuous operation of the system is maintained for 1000 hours from the starting.
In this comparative example, the content of SO 2 in the resultant purge gas, the loss of the adsorbent, and the regeneration cycle of the adsorbent are shown in Table 1.
TABLE 1
As can be seen from Table 1, by adopting the treatment system and the method for the hydrogen sulfide-containing gas provided by the invention, near zero emission of the sulfur device flue gas SO 2 with the emission concentration less than or equal to 10mg/m 3 can be realized, and meanwhile, the loss of the adsorbent in operation for 1000 hours is less than or equal to 1wt%, compared with the existing system and process, the emission concentration of the flue gas SO 2 in the sulfur recovery process is greatly reduced, the use loss of the adsorbent is low, the cycle regeneration period is longer, and the requirement of long-period stable operation of the system is met.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A treatment system for a gas containing hydrogen sulfide, which is characterized by comprising a thermal reaction unit (1), a catalytic reaction unit (2), a tail gas purification unit (3) and an adsorption unit (4) which are connected in sequence;
wherein the thermal reaction unit (1) is used for carrying out thermal reaction on the gas containing hydrogen sulfide to obtain sulfur and process gas;
The catalytic reaction unit (2) is used for carrying out a Claus conversion reaction on the process gas to obtain sulfur and Claus tail gas;
The tail gas purifying unit (3) is used for sequentially carrying out hydrotreatment and dehydrosulfuration on the Claus tail gas to obtain hydrogen-containing dehydrosulfuration tail gas, wherein the hydrogen-containing dehydrosulfuration tail gas is divided into two parts of hydrogen-containing dehydrosulfuration tail gas-I and hydrogen-containing dehydrosulfuration tail gas-II, and the hydrogen-containing dehydrosulfuration tail gas-I is subjected to incineration treatment to obtain the incineration tail gas containing sulfur dioxide;
The adsorption unit (4) comprises a movable adsorption bed (41) and a regenerator (42) which are connected and are loaded with an adsorbent, and the movable adsorption bed is used for carrying out adsorption sulfur dioxide removal treatment on the incineration tail gas by using the adsorbent to obtain purified gas; and performing thermal regeneration treatment on the adsorbent to be regenerated obtained after adsorption and sulfur dioxide removal treatment by using at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II as regeneration gas to obtain a regenerated adsorbent and regeneration gas containing sulfur dioxide;
wherein the regenerated adsorbent is circulated back to the moving adsorbent bed (41), and the regenerated gas containing sulfur dioxide is returned to at least one of the thermal reaction unit (1), the catalytic reaction unit (2) and the exhaust gas purification unit (3).
2. The system according to claim 1, wherein the thermal reaction unit (1) comprises a sulfur producer (11) and a first cooling device (12) connected in sequence;
Preferably, the catalytic reaction unit (2) comprises a primary converter (21) and a secondary converter (22) which are connected in sequence; wherein the primary converter (21) is connected to the first cooling device (12);
Preferably, the catalytic reaction unit (2) further comprises second (23) and third (24) cooling means; wherein the second cooling device (23) is respectively connected with the primary converter (21) and the secondary converter (22); said third cooling means (24) being connected to said secondary converter (22);
preferably, the tail gas purifying unit (3) comprises a hydrogenation device (31), an absorption tower (34) and an incinerator (35) which are connected in sequence; wherein the hydrogenation unit (31) is connected to the third cooling unit (24);
Preferably, the tail gas purification unit (3) further comprises a quenching tower (33), and the quenching tower (33) is respectively connected with the hydrogenation device (31) and the absorption tower (34).
3. The system according to claim 2, wherein the adsorption unit (4) further comprises a waste heat boiler (44), a first heat exchanger (45) and a second heat exchanger (46) connected in sequence;
preferably, the waste heat boiler (44) is connected to the incinerator (35);
Preferably, the first heat exchanger (45) is connected to the absorber (34) and regenerator (42), respectively;
preferably, the second heat exchanger (46) is connected to the moving adsorbent bed (41);
preferably, the adsorption unit (4) further comprises an auxiliary heater (47), the auxiliary heater (47) being connected to the regenerator (42) and the first heat exchanger (45), respectively.
4. A system according to claim 3, wherein the moving adsorbent bed (41) comprises a storage layer (411), an adsorbent layer (412) and a discharge layer (413) arranged in sequence from top to bottom;
Preferably, the reservoir (411) is connected to the regenerator (42);
preferably, the adsorption layer (412) is connected to the second heat exchanger (46);
preferably, the discharge layer (413) is connected to the regenerator (42).
5. The system according to any one of claims 2-4, wherein the regenerator (42) is connected to at least one of the sulfur producing furnace (11), primary converter (21), secondary converter (22) and hydrogenation unit (31).
6. A method for treating a hydrogen sulfide-containing gas, comprising:
(1) Carrying out thermal reaction on the gas containing hydrogen sulfide to obtain sulfur and process gas;
(2) Carrying out a Claus conversion reaction on the process gas to obtain sulfur and Claus tail gas;
(3) The Claus tail gas is subjected to hydrotreatment and dehydrosulfurization in sequence to obtain hydrogen-containing dehydrosulfurization tail gas, wherein the hydrogen-containing dehydrosulfurization tail gas is divided into hydrogen-containing dehydrosulfurization tail gas-I and hydrogen-containing dehydrosulfurization tail gas-II, and the hydrogen-containing dehydrosulfurization tail gas-I is subjected to incineration treatment to obtain sulfur dioxide-containing incineration tail gas;
(4) Absorbing and removing sulfur dioxide from the incineration tail gas by using an adsorbent to obtain purified gas; and performing thermal regeneration treatment on the adsorbent to be regenerated obtained after adsorption and sulfur dioxide removal treatment by using at least part of the hydrogen-containing hydrogen sulfide removal tail gas-II as regeneration gas to obtain a regenerated adsorbent and regeneration gas containing sulfur dioxide;
Wherein the regenerated adsorbent is recycled back to the adsorption sulfur dioxide removal treatment; the sulfur dioxide-containing regeneration gas is recycled back to at least one of the thermal reaction, the claus conversion reaction, and the hydrotreatment.
7. The method according to claim 6, wherein in step (1), the content of H 2 S in the hydrogen sulfide-containing gas is 30-90% by volume, preferably 50-85% by volume;
Preferably, in the step (1), the content of H 2 S in the process gas is 3-10% by volume; the content of SO 2 is 1.5-5% by volume; the content of COS is 0.2-1v%;
Preferably, in the step (2), the content of H 2 S in the Claus tail gas is 0.5-2% by volume; the content of SO 2 is 0.3-1% v; the COS content is 0.01-0.05v%.
8. The process according to claim 6 or 7, wherein in step (3) the hydrogen-containing de-hydrogen sulphide tail gas has a content of H 2 to 2 v%, preferably 3 to 5v%; h 2 S content is 5-200ppm; the content of COS is 2-100ppm;
preferably, the hydrogen-containing hydrogen sulfide removal tail gas-I: the volume ratio of the hydrogen sulfide removal tail gas-II containing hydrogen is (20-50): 1, preferably (30-45): 1, a step of;
Preferably, the content of SO 2 in the incineration tail gas is 50-1000mg/m 3, preferably 50-500mg/m 3.
9. The method according to any one of claims 6-8, wherein in step (4), the adsorbent is selected from at least one of activated carbon, activated coke, metal oxide and molecular sieve, preferably activated carbon;
Preferably, the initial sulfur capacity of the adsorbent is 100-250g sulfur per 1000g adsorbent;
Preferably, the conditions for the adsorption sulfur dioxide removal treatment include: the temperature is 30-120deg.C, preferably 60-105deg.C; the space velocity of the incineration tail gas is 800-1500h -1, preferably 1000-1250h -1;
Preferably, the content of SO 2 in the purified gas is less than or equal to 10mg/m 3, preferably less than or equal to 5mg/m 3.
10. The method according to any one of claims 6 to 9, wherein in step (4), the conditions of the thermal regeneration treatment include: the temperature of the hydrogen-containing hydrogen sulfide removal tail gas-II is 300-450 ℃.
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