CN115285941A - Low-temperature catalytic direct reduction of SO in flue gas 2 Method for preparing sulfur - Google Patents
Low-temperature catalytic direct reduction of SO in flue gas 2 Method for preparing sulfur Download PDFInfo
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- CN115285941A CN115285941A CN202210731444.7A CN202210731444A CN115285941A CN 115285941 A CN115285941 A CN 115285941A CN 202210731444 A CN202210731444 A CN 202210731444A CN 115285941 A CN115285941 A CN 115285941A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 220
- 239000011593 sulfur Substances 0.000 title claims abstract description 197
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 197
- 239000003546 flue gas Substances 0.000 title claims abstract description 117
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 116
- 238000000034 method Methods 0.000 title claims abstract description 52
- 230000009467 reduction Effects 0.000 title claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- 239000007789 gas Substances 0.000 claims abstract description 58
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 34
- 238000006722 reduction reaction Methods 0.000 claims abstract description 33
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 24
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 11
- 239000000428 dust Substances 0.000 claims abstract description 7
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 239000000779 smoke Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 230000008929 regeneration Effects 0.000 claims description 21
- 238000011069 regeneration method Methods 0.000 claims description 21
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 15
- 239000003463 adsorbent Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000006477 desulfuration reaction Methods 0.000 claims description 9
- 230000023556 desulfurization Effects 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- 238000010926 purge Methods 0.000 claims description 8
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 230000009471 action Effects 0.000 claims description 3
- 239000003034 coal gas Substances 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000010419 fine particle Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000010408 sweeping Methods 0.000 claims description 3
- 238000009825 accumulation Methods 0.000 claims description 2
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 2
- 238000002309 gasification Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 86
- 238000010521 absorption reaction Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 6
- 239000007791 liquid phase Substances 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000003570 air Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 description 2
- JJWKPURADFRFRB-UHFFFAOYSA-N carbonyl sulfide Chemical compound O=C=S JJWKPURADFRFRB-UHFFFAOYSA-N 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical compound [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- NBHIDQCTZATZRL-UHFFFAOYSA-N [O-2].[Al+3].[Mo+4].[Co+2] Chemical compound [O-2].[Al+3].[Mo+4].[Co+2] NBHIDQCTZATZRL-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- KFZAUHNPPZCSCR-UHFFFAOYSA-N iron zinc Chemical group [Fe].[Zn] KFZAUHNPPZCSCR-UHFFFAOYSA-N 0.000 description 1
- -1 iron-zinc-cobalt-molybdenum-nickel Chemical compound 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
- C01B17/0434—Catalyst compositions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0452—Process control; Start-up or cooling-down procedures of the Claus process
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Automation & Control Theory (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention belongs to the field of environmental protection and resource recovery, and relates to low-temperature catalytic direct reduction of SO in flue gas 2 In the method for preparing the sulfur, the dedusted raw flue gas is cooled by a primary heat exchanger (7B), micro dust and heavy metal impurities in the flue gas are removed by a washing tower (8), the flue gas is returned to the primary heat exchanger (7B) for preheating, and then the flue gas is heated by a secondary heat exchanger (7C); the sulfide gas such as hydrogen sulfide obtained from a sulfur catalytic reduction reactor (6) and the heated SO obtained in the step 1) 2 The flue gases are mixed and fed together into a catalyst bed (1), SO 2 Forms sulfur by Claus reaction with sulfide gas and gradually accumulates on the surface of the catalyst. Compared with the prior art, the method can be used for reducing SO in the flue gas at a lower temperature 2 The sulfur is efficiently converted, the utilization rate of the reducing agent is close to 100%, the energy consumption can be remarkably reduced, and part of generated hydrogen sulfide gas can be used for treating heavy metals in smoke or washing wastewater, so that the method has a good application and popularization prospect.
Description
Technical Field
The invention belongs to the technical field of environmental protection, mainly aims at the comprehensive recycling treatment of flue gas sulfur dioxide, and relates to a method for directly reducing SO in flue gas by low-temperature catalysis 2 A method for preparing sulfur.
Background
Sulfur dioxide (SO) 2 ) The gas pollutant is widely distributed in a plurality of industries such as steel, electric power, nonferrous metal, petrochemical industry, chemical industry, building materials and the like, has the characteristics of wide distribution, large concentration gradient, difficult treatment and the like, and is easy to cause acid rain, harm an ecological system and destroy the environment due to improper treatment. At present SO 2 The treatment method mainly comprises the steps of absorbing SO by a dry method and a wet method 2 And reduction of SO 2 And (5) preparing sulfur. Absorbing SO by dry and wet methods 2 A large amount of gypsum waste is generated, and the gypsum waste is not easy to recycle, so that not only is precious sulfur resource wasted, but also the environment pollution is caused. The generated gypsum is easy to pollute water and soil by leaching, thereby causing secondary pollution.
Reduction of SO relative to a dry-wet desulfurization process 2 The sulfur preparation not only can eliminate sulfur dioxide pollution, but also can recover solid sulfur with high added value, and has good market prospect. Reduction of SO 2 The method of (2) is mainly divided into gas phase reduction and liquid phase absorption reduction. Compared with gas phase reduction, the efficiency of liquid phase absorption reduction is low, and a large amount of organic solvent or medicament is used, so that the cost is high, and environmental pollution is easily caused by large amount of leakage of the organic solvent. The produced sulfur still needs to be further dried, concentrated and distilled to produce solid sulfur, the operation process is complex, the energy consumption is high, and the existing organic solvent and the like influence the quality of the sulfur on one hand and easily cause the reduction of the recovery rate of the sulfur on the other hand. The problem can be avoided by directly reducing sulfur dioxide into solid sulfur in gas phase, but at present, because the flue gas atmosphere contains a large amount of oxygen, belongs to oxidizing atmosphere, and sulfur dioxide is difficult to directly catalytically reduce (with low efficiency) to produce sulfur, the absorption-regeneration-catalytic reduction process is mainly adopted, so that the process route is complicated, the investment is high, the energy consumption is high and other problems are causedThe problem restricts the practical application of the method.
SO 2 The reduction of sulfur is an important way for realizing sulfur resource, however, the general reducing agent has poor reducing performance at low temperature and is easily consumed by oxygen in the flue gas at high temperature, SO that the utilization rate and SO of the reducing agent are reduced 2 The reduction rate of (2) is low. If the flue gas is deoxidized or SO is treated 2 The separation and purification are carried out, and extra energy consumption or process complexity is increased.
Chinese patent CN201310285646.4 proposes an absorption device for SO 2 Method for co-producing sulfur by adopting calcium sulfide as absorbent to absorb SO 2 Produces sulfur in parallel and obtains good SO 2 Recovering, but the process still adopts methanol and/or ethanol as solvent to absorb SO in liquid phase 2 The process has the problem of using a large amount of organic solvent, and the adopted absorbent is calcium sulfide, so that the absorption efficiency is low. Patent CN201310285646.4 proposes a liquid phase catalytic reduction SO 2 Method for recovering sulfur from flue gas by absorbing SO with organic solvent containing elemental selenium catalyst 2 And reducing the sulfur into sulfur to obtain good SO 2 But the process is still a liquid-phase absorption reduction process and has the problems of low absorption reduction efficiency and the like. Patent CN201310285646.4 proposes a method for preparing sulfur and a system device for preparing sulfur, which adopts SO after absorption and regeneration 2 The solid sulfur is produced under the catalytic reduction, has good solid sulfur recovery effect, but the process relates to SO 2 Is SO without oxygen after purification 2 Not true flue gas atmosphere SO 2 The actual application value is not high, and the adopted reducing agent is not hydrogen sulfide, is harmful to the environment and has high cost. Patent CN202010332495.3 proposes a method and system for recovering sulfur by reducing sulfur dioxide with steel mill tail gas, which adopts steel mill tail gas CO and adds H 2 By reduction of SO 2 The sulfur is prepared with good effect, but the process adopts SO 2 Is SO without oxygen after purification 2 Not true flue gas atmosphere SO 2 And the adopted reducing agent is non-sulfide gas, and has the problems of difficult practical application, high cost and the like。
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for directly reducing SO in flue gas by low-temperature catalysis 2 The method for preparing the sulfur can directly perform catalytic reduction on the sulfur dioxide to produce the sulfur in the smoke atmosphere.
The purpose of the invention can be realized by the following technical scheme: low-temperature catalytic direct reduction of SO in flue gas 2 The method for preparing sulfur mainly comprises the following steps:
a) Flue gas pretreatment: the original flue gas after dust removal is cooled through a primary heat exchanger (hot side), impurities such as micro dust, heavy metals and the like in the flue gas are removed through a washing tower, the flue gas returns to the primary heat exchanger (cold side) for preheating, and then the flue gas is heated through a secondary preheater (cold side);
b) SO in flue gas 2 Low-temperature catalytic reduction of (2): the sulfide gas such as hydrogen sulfide obtained from a sulfur catalytic reduction reactor and the SO-containing gas after temperature rise 2 Mixing the flue gas, introducing into catalyst bed, and introducing into SO 2 Reacting with sulfide gas through Claus to form sulfur, and gradually accumulating on the surface of the catalyst;
c) Recovery of escaping sulfur vapor: the flue gas flowing out of the catalyst bed also carries a small amount of sulfur vapor, the sulfur vapor is efficiently trapped by the sulfur removal bed, and the flue gas is cooled by a secondary heat exchanger (hot side) and then sent to deep desulfurization treatment;
d) Regeneration of catalyst bed or sulphur removal bed and sulphur recovery: the catalyst beds and the sulfur removal beds are respectively provided with at least two groups, when sulfur in one group of catalyst beds or sulfur removal beds is accumulated to a certain degree, the catalyst beds or sulfur removal beds need to be regenerated, the flue gas path is switched to the other group of standby devices by using a valve to operate normally, and under the condition of being isolated from the flue gas, the catalyst beds or sulfur removal beds needing to be regenerated are swept by using nitrogen at higher temperature from top to bottom, so that the sulfur attached to the surfaces of the catalyst or the adsorbent is fully gasified and is carried out along with the gas flow. And then, respectively cooling the sulfur by two stages of sulfur coagulators to coagulate the sulfur into liquid, and flowing the liquid into a sulfur gathering groove for recycling. Then nitrogen is merged into the flue gas, and sulfur vapor which is not collected is captured by a sulfur removal bed;
e) Evaporation and catalytic reduction of sulfur: conveying the regenerated liquid sulfur part to a sulfur evaporator, heating to fully gasify the liquid sulfur, mixing with sulfur reducing agent gas, and allowing the mixture to enter a sulfur catalytic reduction reactor, wherein the sulfur is rapidly reduced into hydrogen sulfide and CS under the action of a catalyst 2 Or carbonyl sulfide and other sulfides to form sulfide mixed gas, then the sulfide mixed gas is cooled by a heat exchanger (hot side), and then the sulfide mixed gas is sent to the inlet of a catalyst bed as required and is mixed with flue gas to be used as SO 2 The reducing agent of (1) is used. A quantity of nitrogen is warmed using a heat exchanger (cold side) and used as a regeneration purge gas for the catalyst bed or sulfur removal bed.
Further, the raw flue gas is dedusted flue gas, wherein SO is 2 0.5-10% of oxygen, 5-30% (oxygen-poor or oxygen-rich smelting/roasting), 150-250 deg.C of flue gas temperature, and a certain amount of heavy metals and fine particles. After being cooled by a primary heat exchanger, the temperature of the flue gas is 100-150 ℃. The cooling washing is a spray tower or a dynamic wave washing device and is provided with a demisting system, and the washed flue gas is 40-70 ℃. The temperature of the washed flue gas is raised through a primary heat exchanger, so that the temperature of the flue gas reaches 120-140 ℃. Then continuously returning the temperature to 150-200 ℃ through a secondary heat exchanger.
Furthermore, the flue gas after being reheated and the sulfide gas obtained by sulfur reduction are premixed and then enter a catalyst bed for reaction, and the catalytic reaction temperature is 150-250 ℃ (because of exothermic reaction, the flue gas temperature after reaction is increased by 10-30 ℃). The amount of gaseous sulfur compounds added to the flue gas (in terms of the molar amount of hydrogen sulfide) is SO 2 1-2 times the amount; if the required sulphide concentration exceeds 3%, 2-3 additional sulphide gas feed ports are added along the length of the catalyst bed to ensure that the sulphide gas concentration per feed is less than 50% of its explosive limit.
Furthermore, the catalyst filled in the catalyst bed is granular alumina or oxygen modified by 1 or more transition metals of Mo, ni, co and TiThe loading amount of the aluminum oxide and the modified transition metal is 0.5-5%. The space velocity of the flue gas in the catalyst bed is 1000-6000h -1 。
Furthermore, the adsorbent filled in the used sulfur removal bed is granular activated alumina, and the space velocity of the flue gas in the sulfur removal bed (2A/B) is 3000-9000h -1 . Furthermore, when the accumulation amount of the sulfur in the catalyst bed or the sulfur removal bed reaches 0.5-5% of the mass of the catalyst or the adsorbent, the catalyst or the sulfur removal bed needs to be regenerated. Before regeneration, the flue gas is switched to another catalyst bed or a desulfurization bed, and the bed is isolated from the flue gas.
Further, the gas used for regeneration is nitrogen, and the sulfur is preheated to 350-500 ℃ by utilizing the heat of the outlet gas of the sulfur catalytic reduction reactor. The volume of nitrogen required for the regeneration of the catalyst bed or the sulfur removal bed is 10-20 times of the volume of the packed catalyst or adsorbent, and the purging time is 30-90 minutes.
Further, sulfur vapor carried by nitrogen purging passes through a secondary sulfur condenser to be cooled to below 200 ℃, and condensed liquid sulfur flows into a sulfur collecting groove to be collected. The heat released by the sulfur condenser is used for preheating nitrogen required by regeneration, and the preheated nitrogen exchanges heat with hot air flow behind the sulfur catalytic reduction reactor to reach the set temperature requirement.
Further, the SO 2 Reducing the amount of sulfide needed, extracting corresponding liquid sulfur from the sulfur condenser, sending the liquid sulfur into a sulfur evaporator, and gasifying the liquid sulfur into steam with the temperature of 450-500 ℃.
Further, the gasified sulfur vapor is mixed with a reducing agent and enters a sulfur catalytic reduction reactor for reaction. The reducing agent is one or more than two of natural gas, coal gas or hydrogen, and is added according to the dosage ratio of reducing sulfur into hydrogen sulfide or carbon disulfide. The catalytic unit uses granular alumina modified by 1 or more transition metals of Mo, ni, co and Ti, and the loading of the modified transition metals is 0.5-5%. The space velocity of the flue gas in the catalyst bed is 50-1000h -1 The reaction temperature is 500-700 ℃.
Further, after reduction of sulfur mainlyThe product is H 2 S, with a small amount of CS 2 Or COS having a total volume concentration in the gas stream of 20-70% and the balance CO 2 And water vapor. Cooling to below 300 deg.C by heat exchanger, mixing with flue gas, and using as SO 2 The reducing agent of (1). The hydrogen sulfide gas generated by the sulfur catalytic reduction reactor can also be partially used for treating heavy metals in flue gas or washing wastewater.
The relevant reaction equation in the invention is as follows:
8H 2 S+4SO 2 →S 8 +8H 2 O (1)
S 8 +2CH 4 +4H 2 O→8H 2 S+2CO 2 (2)
S 8 +8H 2 →8H 2 S (3)
3S 8 +8NH 3 →4N 2 +24H 2 S (4)
S 8 +8CO+8H 2 O→8H 2 S+8CO 2 (5)。
compared with the prior art, the invention has the following advantages:
1) The sulfur dioxide is directly recovered in the smoke atmosphere, the operation is simple, convenient and quick, and high-temperature heating is not needed; the recovery rate is high, and the recovery rate of sulfur dioxide reaches more than 85 percent;
2) The recovered solid sulfur does not need additional treatment, can be directly commercialized, avoids complex absorption, regeneration and distillation, and has extremely low energy consumption; the sulfur has high quality, the purity is more than 98 percent, and the value is high;
3) The adopted reducing agent has wide sources and flexible selectivity, and can be suitable for different industrial requirements.
4) In the process of removing and utilizing sulfur dioxide, only sulfur products are produced, and waste residues and waste water are not produced, so that the method is a clean production process.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the drawings and examples. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
As shown in figure 1, the low-temperature catalytic direct reduction of SO in flue gas 2 The system adopted by the method for preparing the sulfur comprises a flue gas catalytic reduction bed which is used alternately, a catalyst bed 1A, a catalyst bed 1B and a sulfur removal bed: a sulfur removal bed 2A, a sulfur removal bed 2B and a sulfur condenser: a sulfur condenser 3A and a sulfur condenser 3B, a sulfur gathering groove 4, a sulfur evaporator 5, a sulfur catalytic reduction reactor 6, and a gas-gas heat exchanger: the heat exchanger 7A comprises a primary heat exchanger 7B, a secondary heat exchanger 7C, a washing tower 8 and the like. The invention utilizes the recovered SO on site 2 Or sulfur generates sulfide gas, the sulfide gas is used as a reducing agent, and SO in oxygen-containing flue gas is treated at a low temperature of below 200 DEG C 2 Selective catalytic reduction is carried out to prepare high-quality sulfur. The method can remove SO in the flue gas at a lower temperature 2 The sulfur is efficiently converted, the utilization rate of the reducing agent is close to 100 percent, and the energy consumption can be obviously reduced. Meanwhile, part of the generated hydrogen sulfide gas can be used for treating heavy metals in flue gas or washing wastewater, and the method has a good application and popularization prospect, and specifically comprises the following steps:
1. flue gas pretreatment: after the raw flue gas after dust removal is cooled by a primary heat exchanger 7B, the temperature of the flue gas is 100-150 ℃, the tiny dust and heavy metal impurities in the flue gas are removed by a washing tower 8, the temperature of the washed flue gas is 40-70 ℃, the flue gas returns to the primary heat exchanger 7B for preheating, the temperature of the flue gas reaches 120-140 ℃, and then the temperature of the flue gas is heated by a secondary heat exchanger 7C, so that the temperature is raised to 150-200 ℃;
the original flue gas is dedusted flue gas, wherein SO 2 The content is 0.5-10%, the oxygen content is 5-30%, the flue gas temperature is 150-250 ℃, and a certain amount of heavy metal and fine particles are contained, and the temperature is reduced through a primary heat exchanger 7B; the washing tower 8 is a spray tower or a dynamic wave washing device and is provided with a demisting system.
2. SO in flue gas 2 Low-temperature catalytic reduction of (2): sulfur such as hydrogen sulfide obtained from the sulfur catalytic reduction reactor 6The compound gas and the heated SO containing gas obtained in the step 1 2 Mixing the flue gas, introducing into catalyst bed 1, catalytic reacting at 150-250 deg.C, and adding SO in the flue gas according to the molar weight of hydrogen sulfide 2 1-2 times the amount of SO 2 Reacting with sulfide gas through Claus to form sulfur, and gradually accumulating on the surface of the catalyst;
the catalyst filled in the catalyst bed is granular alumina or alumina modified by one or more transition metals of Mo, ni, co and Ti, the loading amount of the modified transition metal is 0.5-5%, and the air speed of the flue gas in the catalyst bed is 1000-6000h -1 ；
3. Recovery of escaping sulfur vapor: the flue gas flowing out of the catalyst bed 1 carries a small amount of sulfur vapor, the sulfur vapor is efficiently trapped by the sulfur removal bed 2, and the flue gas is cooled by the secondary heat exchanger 7C and then sent to deep desulfurization treatment;
the adsorbent filled in the desulfurization bed is granular activated alumina, and the space velocity of the flue gas in the desulfurization bed is 3000-9000h -1 。
4. Regeneration of catalyst bed or sulphur removal bed and sulphur recovery: the catalyst bed 1 comprises two groups connected in parallel: catalyst bed 1A and catalyst bed 1B, the sulfur removal bed 2 comprises two groups in parallel: when the accumulated amount of sulfur in one group of catalyst bed or sulfur removal bed reaches 0.5-5% of the mass of the catalyst or adsorbent, the sulfur is regenerated, the flue gas is switched to the other group of catalyst bed or sulfur removal bed by using a valve before regeneration, the regenerated catalyst bed or sulfur removal bed is isolated from the flue gas, the sulfur accumulated in the catalyst bed or sulfur removal bed to be regenerated is swept from top to bottom by using higher nitrogen (the nitrogen for regeneration sweeping is preheated to 350-500 ℃ by using the heat of gas at the outlet of a sulfur catalytic reduction reactor 6, the nitrogen volume required for regeneration of the catalyst bed or sulfur removal bed is 10-20 times of the volume of the filled catalyst or adsorbent, the sweeping time is 30-90 minutes), the sulfur attached to the surface of the catalyst or adsorbent is fully gasified, the sulfur is carried along with the gas flow, is respectively subjected to temperature reduction treatment by a two-stage sulfur condenser 3 (shown as 3A and 3B in the figure), is cooled to below 200 ℃, the sulfur is condensed into liquid, flows into a sulfur sink 4 to be recovered, and is collected into the sulfur removal bed, and the flue gas is collected by using the nitrogen vapor which is not recovered; the heat released by the condenser 3 is used for preheating the nitrogen required by regeneration, and the preheated nitrogen exchanges heat with the hot air flow behind the sulfur catalytic reduction reactor 6 to reach the set temperature requirement.
5. Evaporation and catalytic reduction of sulfur: according to SO 2 Reducing the amount of sulfide, transferring the regenerated liquid sulfur to a sulfur evaporator 5, heating to gasify the liquid sulfur into steam at 450-500 deg.C, mixing with sulfur reducer gas, and introducing into a catalytic sulfur reduction reactor 6, wherein the reducer is one or more of natural gas, coal gas or hydrogen, and is added according to the dosage ratio of reducing sulfur into hydrogen sulfide or carbon disulfide, and sulfur is rapidly reduced into sulfide (the main product is H) under the action of catalyst 2 S, with a small amount of CS 2 Or COS, with a total volume concentration of 20-70% in the gas stream, and the balance CO 2 And steam) to form a sulfide mixed gas, cooling to a temperature lower than 300 ℃ by a heat exchanger 7A, then feeding the sulfide mixed gas to a catalyst bed inlet as required, and mixing with flue gas to form SO 2 The reducing agent (2) is used as a regeneration purge gas for the catalyst bed or the sulfur removal bed by heating nitrogen gas in the heat exchanger 7A.
The effect of the process of the invention is verified by the following specific examples.
Example 1:
the laboratory tests for preparing sulfur from sulfur dioxide prove that the sulfur is prepared from sulfur dioxide. At S 8 Hydrogenation stage, initial stage using CH 4 Reduction of solid sulphur as a reducing agent to produce hydrogen sulphide, in which CH 4 Relative to S 8 Is 2.05 4 And H 2 The stoichiometric ratio of O is 1 2 As a carrier gas. Adopting a tubular furnace reactor, filling a cobalt-molybdenum-aluminum oxide catalyst as a catalyst, and setting the airspeed for 1000h -1 The reaction temperature is 650 ℃, the yield of the hydrogen sulfide is 97 percent, and the rest is sulfur andunconsumed CH 4 And the like.
In SO 2 In the catalytic reduction stage, the total gas flow is 5L/min, the temperature is 180 ℃, the mixed gas of air, carbon dioxide and sulfur dioxide is adopted to simulate the flue gas atmosphere, the specific sulfur dioxide concentration is 2vol%, the oxygen concentration is 5vol%, and CO 2 The concentration is 5vol%, and the rest is N 2 . Will S 8 H produced by catalytic hydrogenation 2 S is divided into four paths to introduce SO 2 Catalytic reduction furnace, wherein each path of H 2 S concentration 1.5vol%, total H 2 S introduction amount and SO 2 Is 2.1. The catalyst filled in the tube furnace is active alumina with the airspeed of 5000h -1 。
The recovery rate of sulfur dioxide reaches 80-85%; the yield of the export sulfur is 85-95%, the purity is 96%, and the export sulfur can be directly recycled.
Example 2:
and (5) demonstrating the field process of the nonferrous smelting industry. Wherein the flue gas is subjected to denitration and dust removal and then mainly comprises SO 2 (5.3vol％),O 2 (8.3vol％)，CO 2 (9.2 vol%), CO (0.12 vol%), remainder N 2 . The amount of flue gas required to be treated is 3000m 3 The relevant sulfur dioxide recovery experiments were performed.
H in a sulfur hydrogenation reactor 2 S production, heating the produced sulfur through a sulfur gathering groove 4, gasifying the sulfur to 450 ℃ through a sulfur evaporator, and sending the sulfur into a sulfur catalytic reduction reactor 6. By using CO/H 2 Reduction of solid sulphur as a reducing agent to produce hydrogen sulphide, of which CO and H 2 1, CO relative to S in a ratio of 1 8 Is 4.08, water vapor enters by bubbling, CO and H are mixed in 2 The stoichiometric ratio of O is 1.5, N 2 And the carrier gas is also sent to the sulfur catalytic reduction reactor 6 for reaction. The catalyst is nickel-molybdenum-alumina catalyst, and the airspeed is set to 3000h -1 The reaction temperature is 450 ℃, the yield of the hydrogen sulfide is 99 percent, and the balance is sulfur and unconsumed CH 4 And the like. After the reaction, the gas is cooled to 200 ℃ by a gas-gas heat exchanger 7A and then is sent into a catalyst bed 1A for reaction.
In SO 2 CatalysisIn the reduction stage, the hot flue gas is cooled and washed by a gas-gas primary heat exchanger 7B, then is purified by a flue gas washing and purifying washing tower 8, is heated to 160 ℃ by a gas-gas heat exchanger, and is sent to a catalyst bed 1A, the temperature of the catalyst bed 1A is raised to 175 ℃ due to the Claus reaction, and S is obtained 8 H produced by catalytic hydrogenation 2 S is divided into five paths to introduce SO 2 Catalytic reduction furnace, in which each path of H 2 S concentration 3vol%, total H 2 S introduction amount and SO 2 Is 2.15. The catalyst filled in the tube furnace is iron-zinc loaded active alumina, and the airspeed is 3000h -1 . The yield of the sulfur is 88-98%, and the purity is 98.4%. When the sulfur is enriched to 5% of the alumina mass, the valve is switched to the catalyst bed 1B and N is opened 2 The valve was opened to the catalyst bed 1A at a flow rate of 1L/min. The sulfur in the catalyst bed 1A enters a sulfur condenser 3A through hot blowing, flows through a sulfur condenser 3B for secondary condensation, and finally enters a sulfur collection groove 4 for storage.
The recovery rate of sulfur dioxide is 85%, the yield of sulfur is 98%, the purity is 98.7%, the sulfur can be used for vulcanizing rubber, and the contact method for preparing sulfuric acid has great economic value.
The alumina catalyst references in each of the above examples (Shechun, shanghai torch, litong, et al. TiO) 2 And V 2 O 5 Modified Al 2 O 3 Performance of catalyst in catalyzing hydrolysis of organic sulfide [ J]Petrochemical, 2009 (04): 42-46.) by the methods reported in; the iron-zinc-cobalt-molybdenum-nickel loaded alumina catalyst is prepared by the following method: first 10 kg of alumina support are immersed in water and stirred for half an hour. Then adding nitrate corresponding to cobalt molybdenum or nickel according to the range of 0.05-0.2% of the mass of the alumina, then adding a urea chelating agent, and continuing stirring for 10 hours. And carrying out hydrothermal reaction on the obtained suspension at 150 ℃ for 10 hours, naturally cooling, filtering, washing, separating and drying to obtain the supported precursor. Roasting the obtained precursor for 2 hours at 450 ℃ to obtain a final supported catalyst, wherein the molar ratio of cobalt to molybdenum in the cobalt-molybdenum alumina catalyst used in the embodiment is 1; the molar ratio of nickel to molybdenum in the nickel-molybdenum alumina catalyst in example 2 is 1.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Those skilled in the art will readily be able to modify and apply the generic principles of the embodiments to other embodiments without undue experimentation. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. Low-temperature catalytic direct reduction of SO in flue gas 2 The method for preparing the sulfur is characterized by comprising the following steps:
1) Flue gas pretreatment: the dedusted raw flue gas is cooled by a primary heat exchanger (7B), micro dust and heavy metal impurities in the flue gas are removed by a washing tower (8), the flue gas is returned to the primary heat exchanger (7B) for preheating, and then the flue gas is heated by a secondary heat exchanger (7C);
2) SO in flue gas 2 The low-temperature catalytic reduction of (2): sulfide gas obtained from a sulfur catalytic reduction reactor (6) and the heated SO-containing gas obtained in the step 1) 2 The flue gas is mixed and enters the catalyst bed (1), SO 2 Reacting with sulfide gas through Claus to form sulfur, and gradually accumulating on the surface of the catalyst;
3) Recovery of escaping sulfur vapor: the flue gas flowing out of the catalyst bed (1) carries a small amount of sulfur vapor, the sulfur vapor is efficiently captured by the sulfur removal bed (2), and the flue gas is cooled by the secondary heat exchanger (7C) and then sent to deep desulfurization treatment;
4) Regeneration and sulfur recovery of the catalyst bed (1) or the sulfur removal bed (2): sweeping the sulfur accumulated in the catalyst bed (1) or the sulfur removal bed (2) from top to bottom by adopting nitrogen, fully gasifying the sulfur attached to the surface of the catalyst or the adsorbent, carrying out the gasification along with the airflow, respectively cooling by a two-stage sulfur condenser (3), condensing the sulfur into liquid, flowing into a sulfur converging groove (4) for recycling, converging the nitrogen into the flue gas, and trapping the sulfur vapor which is not collected by using the sulfur removal bed;
5) Evaporation and catalytic reduction of sulfur:the liquid sulfur obtained by regeneration is partially conveyed to a sulfur evaporator (5), the liquid sulfur is fully gasified by heating, then is mixed with sulfur reducing agent gas and enters a sulfur catalytic reduction reactor (6), the sulfur is rapidly reduced into sulfide under the action of a catalyst to form sulfide mixed gas, then the sulfide mixed gas is cooled by a heat exchanger (7A), and then is conveyed to the inlet of a catalyst bed (1) as required and is mixed with flue gas to be used as SO 2 The reducing agent (2) is used as a regeneration purge gas for the catalyst bed (1) or the sulfur removal bed (2) by raising the temperature of nitrogen gas by the heat exchanger (7A).
2. The method of claim 1 for direct reduction of SO in flue gas by low temperature catalysis 2 The method for preparing sulfur is characterized in that the raw flue gas in the step 1) is dedusted flue gas, wherein SO is 2 The content of 0.5-10 percent, the oxygen content of 5-30 percent, the temperature of the flue gas is 150-250 ℃, and the flue gas contains a certain amount of heavy metal and fine particles, and the temperature of the flue gas is 100-150 ℃ after the temperature of the flue gas is reduced by a primary heat exchanger (7B);
the washing tower (8) is a spray tower or a dynamic wave washing device and is provided with a demisting system, the washed flue gas is 40-70 ℃, the temperature of the washed flue gas is increased through a primary heat exchanger (7B) to reach 120-140 ℃, and the temperature of the washed flue gas is continuously increased through a secondary heat exchanger (7C) to reach 150-200 ℃.
3. The low-temperature catalytic direct reduction of SO in flue gas according to claim 1 2 The method for preparing the sulfur is characterized in that the catalytic reaction temperature of the catalyst bed (1) is 150-250 ℃, and the amount of the gas sulfide added into the flue gas is SO in terms of the molar weight of the hydrogen sulfide 2 1-2 times the amount.
4. The low-temperature catalytic direct reduction of SO in flue gas according to claim 1 2 The method for preparing the sulfur is characterized in that the catalyst filled in the catalyst bed (1) is granular alumina or alumina modified by one or more transition metals of Mo, ni, co and Ti, and the modified transition metal is loadedThe amount is 0.5-5%, and the space velocity of the flue gas in the catalyst bed is 1000-6000h -1 ；
The adsorbent filled in the desulfurization bed (2) is granular activated alumina, and the space velocity of the flue gas in the desulfurization bed (2) is 3000-9000h -1 。
5. The low-temperature catalytic direct reduction of SO in flue gas according to claim 1 or 4 2 The method for preparing the sulfur is characterized in that the catalyst bed (1) comprises two groups in parallel: catalyst bed (1A) and catalyst bed (1B), the sulphur removal bed (2) comprises two groups connected in parallel: a sulfur removal bed (2A) and a sulfur removal bed (2B),
when the accumulation amount of the sulfur in one group of catalyst beds or sulfur removal beds reaches 0.5-5% of the mass of the catalyst or adsorbent, the catalyst beds or sulfur removal beds are regenerated, the flue gas is switched to the other group of catalyst beds or sulfur removal beds before regeneration, and the regenerated catalyst beds or sulfur removal beds are isolated from the flue gas.
6. The low-temperature catalytic direct reduction of SO in flue gas according to claim 1 2 The method for preparing the sulfur is characterized in that the heat of the gas at the outlet of the sulfur catalytic reduction reactor (6) is utilized to preheat the nitrogen for regeneration and purging to 350-500 ℃; the volume of nitrogen required for regeneration of the catalyst bed (1) or the sulfur removal bed (2) is 10-20 times of the volume of the packed catalyst or adsorbent, and the purging time is 30-90 minutes.
7. The low-temperature catalytic direct reduction of SO in flue gas according to claim 6 2 The method for preparing the sulfur is characterized in that sulfur vapor carried by nitrogen purging is cooled to be below 200 ℃ through a two-stage sulfur condenser (3), condensed liquid sulfur flows into a sulfur gathering groove (4) to be collected, heat released by the sulfur condenser (3) is used for preheating nitrogen needed by regeneration, and the preheated nitrogen exchanges heat with hot air after a sulfur catalytic reduction reactor (6) to meet the set temperature requirement.
8. The low temperature catalytic direct reduction smoke of claim 1SO in gas 2 Process for the production of sulphur, characterised in that it is carried out according to SO 2 Reducing the amount of the required sulfide, extracting corresponding liquid sulfur from the sulfur condenser (3), sending the liquid sulfur into a sulfur evaporator (5), and gasifying the liquid sulfur into steam with the temperature of 450-500 ℃.
9. The low-temperature catalytic direct reduction of SO in flue gas according to claim 1 2 The method for preparing the sulfur is characterized in that the gasified sulfur steam is mixed with a reducing agent and enters a sulfur catalytic reduction reactor (6) for reaction, the used reducing agent is one or more than two of natural gas, coal gas or hydrogen, and the reducing agent is added according to the dosage ratio of reducing the sulfur into hydrogen sulfide or carbon disulfide.
10. The low-temperature catalytic direct reduction of SO in flue gas according to claim 1 2 The method for preparing the sulfur is characterized in that the main product after the sulfur is reduced is H 2 S, with a small amount of CS 2 Or COS, with a total volume concentration of 20-70% in the gas stream, and the balance CO 2 And water vapor, the temperature of the water vapor is reduced to be lower than 300 ℃ through a heat exchanger (7A), and the water vapor is sent to be mixed with the flue gas and used as SO 2 The reducing agent and the hydrogen sulfide gas generated by the catalytic reduction unit (6) can also be partially used for treating heavy metals in flue gas or washing wastewater.
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| US6297189B1 (en) * | 1998-01-14 | 2001-10-02 | The Regents Of The University Of California | Sulfide catalysts for reducing SO2 to elemental sulfur |
| CN101117214A (en) * | 2007-04-30 | 2008-02-06 | 中国石油集团工程设计有限责任公司 | Improved low-temperature Claus sulfur recovery method |
| CN103303872A (en) * | 2013-07-04 | 2013-09-18 | 陕西智惠环保科技有限公司 | System device and method for recycling sulfur dioxide from fume to prepare sulfur |
| CN105314606A (en) * | 2014-06-06 | 2016-02-10 | 中国石油化工股份有限公司 | Liquid sulfur degassing technology |
| CN216584203U (en) * | 2021-12-31 | 2022-05-24 | 镇海石化工程股份有限公司 | Zero-emission shutdown system for flue gas pollutants of sulfur recovery device |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6297189B1 (en) * | 1998-01-14 | 2001-10-02 | The Regents Of The University Of California | Sulfide catalysts for reducing SO2 to elemental sulfur |
| CN101117214A (en) * | 2007-04-30 | 2008-02-06 | 中国石油集团工程设计有限责任公司 | Improved low-temperature Claus sulfur recovery method |
| CN103303872A (en) * | 2013-07-04 | 2013-09-18 | 陕西智惠环保科技有限公司 | System device and method for recycling sulfur dioxide from fume to prepare sulfur |
| CN105314606A (en) * | 2014-06-06 | 2016-02-10 | 中国石油化工股份有限公司 | Liquid sulfur degassing technology |
| CN216584203U (en) * | 2021-12-31 | 2022-05-24 | 镇海石化工程股份有限公司 | Zero-emission shutdown system for flue gas pollutants of sulfur recovery device |
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