CN115285941B - Direct reduction of SO in flue gas by low-temperature catalysis 2 Method for preparing sulfur - Google Patents
Direct reduction of SO in flue gas by low-temperature catalysis 2 Method for preparing sulfur Download PDFInfo
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- CN115285941B CN115285941B CN202210731444.7A CN202210731444A CN115285941B CN 115285941 B CN115285941 B CN 115285941B CN 202210731444 A CN202210731444 A CN 202210731444A CN 115285941 B CN115285941 B CN 115285941B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 219
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 204
- 239000011593 sulfur Substances 0.000 title claims abstract description 204
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000003546 flue gas Substances 0.000 title claims abstract description 118
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 9
- 230000009467 reduction Effects 0.000 title claims description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 91
- 239000007789 gas Substances 0.000 claims abstract description 56
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 35
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 22
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims abstract description 16
- 238000011084 recovery Methods 0.000 claims abstract description 16
- 239000000428 dust Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 239000002351 wastewater Substances 0.000 claims abstract description 5
- 239000012535 impurity Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 44
- 238000006722 reduction reaction Methods 0.000 claims description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 230000008929 regeneration Effects 0.000 claims description 15
- 238000011069 regeneration method Methods 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
- 238000010926 purge Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052723 transition metal Inorganic materials 0.000 claims description 8
- 150000003624 transition metals Chemical class 0.000 claims description 8
- 230000001172 regenerating effect Effects 0.000 claims description 7
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 238000004064 recycling Methods 0.000 claims description 5
- 238000006477 desulfuration reaction Methods 0.000 claims description 4
- 230000023556 desulfurization Effects 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 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
- 239000001257 hydrogen Substances 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000003345 natural gas Substances 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 238000007664 blowing Methods 0.000 claims description 2
- 239000010419 fine particle Substances 0.000 claims description 2
- 239000000203 mixture Substances 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 84
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 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
- WHDPTDWLEKQKKX-UHFFFAOYSA-N cobalt molybdenum Chemical group [Co].[Co].[Mo] WHDPTDWLEKQKKX-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 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
- 239000003570 air Substances 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 239000000779 smoke Substances 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
- 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
- 239000005864 Sulphur Substances 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
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical group [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000011946 reduction process Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 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
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation 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
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient 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
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion 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
- 238000011065 in-situ storage 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
- 150000002739 metals Chemical class 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification 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
- 239000000126 substance Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Classifications
-
- 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 a method for directly reducing SO in flue gas by low-temperature catalysis 2 A method for preparing sulfur, which comprises the steps of,after the temperature of the raw flue gas after dust removal is reduced by the primary heat exchanger (7B), the dust and heavy metal impurities in the flue gas are removed by the washing tower (8), and the flue gas returns to the primary heat exchanger (7B) for preheating and then is heated by the secondary heat exchanger (7C); mixing sulfide gas such as hydrogen sulfide obtained from a sulfur catalytic reduction reactor (6) with SO-containing gas obtained in step 1) after heating 2 Mixing the flue gas and introducing the flue gas into a catalyst bed (1) together SO 2 Sulfur is formed by Claus reaction with the sulfide gas and gradually builds up on the catalyst surface. Compared with the prior art, the method can be used for removing SO in the flue gas at a lower temperature 2 The method has the advantages that the method is efficiently converted into sulfur, the utilization rate of the reducing agent is close to 100%, the energy consumption can be obviously reduced, and the generated partial hydrogen sulfide gas can be used for treating heavy metals in flue gas or washing wastewater, so that the method has good application and popularization prospects.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and mainly aims at recycling comprehensive treatment of sulfur dioxide in flue gas, 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 ) As a gaseous pollutant widely distributed in a plurality of industries such as steel, electric power, colored, petrochemical, chemical industry, building materials and the like, the method has the characteristics of wide distribution, large concentration gradient, difficult treatment and the like, and moreover, the improper treatment is easy to cause acid rain, harm an ecological system and destroy the environment. SO at present 2 The treatment method mainly comprises the steps of dry-wet absorption of SO 2 Reduction of SO 2 And (5) preparing sulfur. Adopting dry and wet method to absorb SO 2 A large amount of gypsum waste is produced, and the gypsum waste is not easy to recycle, so that precious sulfur resources are wasted and environmental pollution is caused. The gypsum is produced byThe leaching is extremely easy to pollute the water body and the soil and cause secondary pollution.
Reduction of SO relative to wet-dry desulfurization processes 2 The sulfur can not only eliminate sulfur dioxide pollution, but also 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 liquid phase absorption reduction has low efficiency, and a large amount of organic solvents or medicaments are used, so that the cost is high, and a large amount of organic solvents leak and leak to easily cause environmental pollution. And the produced sulfur still needs further drying, concentrating and distilling to produce solid sulfur, the operation process is complicated, so that the energy consumption is high, the quality of the sulfur is influenced by the existing organic solvent and the like, and the recovery rate of the sulfur is easily reduced. The problems can be avoided when the sulfur dioxide is directly reduced into solid sulfur by gas phase, but at present, because a great amount of oxygen exists in the flue gas atmosphere, the sulfur is difficult to directly catalyze and reduce (low in efficiency) the sulfur dioxide to produce sulfur, so that the absorption-regeneration-catalytic reduction process is mainly adopted, the problems of complex process route, high investment, high energy consumption and the like are caused, and the practical application is restricted.
SO 2 The reduction process of preparing sulfur is an important way for realizing sulfur recycling, however, the common reducing agent has poorer reduction performance at low temperature, and the common reducing agent is easily consumed by oxygen in flue gas at higher temperature, SO that the utilization rate and SO (sulfur dioxide) are caused 2 The reduction rate of (2) is low. If the flue gas is deoxidized or SO is performed 2 The separation and purification are carried out, and the energy consumption is extra or the process complexity is increased.
Chinese patent CN201310285646.4 proposes an absorption of SO 2 And co-production of sulfur, calcium sulfide is used as absorbent to absorb SO 2 And in combination with sulfur, good SO is obtained 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 of SO 2 Method for recycling sulfur from flue gasAbsorption of SO with organic solvent containing elemental selenium as catalyst 2 And reduced to sulfur, thus obtaining good SO 2 The recovery effect is achieved, but the process is still a liquid phase absorption reduction process, and the problems of low absorption reduction efficiency and the like exist. 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 SO related by the process 2 Is SO which is purified and does not contain oxygen 2 Not a real flue gas atmosphere SO 2 The practical application value is not high, and the adopted reducing agent is not hydrogen sulfide, and is harmful to the environment and high in cost. Patent CN202010332495.3 discloses a method and system for recovering sulfur by reducing sulfur dioxide by using tail gas of steel mill, wherein the tail gas of steel mill is adopted to carry out CO and H is added 2 Is reduced by (a) to SO 2 The sulfur is prepared to obtain good effect, but the SO adopted by the process 2 Is SO which is purified and does not contain oxygen 2 Not a real flue gas atmosphere SO 2 The adopted reducing agent is not sulfide gas, and the problems of difficult practical application, high cost and the like exist.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a method for catalyzing and directly reducing SO in flue gas at low temperature 2 The method for preparing sulfur can directly catalyze and reduce sulfur dioxide to produce sulfur in the flue gas atmosphere.
The aim of the invention can be achieved by the following technical scheme: direct reduction of SO in flue gas by low-temperature catalysis 2 The method for preparing sulfur mainly comprises the following steps:
a) Pretreatment of flue gas: the raw flue gas after dust removal is cooled by a primary heat exchanger (hot side), then the impurities such as tiny dust and heavy metal in the flue gas are removed by a washing tower, and the flue gas returns to the primary heat exchanger (cold side) for preheating, and then is heated by 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 the sulfur catalytic reduction reactor and the heated sulfurSO 2 Mixing the flue gas, and introducing the flue gas into a catalyst bed to obtain SO 2 Forms sulfur with sulfide gas through Claus reaction and gradually accumulates on the surface of the catalyst;
c) Recovery of escaping sulfur vapors: the flue gas flowing out of the catalyst bed also carries a small amount of sulfur vapor, the flue gas 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 sulfur removal bed and sulfur 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 extent, the catalyst beds or sulfur removal beds need to be regenerated, a valve is used for switching a flue gas path to another group of standby devices for normal operation, under the condition of being isolated from flue gas, the catalyst beds or sulfur removal beds needing to be regenerated are purged from top to bottom by utilizing nitrogen with higher temperature, and the sulfur attached to the surface of the catalyst or the adsorbent is fully gasified and carried out along with airflow. And then, respectively carrying out cooling treatment by a two-stage sulfur condenser to condense sulfur into liquid, and flowing into a sulfur collecting tank for recycling. Then nitrogen is led into the flue gas, and sulfur vapor which is not collected is captured by utilizing a sulfur removal bed;
e) Evaporation and catalytic reduction of sulfur: conveying the regenerated liquid sulfur part to a sulfur evaporator, fully gasifying the liquid sulfur by heating, mixing with sulfur reducing agent gas, and introducing into a sulfur catalytic reduction reactor, wherein under the action of a catalyst, the sulfur is rapidly reduced into hydrogen sulfide and CS 2 Or sulfide such as carbonyl sulfide to form sulfide mixed gas, cooling by a heat exchanger (hot side), feeding into an inlet of a catalyst bed as required, mixing with flue gas to obtain SO 2 Is used as the reducing agent. A certain amount of nitrogen is warmed up 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 flue gas after dust removal, wherein SO 2 0.5% -10%, 5-30% oxygen (oxygen-deficient or oxygen-enriched smelting/roasting), 150-250deg.C smoke temperature, and a certain amount ofHeavy metals, fine particulate matter, and the like. After the temperature is reduced by the 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 temperature of the washed flue gas is 40-70 ℃. And heating the washed flue gas by a primary heat exchanger to ensure that the temperature of the flue gas reaches 120-140 ℃. And then the temperature is continuously returned by the secondary heat exchanger, so that the temperature is increased to 150-200 ℃.
Further, the flue gas after temperature recovery is premixed with sulfide gas obtained by sulfur reduction, and then enters a catalyst bed for reaction, the catalytic reaction temperature is 150-250 ℃ (the temperature of the flue gas after reaction is increased by 10-30 ℃ due to exothermic reaction). The amount of gaseous sulphide added to the flue gas (calculated on a molar basis of hydrogen sulphide) is SO 2 1-2 times of the amount; if the required sulfide concentration exceeds 3%, 2-3 sulfide gas supplementing ports should be added in the length direction of the catalyst bed to ensure that the sulfide gas concentration added each time is lower than 50% of the explosion limit.
Further, the catalyst filled in the catalyst bed is granular alumina or alumina modified by using 1 or more transition metals in Mo, ni, co, ti, and the loading amount of the modified transition metals is 0.5-5%. The space velocity of the flue gas in the catalyst bed is 1000-6000h -1 。
Further, the adsorbent filled in the 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 . Further, the catalyst bed or sulfur removal bed needs to be regenerated when the accumulated amount of sulfur in the catalyst bed or sulfur removal bed reaches 0.5-5% of the mass of the catalyst or adsorbent. Before regeneration, the flue gas is switched to another catalyst bed or sulfur removal bed, and the bed is isolated from the flue gas.
Further, the gas used for regeneration is nitrogen, and the heat of the gas at the outlet of the sulfur catalytic reduction reactor is utilized to preheat the gas to 350-500 ℃. The volume of nitrogen required for regenerating the catalyst bed or sulfur removal bed is 10-20 times the volume of the filled catalyst or adsorbent, and the purging time is 30-90 minutes.
Further, the sulfur vapor carried by nitrogen purging is cooled to below 200 ℃ by a secondary sulfur condenser, and condensed liquid sulfur flows into a sulfur sink for collection. 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 after the sulfur catalytic reduction reactor to reach the set temperature requirement.
Further, the SO 2 The amount of sulfide needed for reduction is extracted from the sulfur condenser, and the corresponding liquid sulfur is sent into a sulfur evaporator to be gasified 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 used was particulate alumina modified with 1 or more transition metals of Mo, ni, co, ti, the loading of the modified transition metals being 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, the main product after sulfur reduction is H 2 S, and has a small amount of CS 2 Or COS, the total volume concentration of which in the gas stream is 20-70%, the balance being CO 2 And (3) water vapor. Cooling to below 300 deg.C with heat exchanger, mixing with flue gas, and using as SO 2 Is not limited. The hydrogen sulfide gas generated by the sulfur catalytic reduction reactor can 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) Sulfur dioxide is directly recovered in the flue gas atmosphere, the operation is simple and quick, and high-temperature heating is not needed; the recovery rate is high, and the sulfur dioxide recovery rate is more than 85%;
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 sulfur has higher value;
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, waste residues and waste water are not produced, and 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 with reference to the accompanying drawings and examples. It should be noted that variations and modifications could be made by those skilled in the art without departing from the spirit of the invention. These are all within the scope of the present invention.
As shown in figure 1, SO in low-temperature catalytic direct reduction flue gas 2 The method for preparing sulfur adopts a system comprising a catalyst bed 1A, a catalyst bed 1B and a sulfur removal bed which are used alternately, wherein the system comprises the flue gas catalytic reduction bed: sulfur removal bed 2A and sulfur removal bed 2B, sulfur condenser: sulfur condenser 3A and 3B, sulfur sink 4, sulfur evaporator 5, sulfur catalytic reduction reactor 6, gas-gas heat exchanger: the heat exchanger 7A comprises a primary heat exchanger 7B, a secondary heat exchanger 7C, a washing tower 8 and other units. The invention utilizes the recovered SO in situ 2 Or sulfur generates sulfide gas, and uses the sulfide gas as reducer to treat SO in oxygen-containing flue gas at low temperature below 200deg.C 2 And (3) performing selective catalytic reduction to prepare high-quality sulfur. The method can be used for removing the smoke at a lower temperatureSO 2 The high-efficiency conversion into sulfur is realized, the utilization rate of the reducing agent is close to 100%, and the energy consumption can be obviously reduced. Meanwhile, part of the generated hydrogen sulfide gas can also be used for treating heavy metals in flue gas or washing wastewater, and has better application and popularization prospects, and the method specifically comprises the following steps:
1. pretreatment of flue gas: cooling the raw flue gas subjected to dust removal by a primary heat exchanger 7B, wherein the temperature of the flue gas is 100-150 ℃, removing tiny dust and heavy metal impurities in the flue gas by a washing tower 8, returning the washed flue gas to the primary heat exchanger 7B for preheating at 40-70 ℃ to ensure that the temperature of the flue gas reaches 120-140 ℃, and then heating by a secondary heat exchanger 7C to ensure that the temperature is 150-200 ℃;
the raw flue gas is flue gas after dust removal, wherein SO 2 The content is 0.5-10%, the oxygen content is 5-30%, the temperature of the flue gas is 150-250 ℃, and the flue gas contains a certain amount of heavy metals and fine particles, and the flue gas is cooled 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 defogging system.
2. SO in flue gas 2 Low temperature catalytic reduction of (2): the sulfide gas such as hydrogen sulfide obtained from the sulfur catalytic reduction reactor 6 and the SO-containing gas obtained in the step 1 after the temperature is raised 2 Mixing the flue gas, feeding the mixed flue gas into a catalyst bed 1, wherein the catalytic reaction temperature is 150-250 ℃, and the amount of the added gas sulfide in the flue gas is calculated as SO according to the molar amount of hydrogen sulfide 2 1-2 times of the amount of SO 2 Forms sulfur with sulfide gas through Claus reaction and gradually accumulates 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 in Mo, ni, co, ti, the loading amount of the modified transition metals is 0.5-5%, and the space velocity of flue gas in the catalyst bed is 1000-6000h -1 ；
3. Recovery of escaping sulfur vapors: 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 sulfur removal bed isGranular activated alumina, and the space velocity of the flue gas in the sulfur removal bed is 3000-9000h -1 。
4. Regeneration of catalyst bed or sulfur removal bed and sulfur recovery: the catalyst bed 1 comprises two groups connected in parallel: catalyst bed 1A and catalyst bed 1B, the sulfur removal bed 2 comprising two sets in parallel: when the accumulated quantity of sulfur in one group of catalyst beds or sulfur removal beds reaches 0.5-5% of the mass of the catalyst or adsorbent, regenerating the catalyst beds or sulfur removal beds, switching the flue gas to the other group of catalyst beds or sulfur removal beds by using a valve before regeneration, isolating the regenerated catalyst beds or sulfur removal beds from the flue gas, purging the sulfur accumulated in the catalyst beds or sulfur removal beds to be regenerated from top to bottom by adopting higher nitrogen (preheating the regenerated purging nitrogen to 350-500 ℃ by using the heat of the outlet gas of the sulfur catalytic reduction reactor 6, wherein the volume of the nitrogen required for regenerating the catalyst beds or sulfur removal beds is 10-20 times of the volume of the filled catalyst or adsorbent, and the purging time is 30-90 minutes), fully gasifying the sulfur attached to the surface of the catalyst or adsorbent, carrying out cooling treatment by using a two-stage sulfur condenser 3 (such as 3A and 3B in the figure), cooling the sulfur to below 200 ℃ respectively, enabling the sulfur to flow into a liquid, and collecting the sulfur to flow into a sulfur collecting tank 4, and collecting the sulfur which is not recovered by using the sulfur collecting steam; the heat released by the sulfur condenser 3 is used for preheating nitrogen required by regeneration, and the preheated nitrogen exchanges heat with hot air flow after the sulfur catalytic reduction reactor 6 to reach the set temperature requirement.
5. Evaporation and catalytic reduction of sulfur: according to SO 2 The liquid sulfur part obtained by the regeneration is conveyed to a sulfur evaporator 5 for reducing the required sulfide amount, the liquid sulfur is fully gasified by heating, the gasified liquid sulfur is gasified into steam with the temperature of 450-500 ℃, then the steam is mixed with sulfur reducing agent gas and enters a sulfur catalytic reduction reactor 6, the used reducing agent is one or more than two of natural gas, coal gas or hydrogen, the reducing agent is added according to the dosage ratio of reducing sulfur into hydrogen sulfide or carbon disulfide, under the action of a catalyst, the sulfur is quickly reduced into sulfide (the main product is H 2 S, and has a small amount of CS 2 Or COS, the total volume concentration of which in the gas stream is 20-70%, the balance being CO 2 And steam) to form sulfide mixed gas, cooling to below 300 deg.C by heat exchanger 7A, feeding into the inlet of catalyst bed as required, mixing with flue gas, and making SO 2 The nitrogen is warmed by the heat exchanger 7A and used as a regeneration purge gas for the catalyst bed or sulfur removal bed.
The process effect of the present invention is verified by specific examples below.
Example 1:
laboratory experiment verification of sulfur preparation from sulfur dioxide. At S 8 In the hydrogenation reaction stage, CH is adopted in the initial stage 4 Reduction of solid sulphur as a reducing agent to hydrogen sulphide, wherein CH 4 Relative to S 8 The stoichiometric ratio of (2) to (1) is 2.05:1, and water vapor is introduced by bubbling, CH 4 And H is 2 The stoichiometric ratio of O is 1:2.5, N 2 As a carrier gas. Adopting a tubular furnace reactor, wherein the packed catalyst is cobalt molybdenum alumina catalyst, and the space velocity is set for 1000h -1 The reaction temperature is 650 ℃, the yield of hydrogen sulfide is 97%, and the rest is sulfur and unconsumed CH 4 And (3) waiting for gas.
At SO 2 In the catalytic reduction stage, the total gas flow is 5L/min, the temperature is 180 ℃, the atmosphere of flue gas is simulated by adopting air, carbon dioxide and sulfur dioxide mixed gas, the specific sulfur dioxide concentration is 2vol%, the oxygen concentration is 5vol%, and the CO is 2 The concentration is 5vol%, 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 H of each path 2 S concentration is 1.5vol%, total H 2 S incorporation amount and SO 2 Is 2.1. The catalyst filled in the tube furnace is activated alumina, and the space velocity is 5000h -1 。
The recovery rate of sulfur dioxide reaches 80-85 percent; the yield of the exported sulfur is 85-95%, the purity is 96%, and the exported sulfur can be directly recycled.
Example 2:
the nonferrous smelting industry is nowThe field process is demonstrated. Wherein the main component of the flue gas after denitration and dust removal is SO 2 (5.3vol％),O 2 (8.3vol％)，CO 2 (9.2 vol%), CO (0.12 vol%), the balance N 2 . The amount of smoke required to be treated is 3000m 3 And/h, performing relevant sulfur dioxide recovery experiments.
H is carried out in a sulfur hydrogenation reactor 2 S, heating the produced sulfur by a sulfur sink 4, gasifying the sulfur by a sulfur evaporator to 450 ℃ and sending the sulfur into a sulfur catalytic reduction reactor 6. By CO/H 2 Reduction of solid sulphur as a reducing agent to hydrogen sulphide, wherein CO and H 2 The ratio of CO to S is 1:1 8 The stoichiometric ratio of (2) is 4.08:1, water vapor is bubbled in, and CO and H are mixed 2 The stoichiometric ratio of O is 1:1.5, N 2 As carrier gas, the catalyst is also fed into a sulfur catalytic reduction reactor 6 for reaction. The packed catalyst is nickel molybdenum alumina catalyst, and the space velocity is set for 3000h -1 The reaction temperature is 450 ℃, the yield of hydrogen sulfide is 99 percent, and the rest is sulfur and unconsumed CH 4 And (3) waiting for gas. The gas after reaction is cooled to 200 ℃ by a gas-gas heat exchanger 7A and then is sent into a catalyst bed 1A for reaction.
At SO 2 In the catalytic 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 and washing tower 8, is heated to 160 ℃ by a gas-gas heat exchanger, is fed into a catalyst bed 1A, and the temperature of the catalyst bed 1A is raised to 175 ℃ due to Claus reaction, so that S is generated 8 H produced by catalytic hydrogenation 2 S is divided into five paths to introduce SO 2 Catalytic reduction furnace, wherein H of each path 2 S concentration is 3vol%, total H 2 S incorporation amount and SO 2 The stoichiometric ratio of (2) 15:1. 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 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. Sulfur in the catalyst bed 1A enters the sulfur condenser 3A through hot blowing and flows through the sulfur condenser 3B to be secondarily condensed, and finally enters the sulfur sink 4 to be stored.
The recovery rate of sulfur dioxide reaches 85%, the yield of sulfur is 98%, the purity is 98.7%, the method can be externally applied to vulcanized rubber, and the method for preparing sulfuric acid by contact has great economic value.
Alumina catalyst references (She Chun, upper sense torch, liang Litong, et al. TiO 2 And V 2 O 5 Modified Al 2 O 3 Performance of the catalyst to catalyze hydrolysis of organosulfides [ J]Petrochemical industry, 2009 (04): 42-46.); the iron-zinc-cobalt-molybdenum-nickel supported alumina catalyst is prepared by the following method: first, 10 kg of the alumina carrier was immersed in water and stirred for half an hour. Then adding nitrate corresponding to cobalt molybdenum or nickel according to the mass of the alumina in the interval of 0.05-0.2%, and then adding urea chelating agent and stirring for 10 hours. The obtained suspension is subjected to hydrothermal reaction at 150 ℃ for 10 hours, and is naturally cooled, filtered, washed, separated and dried to obtain the supported precursor. Roasting the obtained precursor for 2 hours at 450 ℃ to obtain a final supported catalyst, wherein the cobalt-molybdenum molar ratio of the cobalt-molybdenum alumina catalyst used in the embodiment is 1:1; the molar ratio of nickel to molybdenum in the nickel molybdenum alumina catalyst of example 2 was 1:1.
The above description of the embodiments is provided to facilitate the understanding and use of the invention by those skilled in the art. Modifications to the embodiments will be readily apparent to those skilled in the art, and the generic principles herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (9)
1. Direct reduction of SO in flue gas by low-temperature catalysis 2 The method for preparing sulfur is characterized by comprising the following steps:
1) Pretreatment of flue gas: after the temperature of the raw flue gas after dust removal is reduced by the primary heat exchanger (7B), the fine dust and heavy metal impurities in the flue gas are removed by the washing tower (8), and the flue gas returns to the primary heat exchanger (7B) for preheating and then is subjected to secondary conversionThe heater (7C) heats up; the raw flue gas is flue gas after dust removal, wherein SO 2 The content is 0.5% -10%, the oxygen content is 5-30%, the flue gas temperature is 150-250 ℃, and the flue gas contains a certain amount of heavy metals and fine particles, and the flue gas temperature is 100-150 ℃ after the flue gas is cooled by a primary heat exchanger (7B);
2) SO in flue gas 2 Low temperature catalytic reduction of (2): the sulfide gas obtained from the sulfur catalytic reduction reactor (6) and the heated SO-containing gas obtained in the step 1) are mixed 2 Mixing the flue gas and introducing the flue gas into a catalyst bed (1) together SO 2 Forms sulfur with sulfide gas through Claus reaction and gradually accumulates on the surface of the catalyst; 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 calculated as SO according to the molar amount of the hydrogen sulfide 2 1-2 times of the amount;
3) Recovery of escaping sulfur vapors: the flue gas flowing out of the catalyst bed (1) carries a small amount of sulfur vapor, the flue gas is efficiently trapped by the sulfur removal bed (2), and the flue gas is cooled by a secondary heat exchanger (7C) and then sent to deep desulfurization treatment;
4) Regeneration of the catalyst bed (1) or the sulfur removal bed (2) and sulfur recovery: blowing 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, taking the sulfur out along with the air flow, respectively carrying out cooling treatment by a two-stage sulfur condenser (3) to condense the sulfur into liquid, and flowing into a sulfur collecting groove (4) for recycling, wherein the nitrogen is collected into the flue gas, and collecting the uncollected sulfur vapor by utilizing the sulfur removal bed;
5) Evaporation and catalytic reduction of sulfur: conveying the regenerated liquid sulfur part to a sulfur evaporator (5), fully gasifying the liquid sulfur by heating, mixing the liquid sulfur with sulfur reducing agent gas, entering a sulfur catalytic reduction reactor (6) together, quickly reducing the sulfur into sulfide under the action of a catalyst to form sulfide mixed gas, cooling by a heat exchanger (7A), conveying the sulfide mixed gas to an inlet of a catalyst bed (1) as required, mixing the sulfur mixed gas with flue gas to obtain SO 2 Is a reducing agent of (2)The nitrogen is heated by a heat exchanger (7A) and used as a regeneration purge gas for the catalyst bed (1) or the sulfur removal bed (2).
2. A low temperature catalytic direct reduction of SO in flue gas according to claim 1 2 The method for preparing sulfur is characterized in that the washing tower (8) in the step 1) 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 by a primary heat exchanger (7B) to 120-140 ℃, and the flue gas is continuously returned by a secondary heat exchanger (7C) to 150-200 ℃.
3. A low temperature catalytic direct reduction of SO in flue gas according to claim 1 2 The method for preparing 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 in Mo, ni, co, ti, the loading of the modified transition metals is 0.5-5%, and the space velocity of flue gas in the catalyst bed is 1000-6000h -1 ；
The adsorbent filled in the sulfur removal bed (2) is granular activated alumina, and the airspeed of the flue gas in the sulfur removal bed (2) is 3000-9000h -1 。
4. A low temperature catalytic direct reduction of SO in flue gas according to claim 1 or 3 2 The method for preparing sulfur is characterized in that the catalyst bed (1) comprises two groups connected in parallel, the sulfur removal bed (2) comprises two groups connected in parallel,
when the accumulated amount of sulfur in one group of catalyst beds or sulfur removal beds reaches 0.5-5% of the mass of the catalyst or adsorbent, regenerating the catalyst beds or sulfur removal beds, switching the flue gas to the other group of catalyst beds or sulfur removal beds before regenerating, and isolating the regenerated catalyst beds or sulfur removal beds from the flue gas.
5. A low temperature catalytic direct reduction of SO in flue gas according to claim 1 2 Method for producing sulfur, whichIs characterized in that the heat of the outlet gas of the sulfur catalytic reduction reactor (6) is utilized to preheat the nitrogen for regenerating and purging to 350-500 ℃; the volume of nitrogen required for regenerating the catalyst bed (1) or the sulfur removal bed (2) is 10-20 times of the volume of the filled catalyst or adsorbent, and the purging time is 30-90 minutes.
6. A low temperature catalytic direct reduction of SO in flue gas according to claim 5 2 The method for preparing the sulfur is characterized in that sulfur vapor carried out by nitrogen purging is cooled to below 200 ℃ through a two-stage sulfur condenser (3), condensed liquid sulfur flows into a sulfur converging groove (4) to be collected, heat released by the sulfur condenser (3) is used for preheating nitrogen required by regeneration, and the preheated nitrogen exchanges heat with hot air flow after a sulfur catalytic reduction reactor (6) to meet the requirement of a set temperature.
7. A low temperature catalytic direct reduction of SO in flue gas according to claim 1 2 A process for producing sulfur, characterized by comprising the steps of 2 The amount of sulfide needed for reduction is extracted from the sulfur condenser (3), and the corresponding liquid sulfur is sent into a sulfur evaporator (5) to be gasified into steam with the temperature of 450-500 ℃.
8. A 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 vapor is mixed with a reducing agent, the mixture enters a sulfur catalytic reduction reactor (6) for reaction, the 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.
9. A 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 reduction of the sulfur is H 2 S, and has a small amount of CS 2 Or COS, the total volume concentration of which in the gas stream is 20-70%, the balance being CO 2 Water and method for producing sameThe steam is cooled to be lower than 300 ℃ by a heat exchanger (7A) and then is sent to be mixed with the flue gas to be used as SO 2 The hydrogen sulfide gas generated by the sulfur catalytic reduction reactor (6) can 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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| 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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