CN102950000B - Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof - Google Patents

Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof Download PDF

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CN102950000B
CN102950000B CN201110255125.5A CN201110255125A CN102950000B CN 102950000 B CN102950000 B CN 102950000B CN 201110255125 A CN201110255125 A CN 201110255125A CN 102950000 B CN102950000 B CN 102950000B
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刘剑利
刘爱华
达建文
陶卫东
刘增让
许金山
王建华
崔云梓
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China Petroleum and Chemical Corp
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Abstract

The invention belongs to the technical field of sulfur recycling, and relates to a catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and a preparation method. A preparation method of a catalyst carrier comprises the steps of: based on silicon dioxide as a raw material, adding an alkali metal oxide and alkaline earth oxide composite modifying agent; and forming by using an extrusion molding mode to prepare the carrier with pore volume of more than 0.5ml/g and average pore diameter of more than 30nm. The catalyst is prepared by dipping an active component, ferric oxide is used as the active component, rare earth oxides are used as active auxiliary agents, and a promoter is added to improve dispersion of metal oxides on the carrier. The catalyst can be used for sulfur recycling devices in the industries, such as petroleum refining, natural gas purification and coal chemical industry, has the characteristics of high coal chemical industry, poor sensitivity on water and no toxicity of the active component, and is capable of improving the sulfur recycling rate of the sulfur recycling devices.

Description

Hydrogen sulfide selective oxidation catalyst for sulphur and preparation method thereof
Technical field
The invention belongs to the catalyst relating in sulphur recovery technical field, relate to a kind of hydrogen sulfide selective oxidation catalyst for sulphur and preparation method thereof, this catalyst can be used for the sulfur recovery unit of the industries such as petroleum refining, natural gas purification and Coal Chemical Industry.
Background technology
In the production process of the industries such as petroleum refining, natural gas purification and Coal Chemical Industry, can produce a large amount of H 2 S-containing gas, it is exactly Claus method that hydrogen sulfide is changed into the method that harmless elementary sulfur the most extensively adopts.The method is first by approximately 1/3rd H 2s burning generates SO 2.In combustion furnace, the majority of organic pollutants in air-flow is also burned to be fallen, remaining H 2s and formed SO 2reaction generting element sulphur, its reaction equation is:
2H 2S+SO 2←→2H 2O+3/nSn
But, due to the restriction of thermodynamical equilibrium, the H in this process 2s can not all change elementary sulfur into, that is to say and in reaction end gas, still has a small amount of H 2s exists.Even if use high activated catalyst and three grades of catalytic conversion process, the sulfur recovery rate of Claus method technique is the highest can only reach 97%.At present, the environmental regulation of China has not allowed discharge containing H 2the waste gas of S, emission standards for sulfur dioxide is for being less than 960mg/m 3, above-mentioned containing H 2after the gas of S burns and becomes sulfur dioxide, discharge is not up to standard yet, so need be to residue H 2s is further processed, and most economical processing mode is to H at present 2s carries out direct oxidation.SuperClaus technique is a kind of in direct oxidation process, is successful, the most most widely used direct oxidation class technique at present.SuperClaus process using improved merely H by changing in the past 2s and SO 2the method of reaction process, after traditional Crouse transforms, afterbody conversion zone is used novel hydrogen sulfide catalyst for selective oxidation, is actually a kind of tail gas treatment process, with this, improves the sulfur recovery technology of claus process.The main reaction of SuperClaus technique is that hydrogen sulfide and oxygen reaction generate sulphur and water, and this reaction is not subject to thermodynamics equilibrium limit, after traditional Crouse transforms, afterbody conversion zone is used hydrogen sulfide catalyst for selective oxidation, the sulfur recovery rate that can improve device, meets national requirements for environmental protection.At present, oneself builds device over 100 covers domestic and international SuperClaus technique, and development rapidly.
At present, the trade mark of the hydrogen sulfide catalyst for selective oxidation of exploitation is less both at home and abroad, on the whole, existing catalyst is not high to the yield of sulphur, there is following problem: (1) catalyst activity component exists the larger material of toxicity, as chromium, misoperation can be prepared personnel to catalyst and damage with device operating personnel; (2) poor selectivity of catalyst to sulphur, causes the yield of sulphur lowlyer, affects the sulfur recovery rate of sulphur unit; (3) catalyst is to water sensitive, it is larger that catalytic activity is affected by water vapour content, some catalyst require to use under low water content (volume content is less than 5%) or anhydrous condition, but in gas, water vapour content, more than 30%, cannot meet this type of catalyst requirement after secondary claus reaction.
United States Patent (USP) 4818740 disclose a kind of selective oxidation sulfur-containing compound particularly hydrogen sulfide become the catalyst of elementary sulfur, this catalyst be take alpha-aluminium oxide as carrier, the oxide of iron and chromium is active component, and the standby catalyst of this patent system has higher conversion ratio and selective.But commercial Application actual result shows, catalyst actual conversion is 95% left and right, selectively less than 80%.Due to selectively poor, can only process the gas that sulfide hydrogen content is lower.
CN200810157750.4 discloses catalyst and the technique that a kind of selective oxidation of sulfureted hydrogen becomes elementary sulfur.This catalyst comprises carrier and active component, and active component adopts di-iron trioxide and/or chrome green, and carrier is the mixed oxide of titanium dioxide and alundum (Al2O3), and in carrier, content of titanium dioxide is 60～95%.The reaction that this catalyst is elementary sulfur for the selective oxidation hydrogen sulfide of hydrogen sulfide-containing mixed gas.Reaction condition is: 160～280 ℃ of reaction temperatures, and reaction pressure 0.02～10.0MPa, gas space velocity is 400～2000h -1, H 2s≤3.0%(V ol%), O 2/ H 2s(mol ratio)=0.6～3.0.Because this catalyst is used titania support, to water sensitive, can only be for the treatment of the gas of anhydrous or low water content (being less than 5%).
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of hydrogen sulfide selective oxidation catalyst for sulphur and preparation method thereof, selects nontoxic rare earth element to substitute the crome metal that toxicity is larger and solves the problem that catalyst activity component exists toxicity; By selecting silica as the raw material of carrier, and add alkali metal oxide and alkaline earth oxide composite modifier, with solve catalyst not high to the yield of sulphur, to problems such as water sensitive; Use silica as the raw material of carrier, in catalyst preparation, add promoter, can improve the decentralization of active component, promote the activity of catalyst.
A kind of hydrogen sulfide selective oxidation of the present invention catalyst for sulphur, it is characterized in that silica is the raw material of preparing carrier, add alkali metal oxide and alkaline earth oxide composite modifier, take iron oxide as active component, rare earth oxide is as coagent, wherein:
Composite modifier accounts for 0.5～5% of carrier mass content, and in composite modifier, the molar ratio of alkali metal oxide and alkaline earth oxide is 4:1 to 1:2;
The specific surface of silica is 100～200m 2/ g, pore volume are 0.5～1.4ml/g;
Iron oxide content accounts for catalyst quality content 2～10%;
Rare earth oxide content accounts for catalyst quality content 0.5～3%, and rare earth oxide is selected from the oxide of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium or gadolinium.
More specific scheme is:
Take silica as carrier, add alkali metal oxide and alkaline earth oxide composite modifier, through moulding, oven dry, roasting, be prepared into carrier, take iron oxide as active component, rare earth oxide is as coagent, add promoter, employing impregnating method preparation technique is prepared from, wherein active component, promoter and coagent join in deionized water, form activity component impregnation liquid, promoter is selected from glycerine, ethylene glycol or phosphoric acid, and its addition is 5～20% of activity component impregnation liquid volume content.
Because existing hydrogen sulfide catalyst for selective oxidation exists, catalyst activity not high on the yield of sulphur to be subject to water vapour content to affect large, catalyst activity component, there is the problems such as toxicity, invented a kind of catalyst and preparation method for hydrogen sulfide Selective Oxidation sulphur.By optimization, select nontoxic rare earth element to substitute the crome metal that toxicity is larger and solve the problem that catalyst activity component exists toxicity; By selecting silica as the raw material of carrier, and add alkali metal oxide and alkaline earth oxide composite modifier, can solve catalyst not high to the yield of sulphur, to problems such as water sensitive; Use silica as the raw material of carrier, in catalyst preparation, add promoter, can improve the decentralization of active component, promote the activity of catalyst.
The preparation method of catalyst of the present invention comprises:
By specific surface, be 100～200m 2the silica that/g, pore volume are 0.5～1.4ml/g and expanding agent, composite modifier together with water after kneading, are made carrier through extrusion, dry, roasting.In deionized water, add active component promoter and active component salt, form activity component impregnation liquid, carrier is after activity component impregnation immersion stain, and further hydrogen sulfide selective oxidation catalyst for sulphur is made in drying, roasting.
Expanding agent is polyvinyl alcohol, polyacrylamide, sesbania powder, citric acid, starch etc., preferably sesbania powder.Its addition is 1～5% of carrier mass content.
Promoter is glycerine, ethylene glycol or phosphoric acid, and its amount is 5～20% of maceration extract volume content.
Composite modifier accounts for carrier mass content 0.5～5%, is preferably 1～3%.
In composite modifier, alkali metal oxide and alkaline earth oxide ratio are 4:1 to 1:2(oxide mol ratio), be preferably 2:1 to 1:1.
In composite modifier, alkali metal oxide is mainly the oxide of lithium, sodium, potassium, rubidium, caesium etc., is preferably the oxide of potassium, sodium.
In composite modifier, alkaline earth oxide is mainly the oxide of beryllium, magnesium, calcium, strontium, barium etc., is preferably calcium oxide.
The sintering temperature of carrier is 500～700 ℃, preferably 600 ℃.
The carrier pore volume making should be greater than 0.5ml/g, and average pore size is greater than 30nm.
Carrier outward appearance is preferably bar shaped.
Catalyst preparation adopts equi-volume impregnating preparation.
The active constituent of catalyst is iron oxide, and iron oxide content accounts for catalyst quality content 2～10%, is preferably 4～7%, and iron oxide adds with the form of the soluble ferric iron salt such as ferric nitrate, ferric citrate, iron chloride.
Catalyst activity auxiliary agent is rare earth oxide, and rare earth oxide is mainly the oxide of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium etc., is preferably the oxide of lanthanum and cerium, and rare earth oxide adds with the form of the soluble ferric iron salt such as nitrate.
Rare earth oxide content accounts for catalyst quality content 0.5～3%, is preferably 0.5～1.5%.
In rare earth oxide, the ratio of lanthana and cerium oxide is 2:1 to 1:4(oxide mol ratio), be preferably 1:1 to 1:2;
In catalyst impregnating solution, add promoter, promoter is glycerine, ethylene glycol, phosphoric acid etc., is preferably glycerine.
The sintering temperature of catalyst is 300～600 ℃, and preferably temperature is 400 ℃.
The concrete preparation process of the present invention is as follows:
The preparation of l, carrier
Choosing specific surface is 100～200m 2the silica that/g, pore volume are 0.5～1.4ml/g, and composite modifier, water, expanding agent add kneader.Said mixture is through mediating, and ф 3mm stripe shape orifice plate extruded moulding, in 110～150 ℃ of oven dry 2～4 hours, in 600 ℃ of roastings 2～5 hours, can be made into carrier.The pore volume of carrier should be greater than 0.5ml/g, and average pore size is greater than 30nm.Use N 2determination of adsorption method pore volume and average pore size.
2, catalyst preparation
Get a certain amount of deionized water, add active component promoter, add soluble ferric iron salt and the rare earth salts of aequum under constantly stirring, make it to form stable solution, be stirred to completely and dissolve, constant volume obtains activity component impregnation liquid.Get a certain amount of above-mentioned co-impregnated solution, impregnated carrier 10 minutes～3 hours, preferably 0.5～1 hour, in 110～150 ℃ of oven dry 2～6 hours, in 300～600 ℃ of roastings 2～6 hours, obtains catalyst of the present invention.What catalyst preparation adopted is equi-volume impregnating.
Advantage of the present invention:
The catalyst that adopts the present invention to prepare has the advantages such as catalytic activity is high, poor to water sensitivity, active constituent is nontoxic.Use this catalyst under certain condition hydrogen sulfide conversion ratio can reach more than 99%, sulfur dioxide selectively reaches more than 90%, sulphur yield can reach more than 90%, thereby improves the sulfur recovery rate of sulfur recovery unit, has significant economic benefit and social benefit.
The specific embodiment
Embodiment 1: by 200 grams of silica, (specific area is 145m 2/ g, pore volume is 1.2ml/g) mix with 0.8 gram of calcium oxide, 8.4 grams of citrate dihydrate trisodiums, 4 grams of sesbania powder, 300 grams of distilled water, extruded moulding on banded extruder, is dried 4 hours at 120 ℃, 650 ℃ of roastings 6 hours, the carrier specific area making was thus 75m 2/ g, pore volume is 0.61ml/g, average pore size is 35nm.
By 65.2 grams of Fe (NO 3) 3﹒ 9H 2o, 2.86 grams of Ce (NO 3) 3.6H 2o, 2.86 grams of La (NO 3) 3.6H 2o, 20ml glycerine join in 180 grams of water, mixes, and the carrier making by step in the solution impregnation obtaining, dip time is 10 hours, at 120 ℃, is dried 10 hours, and at 500 ℃, roasting is 6 hours, and the specific surface area of catalyst making is thus 67m 2/ g, pore volume is 0.53ml/g, average pore size is 32nm, catalyst oxidation iron amount is 6%(quality), rare earth oxide content is 1%(quality).
Embodiment 2: by 200 grams of silica, (specific area is 145m 2/ g, pore volume is 1.2ml/g) mix with 0.8 gram of calcium oxide, 8.4 grams of citrate dihydrate trisodiums, 4 grams of sesbania powder, 300 grams of distilled water, extruded moulding on banded extruder, is dried 4 hours at 120 ℃, 650 ℃ of roastings 6 hours, the carrier specific area making was thus 75m 2/ g, pore volume is 0.61ml/g, average pore size is 35nm.
By 65.2 grams of Fe (NO 3) 3﹒ 9H 2o, 20ml glycerine join in 180 grams of water, mix the carrier making by step in the solution impregnation obtaining, dip time is 10 hours, at 120 ℃, be dried 10 hours, at 500 ℃, roasting is 6 hours, and the catalyst oxidation iron amount making is thus 6%(quality).
Embodiment 3: by 200 grams of silica, (specific area is 145m 2/ g, pore volume is 1.2ml/g) mix with 0.8 gram of calcium oxide, 8.4 grams of citrate dihydrate trisodiums, 4 grams of sesbania powder, 300 grams of distilled water, extruded moulding on banded extruder, is dried 4 hours at 120 ℃, 650 ℃ of roastings 6 hours, the carrier specific area making was thus 75m 2/ g, pore volume is 0.61ml/g, average pore size is 35nm.
By 65.2 grams of Fe (NO 3) 3﹒ 9H 2o, 2.86 grams of Ce (NO 3) 3.6H 2o, 2.86 grams of La (NO 3) 3.6H 2o joins in 180 grams of water, mix, the carrier making by step in the solution impregnation obtaining, dip time is 10 hours, at 120 ℃, be dried 10 hours, at 500 ℃, roasting is 6 hours, and the catalyst oxidation iron amount making is thus 6%(quality), rare earth oxide content is 1%(quality).
Embodiment 4: by 200 grams of silica, (specific area is 145m 2/ g, pore volume is 1.2ml/g) mix with 4 grams of sesbania powder, 300 grams of distilled water, extruded moulding on banded extruder, is dried 4 hours at 120 ℃, and 650 ℃ of roastings 6 hours, the carrier specific area making was thus 75m 2/ g, pore volume is 0.61ml/g, average pore size is 35nm.
By 65.2 grams of Fe (NO 3) 3﹒ 9H 2o, 2.86 grams of Ce (NO 3) 3.6H 2o, 2.86 grams of La (NO 3) 3.6H 2o, 20ml glycerine join in 180 grams of water, mix, the carrier making by step in the solution impregnation obtaining, dip time is 10 hours, at 120 ℃, be dried 10 hours, at 500 ℃, roasting is 6 hours, and the catalyst oxidation iron amount making is thus 6%(quality), rare earth oxide content is 1%(quality).
Embodiment 5: by 200 grams of silica, (specific area is 145m 2/ g, pore volume is 1.2ml/g) mix with 4 grams of sesbania powder, 300 grams of distilled water, extruded moulding on banded extruder, is dried 4 hours at 120 ℃, and 650 ℃ of roastings 6 hours, the carrier specific area making was thus 75m 2/ g, pore volume is 0.61ml/g, average pore size is 35nm.
By 42.2 grams of Fe (NO 3) 3﹒ 9H 2o, 2.86 grams of Ce (NO 3) 3.6H 2o, 2.86 grams of La (NO 3) 3.6H 2o, 20ml glycerine join in 180 grams of water, mix, the carrier making by step in the solution impregnation obtaining, dip time is 10 hours, at 120 ℃, be dried 10 hours, at 500 ℃, roasting is 6 hours, and the catalyst oxidation iron amount making is thus 4%(quality), rare earth oxide content is 1%(quality).
Embodiment 6: by 200 grams of silica, (specific area is 145m 2/ g, pore volume is 1.2ml/g) mix with 4 grams of sesbania powder, 300 grams of distilled water, extruded moulding on banded extruder, is dried 4 hours at 120 ℃, and 650 ℃ of roastings 6 hours, the carrier specific area making was thus 75m 2/ g, pore volume is 0.61ml/g, average pore size is 35nm.
By 65.2 grams of Fe (NO 3) 3﹒ 9H 2o, 5.72 grams of Ce (NO 3) 3.6H 2o, 20ml glycerine join in 180 grams of water, mix, the carrier making by step in the solution impregnation obtaining, dip time is 10 hours, at 120 ℃, be dried 10 hours, at 500 ℃, roasting is 6 hours, and the catalyst oxidation iron amount making is thus 6%(quality), cerium oxide content is 1%(quality).
Embodiment 7: on sulphur micro anti-evaluation device, the catalyst of embodiment 1 to embodiment 6 preparation is carried out to activity rating, the stainless steel tube that the reactor of micro-reactor is 20mm by internal diameter is made, and reactor is placed in insulating box.Loaded catalyst is 10ml, the quartz sand mixing preheating of top filling same particle sizes.Adopt H in Japanese Shimadzu GC-2014 gas chromatograph on-line analysis reactor inlet and exit gas 2s, SO 2and O 2content, adopt GDX-301 carrier to analyze sulfide, adopt 5A molecular sieve to analyze O 2content, 120 ℃ of column temperatures, adopt thermal conductivity detector (TCD), do carrier gas, flow velocity 25ml/min after post with hydrogen.
With 2H 2s+O 2→ 2S+2H 2o, 2H 2s+3O 2→ 2SO 2+ 2H 2o is index reaction, investigates the catalytic activity of catalyst, and inlet gas consists of H 2s1%, O 21.5%, H 2o30%, all the other are N 2, gas volume air speed is 1600h -1, according to the H of following formula calculating catalyst 2s conversion ratio η act:
η Act = M 0 - M 1 M 1 × 100 %
M wherein 0, M 1represent respectively entrance and exit H 2the volumetric concentration of S.
According to following formula, calculate the H of catalyst 2s transforms the selective η that generates sulphur sel:
η Sel = M 0 - M 1 - C 0 M 0 - M 1 × 100 %
M wherein 0, M 1represent respectively entrance and exit H 2the volumetric concentration of S, C 0volumetric concentration for exit sulfur dioxide.
According to following formula, calculate the H of catalyst 2s transforms and generates sulphur productive rate η yld:
η Yld＝η Act×η Sel
Embodiment 1 catalyst
Reaction temperature/℃ Conversion ratio η Act ％ Selective η Sel ％ Yield η Yld ％
180 98 95 93
200 100 95 95
220 100 93 93
240 100 89 90
260 100 83 83
Embodiment 2 catalyst
Embodiment 3 catalyst
Reaction temperature/℃ Conversion ratio η Act ％ Selective η Sel ％ Yield η Yld%
180 97 95 92
200 98 94 92
220 99 92 91
240 99 89 88
260 100 82 82
Embodiment 4 catalyst
Reaction temperature/℃ Conversion ratio η Act% Selective η Sel% Yield η Yld%
180 98 92 90
200 100 91 91
220 100 90 90
240 100 83 83
260 100 79 79
Embodiment 5 catalyst
Reaction temperature/℃ Conversion ratio η Act ％ Selective η Sel ％ Yield η Yld ％
180 96 95 91
200 98 95 93
220 98 93 91
240 99 89 88
260 100 83 83
Embodiment 6 catalyst
Reaction temperature/℃ Conversion ratio η Act ％ Selective η Sel ％ Yield η Yld ％
180 98 94 92
200 100 94 94
220 100 91 91
240 100 86 86
260 100 82 82

Claims (13)

1. a hydrogen sulfide selective oxidation catalyst for sulphur, it is characterized in that take that silica is as carrier, add alkali metal oxide and alkaline earth oxide composite modifier, be prepared into carrier, take iron oxide as active component, rare earth oxide is as coagent, composite modifier accounts for 0.5～5% of carrier mass content, in composite modifier, the molar ratio of alkali metal oxide and alkaline earth oxide is 4: 1 to 1: 2, iron oxide content accounts for 2～10% of catalyst quality content, and rare earth oxide content accounts for catalyst quality content 0.5～3%.
2. catalyst according to claim 1, it is characterized in that take that silica is as carrier, add alkali metal oxide and alkaline earth oxide composite modifier, through moulding, dry, roasting is prepared into carrier, take iron oxide as active component, rare earth oxide is as coagent, add promoter, employing impregnating method preparation technique is prepared from, active component wherein, promoter and coagent join in deionized water, form activity component impregnation liquid, promoter is selected from glycerine, ethylene glycol or phosphoric acid, its addition is 5～20% of activity component impregnation liquid volume content.
3. catalyst according to claim 1, the specific surface that it is characterized in that silica is 100～200m 2/ g, pore volume are 0.5～1.4ml/g.
4. catalyst according to claim 1, is characterized in that composite modifier accounts for 1～3% of carrier mass content, and in composite modifier, the molar ratio of alkali metal oxide and alkaline earth oxide is 2: 1 to 1: 1.
5. catalyst according to claim 1, is characterized in that iron oxide content accounts for catalyst quality content 4～7%.
6. catalyst according to claim 1, is characterized in that rare earth oxide is selected from one or both in the oxide of lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium or gadolinium.
7. catalyst according to claim 6, is characterized in that rare earth oxide is comprised of lanthana and cerium oxide, and the molar ratio of lanthana and cerium oxide is 2: 1 to 1: 4.
8. catalyst according to claim 1, is characterized in that alkali metal oxide is the oxide of lithium, sodium, potassium, rubidium or caesium, and alkaline earth oxide is the oxide of beryllium, magnesium, calcium, strontium or barium.
9. catalyst according to claim 8, is characterized in that alkali metal oxide is the oxide of lithium, sodium or potassium, the oxide that alkaline earth oxide is calcium.
10. a method of preparing one of claim 1-9 described catalyst, is characterized in that comprising the steps:
(1), the preparation of carrier
Silica and composite modifier, water, expanding agent mix, and through mediating, extrusion molding, in 110～150 ℃ of oven dry 2～4 hours, in 500～700 ℃ of roastings 2～5 hours, makes carrier;
(2), catalyst preparation
In deionized water, add active component promoter, the soluble ferric iron salt and the rare earth salts that under constantly stirring, add aequum, make it to form stable solution, obtain activity component impregnation liquid, with maceration extract impregnated carrier 10 minutes～3 hours, in 110～150 ℃ of oven dry 2～6 hours, in 300～600 ℃ of roastings 2～6 hours, obtain catalyst.
11. preparation methods according to claim 10, is characterized in that expanding agent is selected from one or more in polyvinyl alcohol, polyacrylamide, sesbania powder, citric acid, starch, and its addition is 1～5% of carrier mass content.
12. preparation methods according to claim 10, is characterized in that promoter is glycerine, ethylene glycol or phosphoric acid, and its addition is 5～20% of maceration extract volume content.
13. preparation methods according to claim 10, is characterized in that carrier outward appearance is in strip.
CN201110255125.5A 2011-08-31 2011-08-31 Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation method thereof Active CN102950000B (en)

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CN104248966B (en) * 2013-06-25 2016-08-17 中国石油化工股份有限公司 Hydrogen sulfide selective oxidation catalyst for sulphur and preparation method thereof
CN106311257A (en) * 2015-06-17 2017-01-11 中国石油化工股份有限公司 Catalytic incineration catalyst used for processing hydrogen sulfide-containing exhaust gas and preparation method thereof
CN105126848B (en) * 2015-08-21 2017-05-24 山东迅达化工集团有限公司 Catalyst having macro-porous structure and used for production of sulfur through selective oxidation of H2S, and preparation method thereof
CN105126850B (en) * 2015-08-21 2017-08-25 山东迅达化工集团有限公司 Selective oxidation H2Catalyst of S production sulphur and preparation method thereof
CN105126849B (en) * 2015-08-21 2017-05-24 山东迅达化工集团有限公司 Fe2O3/diatomite catalyst for generation of elemental sulfur through selective oxidation of H2S, and preparation method thereof
CN110127602B (en) * 2018-02-09 2020-09-25 中国石油化工股份有限公司 Method for decomposing hydrogen sulfide by using catalyst
CN111068746B (en) * 2018-10-22 2023-12-05 中国石油化工股份有限公司 Multifunctional sulfur recovery catalyst and preparation method thereof
CN112973723B (en) * 2021-03-01 2023-09-19 府谷县泰达煤化有限责任公司 Catalyst for preparing alcohol from coke quenching waste gas and preparation method thereof
CN113600172B (en) * 2021-08-23 2022-07-12 南京工业大学 Alkaline catalyst and preparation method and application thereof
CN115569649B (en) * 2022-11-07 2024-02-13 青岛联信催化材料有限公司 Catalyst for preparing sulfur by selective oxidation of hydrogen sulfide and preparation and use methods thereof

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