CN102500362A - Catalyst for removing H2S from gas by catalytic oxidation, preparation method and application - Google Patents
Catalyst for removing H2S from gas by catalytic oxidation, preparation method and application Download PDFInfo
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- CN102500362A CN102500362A CN2011103939164A CN201110393916A CN102500362A CN 102500362 A CN102500362 A CN 102500362A CN 2011103939164 A CN2011103939164 A CN 2011103939164A CN 201110393916 A CN201110393916 A CN 201110393916A CN 102500362 A CN102500362 A CN 102500362A
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Abstract
A catalyst for removing H2S from gas by catalytic oxidation contains a metal oxide as active component, and active carbon as carrier, wherein the weight percentages of the two components are as follows: active carbon 95.0% to 99.9%, and metal oxide 0.1% to 5%; active carbon has a specific surface area of 850 to 900 m<2>/g, total pore volume of 0.45 cm<3>/g, and micro-pore volume of 0.154 cm<3>/g; and the metal oxide is oxide of Fe, V, Mn, Cu, Ce or Co. The catalyst provided by the invention has a simple preparation method, and can remarkably improve the desulfurization activity and selectivity of active carbon and greatly improve breakthrough sulfur capacity of desulfurizer.
Description
Technical field
The invention belongs to a kind of catalyst and preparation method and application, relate to catalyst and preparation method and the application of H2S in a kind of catalytic oxidative desulfurization coal gas specifically.
Background technology
The clean coal technology that turns to the basis with coal gas is to realize one of main path that coal high-efficiency, environmental protection utilize.Sulfide is one of major pollutants in the coal gas, can cause problems such as equipment corrosion, catalyst poisoning and environmental pollution, therefore is that the key issue of clean coal technology realizes that the economical and efficient of sulfide in the coal gas removes.The low-temp methanol method is adopted in the extensive desulfurization of industry at present mostly, but this technology is the foreign patent technology, and because operating temperature is low; Cause problems such as investment height, energy consumption height; During especially for the Coal (syngas) polygeneration system, cause the gas heat loss, reduced system thermal efficiency.Metal oxide is used for coal gas of high temperature desulfurization (＞400 ℃) as desulfurizing agent; Remove sulfide through vulcanization reaction; Be the forward position and the developing direction of current coal gas desulfurization technology; But, can not adapt to the commercial Application requirement because intensity of desulfurizer requires the technical barriers such as bottleneck of height, upper reaches high-temperature dust removal technical development.Current, advanced pressurized gasification technology (shell, Texaco) is after pressurized wash waterization, and gas temperature still can reach about 200 ℃, and the efficient desulfurizing agent in the exploitation purification temperature under the low temperature has more using value.
Active carbon (AC) has bigger specific area and pore volume, has good absorption and catalytic reaction activity, can adsorb the hydrogen sulfide in the coal gas and it is oxidized to elemental sulfur, and elemental sulfur is stored in the pore structure of active carbon.The agent of active carbon low-temp desulfurization is used in industry, but serviceability temperature generally is no more than 60 ℃.High temperature can cause the rapid decline of desulfurizing agent Sulfur capacity and desulfurization precision, and desulfurizing agent dynamic performance and regenerability are poor.Therefore, only be suitable for the smart desulfurization of synthesis gas, to the raw gas of high temperature, high-sulfur and be not suitable for.Method through preparation method's optimization, surface modification improves the removal effect of active carbon to sulfide in the heating gas.U.S.'s Oak Ridge National Laboratory shows that to the result of study that active carbon is used for the fuel gas desulfurization active carbon can be an elemental sulfur with the hydrogen sulfide selective catalytic oxidation in recent years, but Sulfur capacity is relatively low.Metal oxide has fine catalytic oxidation selectivity, Fe to sulfide
2O
3, CuO, V
2O
3, Al
2O
3, TiO
2, catalyst based to have a good claus reaction active for Ce-Zr, and the direct catalytic oxidation hydrogen sulfide of available usefulness generates elemental sulfur.Therefore; The activated carbon catalysis adsorption desulfurizing agent of exploitation carrying metal oxide; The metal oxide that utilization supports improves active carbon to the removal efficiency of sulfide and the selectivity of reaction; And utilize the adsorption capacity of active carbon to be stored in elemental sulfur absorption in the pore passage structure, obtain the elemental sulfur resource of high value.
Summary of the invention
The purpose of this invention is to provide a kind of H in the coal gas that efficiently removes
2The Catalysts and its preparation method of S and application.
The present invention is used for catalytic oxidative desulfurization H
2The catalyst of S is that catalyst is active component with the metal oxide, and active carbon is a carrier, and the percentage by weight of each component is: active carbon 95.0%～99.9%, metal oxide 0.1%～5%.
Aforesaid active carbon is that specific area is 850～900m
2/ g, total pore volume is 0.45cm
3It is 0.154cm that/g, micropore hold
3/ g.
Aforesaid metal oxide is the oxide of Fe, V, Mn, Cu, Ce or Co.
Preparation of catalysts method of the present invention is following:
Press catalyst and form, in the solution of active component soluble salt, room temperature is placed 3-6h under the room temperature then with the active carbon incipient impregnation; Impregnated active carbon earlier at 50-60 ℃ of freeze-day with constant temperature 4-10h, and is continued dry 4-10h at 100-110 ℃, and activation 3-6h in 300-600 ℃ temperature and nitrogen atmosphere obtains required catalyst then.
Aforesaid active component soluble salt Ce (NO
3)
36H
2O, Fe (NO
3)
39H
2O, Cu (NO
3)
23H
2O, Co (NO
3)
26H
2O, Mn (NO
3)
2Or NH
4VO
3
Application of Catalyst method of the present invention is that this catalyst is packed in fixed bed or the fluidized-bed reactor, at normal pressure, and 150-250 ℃, air speed 1000-8000h
-1Under the condition, aerating oxygen, the amount of aerating oxygen is O
2: H
2The S mol ratio is 1-2: 1-2, the H in the catalytic eliminating gas
2S.
The present invention has the following advantages:
1. this method for preparing catalyst is simple, through to the modification of active carbon dipping corresponding metal oxide, has improved the desulphurizing activated and selectivity of active carbon significantly, has greatly improved the Sulfur capacity that penetrates of desulfurizing agent.
2. be applicable to that under 150-250 ℃ micro amount of oxygen exists down, removes H efficiently
2S can effectively utilize sensible heat in the coal gas.
3. the main sulphur of the product after the desulfurization is adsorbed in the duct of catalyst, can effectively realize the recycling of elemental sulfur.
The specific embodiment
Calculating penetrates Sulfur capacity and desulfuration efficiency, with definition outlet H
2Be breakthrough concentration when S concentration reaches 100ppm, calculate and penetrate Sulfur capacity and desulfuration efficiency.
Embodiment 1
With manganese concentration is the Mn (NO of 0.0212g/ml
3)
2Solution, equal-volume evenly are impregnated on the active carbon of 30～60 order 5g, and room temperature is placed 6h, 60 ℃ of dry 10h, and 100 ℃ of dry 10h, and then 400 ℃ of nitrogen atmospheres calcining 4h down promptly obtain mass percent and are 1% Mn/AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 180 ℃, air speed 3000h
-1, H in the unstripped gas
2S content 3000ppm feeds O
2/ H
2The S ratio is 1: 1 O
2, balance gas N
2, it penetrates Sulfur capacity is 14.2%, desulfuration efficiency is 99.2%.
Embodiment 2
With concentration of iron is the Fe (NO of 0.00343g/ml
3)
3Solution, equal-volume evenly are impregnated on 30～60 purpose 5g active carbons, and room temperature is placed 3h, 60 ℃ of dry 8h, and 100 ℃ of dry 10h, and then 300 ℃ of nitrogen atmospheres calcining 3h down promptly obtain mass percent and are 0.1% Fe/AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 150 ℃, air speed 8000h
-1, H in the unstripped gas
2S content 2500ppm feeds O
2/ H
2The S ratio is 1: 2 O
2, CO30%, H
240%, CO
221%, CH
41.7%, balance gas N
2It penetrates Sulfur capacity is 5.82%, and desulfuration efficiency is 99.2%.
Embodiment 3
With a vanadium concentration is the NH of 0.0747g/ml
4VO
3Oxalic acid solution, equal-volume evenly are impregnated on 30～60 purpose 5g active carbons, and room temperature is placed 3h, 50 ℃ of dry 4h, and 100 ℃ of dry 8h, and then 450 ℃ of nitrogen atmospheres calcining 3h down promptly obtain mass percent and are 5% V/AC catalyst.This catalyst is packed in the fixed bed reactors, and reaction temperature is controlled at 250 ℃, air speed 8000h
-1, H in the unstripped gas
2S content 2500ppm feeds O
2/ H
2The S ratio is 1: 2 O
2, CO30%, H
240%, CO
221%, CH
41.7%, balance gas N
2It penetrates Sulfur capacity is 3.82%, and desulfuration efficiency is 96.5%.
Embodiment 4
With vanadium concentration is the Ce (NO of 0.0201g/ml
3)
3Solution, equal-volume evenly are impregnated on 30～60 purpose 5g active carbons, and room temperature is placed 3h, 50 ℃ of dry 10h, and 110 ℃ of dry 10h, and then 500 ℃ of nitrogen atmospheres calcining 3h down promptly obtain mass percent and are 1% Ce/AC catalyst.This catalyst is packed in the fluidized-bed reactor, and reaction temperature is controlled at 250 ℃, air speed 3000h
-1, H2S content 3000ppm in the unstripped gas feeds O
2/ H
2The S ratio is 2: 1 O
2, balance gas N
2It penetrates Sulfur capacity is 4.85%, and desulfuration efficiency is 98.5%.
Embodiment 5
That prepare copper concentration is the Cu (NO of 0.0247g/ml
3)
2Solution, equal-volume evenly are impregnated on 30～60 purpose 5g active carbons, and room temperature is placed 6h, 50 ℃ of dry 10h, and 110 ℃ of dry 4h, and then 300 ℃ of nitrogen atmospheres calcining 6h down promptly obtain mass percent and are 1% Cu/AC catalyst.This catalyst is packed in the fluidized-bed reactor, and reaction temperature is controlled at 150 ℃, air speed 3000h
-1, H in the unstripped gas
2S content 3000ppm feeds O
2/ H
2The S ratio is 2: 1 O
2, balance gas N
2It penetrates Sulfur capacity is 13.8%, and desulfuration efficiency is 99.1%.
Embodiment 6
That prepare cobalt concentration is the Co (NO of 0.0247g/ml
3)
2Solution, equal-volume evenly are impregnated on 30～60 purpose 5g active carbons, and room temperature is placed 5h, 50 ℃ of dry 10h, and 110 ℃ of dry 10h, and then 300 ℃ of nitrogen atmospheres calcining 6h down promptly obtain mass percent and are 1% Co/AC catalyst.This catalyst is packed in the fluidized-bed reactor, and reaction temperature is controlled at 150 ℃, air speed 3000h
-1, H in the unstripped gas
2S content 3000ppm feeds O
2/ H
2The S ratio is 1: 2 O
2, balance gas N
2It penetrates Sulfur capacity is 4.81%, and desulfuration efficiency is 97.1%.
Claims (4)
1. H in the catalytic oxidative desulfurization coal gas
2The catalyst of S is characterized in that catalyst is active component with the metal oxide, and active carbon is a carrier, and the percentage by weight of each component is: active carbon 95.0%～99.9%, metal oxide 0.1%～5%.
Described active carbon is that specific area is 850～900m
2/ g, total pore volume is 0.45cm
3It is 0.154cm that/g, micropore hold
3/ g.
Described metal oxide is the oxide of Fe, V, Mn, Cu, Ce or Co.
2. H in a kind of catalytic oxidative desulfurization coal gas as claimed in claim 1
2The Preparation of catalysts method of S is characterized in that comprising the steps:
Press catalyst and form, in the solution of active component soluble salt, room temperature is placed 3-6h under the room temperature then with the active carbon incipient impregnation; Impregnated active carbon earlier at 50-60 ℃ of freeze-day with constant temperature 4-10h, and is continued dry 4-10h at 100-110 ℃, and activation 3-6h in 300-600 ℃ temperature and nitrogen atmosphere obtains required catalyst then.
3. H in a kind of catalytic oxidative desulfurization coal gas as claimed in claim 2
2The Preparation of catalysts method of S is characterized in that described active component soluble salt is Ce (NO
3)
36H
2O, Fe (NO
3)
39H
2O, Cu (NO
3)
23H
2O, Co (NO
3)
26H
2O, Mn (NO
3)
2Or NH
4VO
3
4. H in a kind of catalytic oxidative desulfurization coal gas as claimed in claim 1
2The Application of Catalyst of S is characterized in that catalyst is packed in fixed bed or the fluidized-bed reactor, at normal pressure, and 150-250 ℃, air speed 1000-8000h
-1Under the condition, aerating oxygen, the amount of aerating oxygen is O
2: H
2The S mol ratio is 1-2: 1-2, the H in the catalytic eliminating gas
2S.
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|---|---|---|---|
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|---|---|---|---|
| CN2011103939164A CN102500362A (en) | 2011-12-02 | 2011-12-02 | Catalyst for removing H2S from gas by catalytic oxidation, preparation method and application |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706353A (en) * | 2013-12-19 | 2014-04-09 | 绍兴文理学院 | AlMn composite pillared clay supported CrCe catalyst, and preparation method and application of catalyst |
| CN104785236A (en) * | 2015-04-21 | 2015-07-22 | 太原理工大学 | Mesoporous desulfurizer carrier and preparation method thereof |
| CN105032389A (en) * | 2015-07-24 | 2015-11-11 | 四川大学 | Mn-Ce bimetal doped activated carbon base desulfurization catalyst and preparation method thereof |
| CN105802676A (en) * | 2016-04-21 | 2016-07-27 | 安庆师范学院 | Method of removing H2S and Hg<0> in coal gas at same time through Fe2O3/carbon carrier catalyst |
| CN105903324A (en) * | 2016-05-18 | 2016-08-31 | 天津普瑞特净化技术有限公司 | Copper oxide loaded active carbon desulfurizing agent and preparation process thereof |
| CN109225137A (en) * | 2018-10-31 | 2019-01-18 | 榆林学院 | A kind of preparation method of the cobalt improved apricot shell active carbon of chlorination |
| CN113522348A (en) * | 2020-04-14 | 2021-10-22 | 中国石油化工股份有限公司 | Hydrogen sulfide remover and preparation method and application thereof |
| CN114192175A (en) * | 2021-12-30 | 2022-03-18 | 福州大学 | Metal-doped ordered mesoporous carbon desulfurization catalyst and preparation method and application thereof |
| CN116371392A (en) * | 2023-03-07 | 2023-07-04 | 中国科学院过程工程研究所 | Integrated desulfurization and decyanation catalyst and preparation method and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103706353A (en) * | 2013-12-19 | 2014-04-09 | 绍兴文理学院 | AlMn composite pillared clay supported CrCe catalyst, and preparation method and application of catalyst |
| CN103706353B (en) * | 2013-12-19 | 2015-09-23 | 绍兴文理学院 | AlMn composite axis system load C rCe catalyst, preparation method and application thereof |
| CN104785236A (en) * | 2015-04-21 | 2015-07-22 | 太原理工大学 | Mesoporous desulfurizer carrier and preparation method thereof |
| CN105032389A (en) * | 2015-07-24 | 2015-11-11 | 四川大学 | Mn-Ce bimetal doped activated carbon base desulfurization catalyst and preparation method thereof |
| CN105802676A (en) * | 2016-04-21 | 2016-07-27 | 安庆师范学院 | Method of removing H2S and Hg<0> in coal gas at same time through Fe2O3/carbon carrier catalyst |
| CN105903324A (en) * | 2016-05-18 | 2016-08-31 | 天津普瑞特净化技术有限公司 | Copper oxide loaded active carbon desulfurizing agent and preparation process thereof |
| CN109225137A (en) * | 2018-10-31 | 2019-01-18 | 榆林学院 | A kind of preparation method of the cobalt improved apricot shell active carbon of chlorination |
| CN113522348A (en) * | 2020-04-14 | 2021-10-22 | 中国石油化工股份有限公司 | Hydrogen sulfide remover and preparation method and application thereof |
| CN113522348B (en) * | 2020-04-14 | 2023-09-05 | 中国石油化工股份有限公司 | Hydrogen sulfide remover and preparation method and application thereof |
| CN114192175A (en) * | 2021-12-30 | 2022-03-18 | 福州大学 | Metal-doped ordered mesoporous carbon desulfurization catalyst and preparation method and application thereof |
| CN116371392A (en) * | 2023-03-07 | 2023-07-04 | 中国科学院过程工程研究所 | Integrated desulfurization and decyanation catalyst and preparation method and application thereof |
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Application publication date: 20120620 |