CN115583630A - Method for preparing synthesis gas by photo-thermal catalytic decomposition of hydrogen sulfide and carbon dioxide - Google Patents
Method for preparing synthesis gas by photo-thermal catalytic decomposition of hydrogen sulfide and carbon dioxide Download PDFInfo
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- CN115583630A CN115583630A CN202211143488.4A CN202211143488A CN115583630A CN 115583630 A CN115583630 A CN 115583630A CN 202211143488 A CN202211143488 A CN 202211143488A CN 115583630 A CN115583630 A CN 115583630A
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a method for preparing synthesis gas by decomposing hydrogen sulfide and carbon dioxide through photo-thermal catalysis, and belongs to the field of hydrogen production and harmful gas treatment. The invention is characterized in that high temperature is generated by solar energy condensation to decompose hydrogen sulfide and carbon dioxide or gas containing hydrogen sulfide and carbon dioxide, and the hydrogen sulfide and carbon dioxide are decomposed into carbon monoxide and hydrogen (synthesis gas) in the presence of a catalyst; the energy of photons in the catalyst can be utilized to promote the synergistic conversion of the hydrogen sulfide and the carbon dioxide by heating and adding light at the same time. The method is particularly suitable for treating the gas containing hydrogen sulfide and carbon dioxide in the chemical industry of natural gas, petroleum and coal, and can also be used for dissociating the gas containing hydrogen sulfide and carbon dioxide to prepare the synthesis gas in metallurgy, ocean and the like. The method has no special requirements or limitations on the source and the composition of the gas, so that the method has universality on the synergistic conversion of the hydrogen sulfide and the carbon dioxide into the synthetic gas.
Description
Technical Field
The invention belongs to the field of hydrogen production and harmful gas treatment, and relates to a method for decomposing harmful hydrogen sulfide and carbon dioxide into synthesis gas.
Background
With the increasing demand of people for clean energy, natural gas is more and more valued. While natural gas is rich in CO 2 And H 2 The acid gas of S is more than 2600 multiplied by 10 in the whole country 12 ft 3 Approximately 40% of the world's natural gas reserves. However, the exploitation of acid gas reservoirs also faces a number of difficulties: (1) CO 2 2 And H 2 The separation and treatment of S requires high technical cost; (2) The mining process must meet the basic requirements of environmental protection (reduction of CO) 2 And H 2 Discharge of S); (3) H 2 S has strong toxicity and great potential safety hazard.
Faced with these challenges, researchers have developed various techniques and processes to remove CO either separately or simultaneously 2 And H 2 And S. Most of these separation techniques are industrially mature, but still have the disadvantages of high investment and operation costs, and huge energy consumption. From CO 2 And H 2 And carbon and hydrogen resources are recovered in S, so that economic loss caused by the recovery can be compensated. Introducing CO 2 And H 2 S is synergistically converted into syngas (CO and H) 2 ) Is currently the most promising CO 2 And H 2 The S treatment method, the production and the application of the synthesis gas have extremely important positions in the chemical industry, and the synthesis gas can be used for producing ammonia and products thereof, methanol and products thereof, fischer-Tropsch synthesis products and hydroformylation products. Therefore, the synergistic conversion of hydrogen sulfide and carbon dioxide into synthesis gas is a technical field of major attention of domestic and foreign researchers.
At present, the method for the synergistic conversion of hydrogen sulfide and carbon dioxide mainly comprises the following steps: thermal decomposition, electrochemical, non-thermal plasma, and the like. The thermal decomposition method means that hydrogen sulfide and carbon dioxide are decomposed by high temperature under the action of a catalyst, althoughThe method obtains high conversion rate of hydrogen sulfide and carbon dioxide, but the method needs a large amount of energy and has more requirements on the selection of the catalyst, and the catalyst is easy to generate carbon deposition under high temperature condition to cause inactivation. Although the electrochemical method can treat high-concentration hydrogen sulfide and carbon dioxide gas and has high synthesis gas recovery rate, the electrochemical method still has the defects of multiple operation steps, serious equipment corrosion, poor reaction stability, low efficiency and the like. The non-thermal plasma method is a method in which high-energy electrons inelastically collide with gas molecules in a non-thermal plasma, and the energy is transferred to the molecules to generate excited molecules, atoms, and ions, thereby promoting CO 2 And H 2 And (4) decomposing S. Although this method has the advantages of simple operation, small device size, high energy efficiency, etc., it consumes a large amount of energy. In order to solve the defects of high energy consumption, complex operation, limited catalyst selection, easy carbon deposition and the like of the method for synergistically converting the hydrogen sulfide and the carbon dioxide, it is necessary to develop a novel technology.
The photo-thermal catalysis method is an emerging catalysis method in recent years and has the following advantages: (1) Higher catalytic efficiency is shown at lower temperature, and the catalytic efficiency is greatly reduced; (2) The introduction of light energy can adjust the catalytic selectivity of products which cannot be obtained by the traditional thermal catalysis; (3) improving the catalytic stability; (4) more convenient and economical; (5) instantaneous control of the reaction can be achieved.
Disclosure of Invention
The invention aims to solve the technical problem that the existing method for decomposing CO 2 And H 2 The technical method of S has the problems of high energy consumption, easy inactivation of the catalyst, complex operation and the like, and provides a novel method for decomposing CO 2 And H 2 And (S) a method.
In order to solve the problems, the invention provides a method for preparing synthesis gas by decomposing hydrogen sulfide and carbon dioxide by photo-thermal catalysis, which comprises the following steps:
the invention realizes two types of photo-thermal catalysis: (1) One is to use a 20-50W xenon lamp to simulate sunlight, concentrate a light source through a condenser lens, and the light source is concentrated by high times, so that light beams can provide certain heat energy, thereby realizing photo-thermal concerted catalysis; (2) The other method is that a heating device (controllable temperature) is used for heating to a certain temperature, and then a light source is added, so that photo-thermal concerted catalysis is realized. The photocatalysis and thermocatalysis methods have certain promotion effect on the conversion of hydrogen sulfide and carbon dioxide.
A method for preparing synthesis gas by decomposing hydrogen sulfide and carbon dioxide through photo-thermal catalysis comprises the following steps:
(1) Passing hydrogen sulfide and carbon dioxide gas through a quartz tube loaded with a catalyst, and using a feed gas of 2 to 100% by weight of CO 2 Ar and 2-5%H 2 The ratio of S/Ar is 1:1;
(2) Condensing with 20-50W xenon lamp via condenser to make the light beam concentrate on the surface of the catalyst at 500-900 deg.c and gas product (H) 2 CO) can be detected by connecting gas chromatography.
Another method for preparing synthesis gas by photothermal catalytic decomposition of hydrogen sulfide and carbon dioxide comprises the following steps:
(1) Passing hydrogen sulfide and carbon dioxide gas through a quartz tube loaded with a catalyst, and using a feed gas of 2 to 100% by weight of CO 2 And 2 to 5%H 2 The ratio of S is 1:1;
(2) Heating the catalyst to a certain temperature by using resistance wire heating, then irradiating light on the surface of the catalyst, wherein the reaction temperature is 600-900 ℃, and the gas product (H) is obtained 2 CO) can be detected by a linked gas chromatograph.
The photo-thermal catalyst filled in the light irradiation area is solid particles or powder, and the solid photo-thermal catalyst with photo-thermal catalytic activity is applicable to the invention. For example, cerium oxide, bismuth telluride, cobalt oxide, tungsten oxide, indium oxide, gallium oxide, aluminum oxide, strontium titanate, magnesium oxide, molybdenum oxide, titanium dioxide, zinc ferrite, and a mixture of two or more thereof. The photothermal catalyst can be modified and modified by metals (including Fe, cu, co, mo, ni, ag, au, ca, bi, ga and Ce) and non-metal elements (including N, C, S, F) to improve the catalytic reaction performance.
The component with photocatalytic activity can also be loaded on a porous material to prepare a loaded catalyst, the used carrier is not particularly limited, and can be one or a mixture of two or more of activated carbon, a carbon molecular sieve, a carbon nanotube, carbon fibers, graphene, fullerene, cerium oxide, bismuth telluride, cobalt oxide, tungsten oxide, indium oxide, gallium oxide, aluminum oxide, strontium titanate, magnesium oxide, molybdenum oxide, titanium dioxide, zinc ferrite, cadmium sulfide, molybdenum disulfide, a zeolite molecular sieve, a mesoporous-microporous composite material, a high-specific surface area macroporous material, a high polymer and porous metal. The loading method is to contact the carrier and the raw material containing the active metal component in the presence of the solvent, and the contact conditions are as follows: the temperature is 0-100 ℃, the time is 1-24 h, the solvent is at least one selected from water, methanol, ethanol, dimethyl sulfoxide, tetrahydrofuran, pyridine, acetonitrile, n-propanol and dimethylformamide, and the loading capacity of the load on the carrier is more than 0.1 wt%.
Compared with the prior art, the technical scheme of the invention has the following advantages that:
(1) The simulated sunlight is used as an energy source, so that the solar energy-saving heat-storage water heater is a renewable green energy source, and makes up for the disadvantage of high pure thermocatalysis energy consumption;
(2) The invention utilizes photo-thermal concerted catalysis, and utilizes sunlight to break the thermodynamic equilibrium of decomposition of hydrogen sulfide and carbon dioxide, thereby realizing effective decomposition of hydrogen sulfide and carbon dioxide at low temperature;
(3) The invention can carry out harmless treatment on the hydrogen sulfide and the carbon dioxide, and can prepare the synthesis gas through the cooperative conversion of the hydrogen sulfide and the carbon dioxide;
(4) The photo-thermal catalysis used in the invention decomposes hydrogen sulfide and carbon dioxide, greatly reduces the carbon deposition phenomenon of the catalyst, and has obvious improvement effect on the stability of the catalyst;
(5) The invention has no special requirements or limitations on the source and the composition of the gas, thereby having general applicability to the hydrogen production by decomposition of hydrogen sulfide with various concentrations.
(6) The catalyst used in the invention is widely selected.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings for implementing the technical apparatus will be briefly described.
FIG. 1 is a schematic view of the structure of a photothermal catalytic reactor used in the test example of the present invention.
Description of reference numerals:
1-CO 2 gas cylinder, 2-H 2 S gas cylinder, 3-CO 2 Gas flowmeter, 4-H 2 The system comprises an S gas flowmeter, a 5-gas mixing device, a 6-solar condenser, a 7-reactor metal shell, an 8-heat insulation layer, a 9-resistance wire, a 10-quartz tube, an 11-product collecting device and a 12-tail gas treatment device.
Detailed Description
The following describes specific embodiments of the present invention in detail with reference to the technical solutions.
Example 1: the catalyst used in the preparation of syngas by photothermal catalytic decomposition of hydrogen sulfide and carbon dioxide in this example was Ga 2 O 3 。
Catalyst granulation: adding commercial Ga 2 O 3 The solid powder is shaped under pressure and then screened to 20-40 mesh particles.
Pretreatment of a catalyst: ga obtained 2 O 3 The resulting mixture was charged into a silica tube for vulcanization and a vulcanizing agent (5%H) was introduced at a flow rate of 50sccm 2 S/Ar), raised to 500 ℃ over 60 minutes and held for 60 minutes.
The particulate catalyst was placed in a quartz glass tube and nitrogen was introduced for 5 minutes to remove oxygen from the reactor. The mixed gas containing 2 percent of hydrogen sulfide and 2 percent of carbon dioxide passes through the catalyst bed layer at a certain flow rate under the control of a mass flow meter. After the gas is stabilized, adding light to carry out photo-thermal catalytic reaction. After the reacted gas is absorbed by sodium hydroxide aqueous solution and copper sulfate aqueous solution in two stages, the content of carbon monoxide and hydrogen in the tail gas is analyzed on line by a chromatograph. And calculating the conversion rate of the hydrogen sulfide and the carbon dioxide and the proportion of the synthesis gas according to the chromatographic quantitative analysis result.
The coupling decomposition reaction of hydrogen sulfide and carbon dioxide is carried out in the presence of a solid photo-thermal catalyst by adopting the reaction device and the reaction steps. The light source used a 20W xenon lamp, the catalyst loading was 200mg, and the reaction gas (2%H) 2 S/Ar and 2% of CO 2 Mixed gas of/Ar) at a flow rate of 60sccm. From the results of the quantitative chromatographic analysis, the conversion of hydrogen sulfide was calculated to be 33.5% and the conversion of carbon dioxide was calculated to be 19%, giving the ratio of synthesis gas (H) 2 CO) is 0.8, the carbon deposition on the surface of the catalyst is not obvious, but the sulfuration phenomenon is obvious.
Example 2: the catalyst employed in the photothermal catalytic decomposition of hydrogen sulfide and carbon dioxide to produce syngas in this example was 2wt% Mo/MgO.
Preparing a catalyst: mo was loaded into commercially available MgO at a content of 2wt% by an impregnation method, and a solid powder thereof was molded under pressure, followed by sieving 20 to 40 mesh particles.
Pretreatment of a catalyst: the obtained 2wt% Mo/MgO was charged into a quartz tube for vulcanization and a vulcanizing agent (5%H) was fed at a flow rate of 50sccm 2 S/Ar), raised to 600 ℃ over 60 minutes and held for 60 minutes.
The particulate catalyst was placed in a quartz glass tube and nitrogen was introduced for 5 minutes to remove oxygen from the reactor. The mixed gas containing 5 percent of hydrogen sulfide and 5 percent of carbon dioxide passes through the catalyst bed layer at a certain flow rate under the control of a mass flow meter. After the gas is stabilized, adding light to carry out photo-thermal catalytic reaction. After the reacted gas is absorbed by sodium hydroxide aqueous solution and copper sulfate aqueous solution in two stages, the content of carbon monoxide and hydrogen in the tail gas is analyzed on line by a chromatograph. And calculating the conversion rate of the hydrogen sulfide and the carbon dioxide and the proportion of the synthesis gas according to the chromatographic quantitative analysis result.
The above reaction apparatus and reaction steps are employed to carry out the decomposition reaction of hydrogen sulfide and carbon dioxide in the presence of a solid photo-thermal catalyst. The light source used a 30W xenon lamp, the catalyst loading was 200mg, and the reaction gas (5%H) 2 S/Ar and 5% CO 2 Mixed gas of/Ar) at a flow rate of 60sccm. The conversion of hydrogen sulfide was calculated to be 50.4% and the conversion of carbon dioxide was calculated to be 23.2% from the results of the quantitative chromatographic analysis, and the ratio of the synthesis gas (H) was obtained 2 CO) is 1.4, the carbon deposition on the surface of the catalyst is not obvious, but the phenomenon of vulcanization is obvious.
Example 3: the example photothermal catalytic decomposition of Hydrogen sulfide and carbon dioxide to Synthesis gas employed a catalyst of 2wt%o/Al 2 O 3 。
Preparation of the catalyst: loading of Co to commercial Al by impregnation method 2 O 3 The solid powder is molded under pressure, and then the granules of 20 to 40 meshes are screened out.
Pretreatment of a catalyst: 2wt% of the obtained Co/Al 2 O 3 The resulting mixture was charged into a quartz tube for vulcanization and a vulcanizing agent (5%H) was introduced at a flow rate of 50sccm 2 S/Ar), raised to 700 ℃ over 60 minutes and held for 60 minutes.
The particulate catalyst was placed in a quartz glass tube and nitrogen was introduced for 5 minutes to remove oxygen from the reactor. The mixed gas containing 5 percent of hydrogen sulfide and pure carbon dioxide passes through the catalyst bed layer at a certain flow rate under the control of a mass flow meter. After the gas is stabilized, adding light to carry out photo-thermal catalytic reaction. After the reacted gas is absorbed by sodium hydroxide aqueous solution and copper sulfate aqueous solution in two stages, the content of carbon monoxide and hydrogen in the tail gas is analyzed on line by a chromatograph. And calculating the conversion rate of the hydrogen sulfide and the carbon dioxide and the proportion of the synthesis gas according to the chromatographic quantitative analysis result.
The above reaction apparatus and reaction steps are employed to carry out the decomposition reaction of hydrogen sulfide and carbon dioxide in the presence of a solid photo-thermal catalyst. The light source used a 30W xenon lamp, the catalyst loading was 200mg, and the reaction gas (5%H) 2 S/Ar and pure CO 2 Mixed gas of (2) at a flow rate of 60sccm. The conversion of hydrogen sulfide was 53.7% and the conversion of carbon dioxide was 36.1% as calculated from the results of the quantitative chromatographic analysis, and the ratio of the obtained synthesis gas (H) was obtained 2 CO) is 0.9, the carbon deposition phenomenon exists on the surface of the catalyst, and the obvious vulcanization phenomenon exists.
Example 4: the example photothermal catalytic decomposition of hydrogen sulfide and carbon dioxide to produce syngas employs a catalyst of 2wt% Ag/MoS 2 。
Preparation of the catalyst: loading of 2wt% Ag to commercial MoS by impregnation 2 The solid powder is molded under pressure, and then the granules of 20 to 40 meshes are screened out.
2wt% Ag/MoS of the obtained 2 The resulting mixture was charged into a quartz tube for vulcanization and a vulcanizing agent (5%H) was introduced at a flow rate of 50sccm 2 S/Ar), raised to 900 ℃ over 60 minutes and held for 60 minutes.
The particulate catalyst was placed in a quartz glass tube and nitrogen was introduced for 5 minutes to remove oxygen from the reactor. The mixed gas containing 10 percent of hydrogen sulfide and pure carbon dioxide passes through the catalyst bed layer at a certain flow rate under the control of a mass flow meter. After the gas is stabilized, adding light to carry out photo-thermal catalytic reaction. After the reacted gas is absorbed by sodium hydroxide aqueous solution and copper sulfate aqueous solution in two stages, the content of carbon monoxide and hydrogen in the tail gas is analyzed on line by a chromatograph. And calculating the conversion rate of the hydrogen sulfide and the carbon dioxide and the proportion of the synthesis gas according to the chromatographic quantitative analysis result.
The above reaction apparatus and reaction steps are employed to carry out the decomposition reaction of hydrogen sulfide and carbon dioxide in the presence of a solid photo-thermal catalyst. The light source used a 50W xenon lamp, the catalyst loading was 200mg, and the reaction gas (10% by weight H) 2 S/Ar and pure CO 2 Mixed gas of (2) at a flow rate of 60sccm. The conversion of hydrogen sulfide was calculated to be 61.6% and the conversion of carbon dioxide was calculated to be 49% from the results of the quantitative chromatographic analysis, and the ratio of the synthesis gas (H) was obtained 2 CO) is 0.7, the surface of the catalyst has obvious carbon deposition, and the tail part of the quartz tube has obvious sulfur deposition.
Example 5: the catalyst used in the photothermal catalytic decomposition of hydrogen sulfide and carbon dioxide to produce syngas was 2wt% Au/CdS.
Preparation of the catalyst: au was loaded into commercially available CdS at a content of 2wt% by the dipping method, and the solid powder thereof was molded under pressure, and then particles of 20 to 40 mesh were screened.
The obtained Au/CdS was charged into a quartz tube for vulcanization in an amount of 2wt% and a vulcanizer (5%H) was introduced at a flow rate of 50sccm 2 S/Ar), raised to 900 ℃ over 60 minutes and held for 60 minutes.
The particulate catalyst was placed in a quartz glass tube and nitrogen was introduced for 5 minutes to remove oxygen from the reactor. The mixed gas containing 10 percent of hydrogen sulfide and pure carbon dioxide passes through the catalyst bed layer at a certain flow rate through the control of a mass flow meter. And starting heating after the gas is stable, and adding light after the gas is heated to the set temperature. After the reacted gas is absorbed by sodium hydroxide aqueous solution and copper sulfate aqueous solution in two stages, the content of carbon monoxide and hydrogen in the tail gas is analyzed on line by a chromatograph. And calculating the conversion rate of the hydrogen sulfide and the carbon dioxide and the proportion of the synthesis gas according to the chromatographic quantitative analysis result.
The above reaction apparatus and reaction steps are employed to carry out the decomposition reaction of hydrogen sulfide and carbon dioxide in the presence of a solid photo-thermal catalyst. Temperature 900 ℃ and light Source 30W xenon lamp, catalyst loading 200mg, reaction gas (10% by weight) 2 S/Ar and pure CO 2 Mixed gas of (2) at a flow rate of 60sccm. The conversion of hydrogen sulfide was 65.4% and the conversion of carbon dioxide was 53% as calculated from the results of the quantitative chromatographic analysis, and the ratio of the synthesis gas (H) was obtained 2 CO) is 0.8, the surface of the catalyst has obvious carbon deposition, and the tail part of the quartz tube has obvious sulfur deposition.
The specific reaction conditions, hydrogen sulfide conversion, carbon dioxide conversion and syngas ratio results of examples 1-4 are shown in table 1.
TABLE 1
The results in table 1 show that when the method for the photo-thermal catalytic hydrogen sulfide and carbon dioxide synergistic conversion provided by the invention is used for decomposing hydrogen sulfide and carbon dioxide, higher conversion rates of hydrogen sulfide and carbon dioxide can be maintained at lower temperature, the stability of the catalyst is improved, and a certain proportion of synthesis gas is obtained.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (7)
1. A method for preparing synthesis gas by decomposing hydrogen sulfide and carbon dioxide by photo-thermal catalysis is characterized in that the decomposition of the hydrogen sulfide and the carbon dioxide is realized by the cooperation of the thermal catalysis and the photo-catalysis, and the method comprises the following steps: hydrogen sulfide and carbon dioxide or a gas containing hydrogen sulfide and carbon dioxide can be decomposed by generating high temperature through solar energy condensation, and the hydrogen sulfide and the carbon dioxide are decomposed into synthesis gas in the presence of a catalyst; or the decomposition of hydrogen sulfide and carbon dioxide or the gas containing hydrogen sulfide and carbon dioxide into synthesis gas can be promoted by heating and adding light at the same time under the action of a catalyst and under the action of high temperature and illumination.
2. The method of claim 1, wherein the conditions for the hydrogen sulfide and carbon dioxide decomposition reaction comprise: the reaction temperature is 40-1000 ℃, the illumination intensity is more than 0.1W, and the reaction pressure is-0.06 MPa-0.6 MPa.
3. The method of claim 1, wherein the photothermal catalyst is a solid particle or powder.
4. The method of claims 1 and 3, wherein the solid photothermal catalyst comprises cerium oxide, bismuth telluride, cobalt oxide, tungsten oxide, indium oxide, gallium oxide, aluminum oxide, strontium titanate, magnesium oxide, molybdenum oxide, titanium dioxide, zinc ferrite, and mixtures of two or more thereof.
5. The method of claims 1, 3, and 4, wherein the photothermal catalyst is modified and decorated with metals (including Fe, cu, co, mo, ni, ag, au, ca, bi, ga, ce) and non-metals (including N, C, S, F) to improve catalytic performance.
6. The method according to claims 1, 3 and 4, wherein the component having photocatalytic activity can be supported on a porous material to form a supported catalyst, and the carrier used is not particularly limited and may be one or a mixture of two or more of activated carbon, carbon molecular sieve, carbon nanotube, carbon fiber, graphene, fullerene, cerium oxide, bismuth telluride, cobalt oxide, tungsten oxide, indium oxide, gallium oxide, aluminum oxide, strontium titanate, magnesium oxide, molybdenum oxide, titanium dioxide, zinc ferrite, cadmium sulfide, molybdenum disulfide, zeolite molecular sieve, mesoporous-microporous composite material, high specific surface area macroporous material, high molecular polymer and porous metal.
7. The method of claim 5,6 further characterized in that the loading on the support is above 0.1 wt%.
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