CN110201540B - Process for removing methyl mercaptan from carbon dioxide gas - Google Patents
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Abstract
The invention discloses a process for removing methyl mercaptan from carbon dioxide gas, which comprises the following steps: uniformly mixing carbon dioxide gas containing methyl mercaptan and air to obtain mixed gas, wherein the molar ratio of oxygen to methyl mercaptan in the mixed gas is (0.6-2.5): 1; and secondly, reacting the mixed gas under the action of a mercaptan removing catalyst to obtain carbon dioxide gas with the volume content of sulfur not more than 0.1ppm, wherein the mercaptan removing catalyst is prepared from a waste zinc oxide desulfurizer, zinc salt, manganese salt, potassium salt and a binder. The invention mixes the carbon dioxide gas containing methyl mercaptan with air, reacts under the action of the methyl mercaptan removing catalyst, and converts the methyl mercaptan into hydrogen sulfide and then absorbed by the methyl mercaptan removing catalyst by controlling the molar ratio of the methyl mercaptan to the oxygen, thereby realizing the removal of the methyl mercaptan in the carbon dioxide gas, avoiding the generation of impurity gases and greatly improving the removal effect of the methyl mercaptan in the carbon dioxide gas.
Description
Technical Field
The invention belongs to the technical field of gas phase desulfurization, and particularly relates to a process for removing methyl mercaptan from carbon dioxide gas.
Background
Natural gas is used as an ideal clean civil fuel, and the application range of the natural gas is wider and wider. In recent years, the natural gas exploitation amount of China is gradually increased year by year, a large number of high-yield gas fields are successively developed, but CO in the exploited natural gas2The content is different, wherein the average value of the carbon dioxide content in the III natural gasAt 26% carbon dioxide is higher in group iv natural gas, so the natural gas must be decarbonized to reduce the carbon dioxide content to less than 3% for use as a domestic natural gas. However, due to the limitation of the decarburization process, a large amount of methyl mercaptan is accumulated in the carbon dioxide gas enriched after the decarburization treatment. Only after the methyl mercaptan is removed, the carbon dioxide can reach the environmental emission standard.
At present, the research on the removal of methyl mercaptan in carbon dioxide gas is few, only a few relevant patents and documents adopt a solvent absorption or wet oxidation treatment method, the process flow is long, the operation is complex, the equipment investment is large, the energy consumption is high, and the wastewater needs to be treated again to generate secondary pollution. With the stricter emission standard of carbon dioxide gas, the low-cost removal of the methyl mercaptan in the carbon dioxide gas can not only solve the environmental problem caused by the emission of the methyl mercaptan, but also improve the economic benefit and social benefit of enterprises.
Fangjian Dynasty et al (Natural gas chemical, volume 38 of 2013, pages 9-12) adopt a TS-1 molecular sieve and a hydrogen peroxide solution to remove methyl mercaptan in carbon dioxide gas. The method needs to add a large amount of hydrogen peroxide solution, a large amount of sulfur-containing wastewater can be generated subsequently, and the molecular sieve has the problems of abrasion and separation in the hydrogen peroxide solution.
Chinese patent CN203139886U discloses a device for removing malodorous gas of methyl mercaptan by using chlorine dioxide, which adopts the reaction of chlorine dioxide and malodorous gas of methyl mercaptan in an odor reactor, and then the reaction is absorbed by an alkali absorption tower and a tail gas absorption tower, thereby achieving the purpose of deodorization. The method produces a large amount of alkali absorption waste liquid, and chlorine dioxide is also a highly toxic gas with strong pungent odor.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process for removing methyl mercaptan from carbon dioxide gas, aiming at the defects of the prior art. The process uniformly mixes the carbon dioxide gas containing the methyl mercaptan with air, reacts under the action of the methyl mercaptan removing catalyst, and converts the methyl mercaptan into hydrogen sulfide and then is absorbed by the methyl mercaptan removing catalyst by controlling the molar ratio of the methyl mercaptan to the oxygen, so that the removal of the methyl mercaptan in the carbon dioxide gas is realized, the generation of impurity gases is avoided, and the removal effect of the methyl mercaptan in the carbon dioxide gas is greatly improved.
In order to solve the technical problems, the invention adopts the technical scheme that: a process for removing methyl mercaptan from carbon dioxide gas is characterized by comprising the following steps:
step one, introducing carbon dioxide gas containing methyl mercaptan into a gas distribution system and uniformly mixing the carbon dioxide gas with air to obtain mixed gas; the molar ratio of oxygen to methyl mercaptan in the mixed gas is (0.6-2.5): 1;
step two, introducing the mixed gas obtained in the step one into a reaction system, and performing a mercaptan removal reaction in the presence of a mercaptan removal catalyst to obtain carbon dioxide gas; the pressure of the mercaptan removing reaction is 0.1MPa to 5.0MPa, the temperature is 150 ℃ to 350 ℃, and the space velocity of the mixed gas is 500h-1～3000h-1(ii) a The mercaptan removing catalyst is prepared from a waste zinc oxide desulfurizer, zinc salt, manganese salt, potassium salt and a binder, wherein the mass percent of the waste zinc oxide desulfurizer is 30-80%, the total mass percent of the zinc salt, the manganese salt and the potassium salt is 8-50%, the mass percent of the binder is 3-20%, and the waste zinc oxide desulfurizer is a zinc oxide desulfurizer after desulfurization reaction; the sulfur content of the carbon dioxide gas is less than 0.1ppm by volume.
The process of the invention is divided into two steps of gas distribution and mercaptan removal reaction, firstly, carbon dioxide gas containing methyl mercaptan and air are uniformly mixed, then the mixture is introduced into a reaction system to carry out reaction (1) in the presence of a mercaptan removal catalyst, and the reaction formula of the reaction (1) is as follows: 3O2(g)+2CH4S(g)＝2H2S(g)+2CO2(g)+2H2And O (g), namely, methyl mercaptan in the carbon dioxide gas and oxygen in the air are subjected to catalytic reaction under the action of the methyl mercaptan removing catalyst to be converted into hydrogen sulfide, and the hydrogen sulfide is absorbed and removed by the methyl mercaptan removing catalyst, so that the removal of the methyl mercaptan in the carbon dioxide gas is realized.
The mercaptan removal catalyst is prepared from a waste zinc oxide desulfurizer, the waste zinc oxide desulfurizer is a product obtained by removing hydrogen sulfide impurities from gas by using a zinc oxide desulfurizer in the field of industrial gas purification, the zinc oxide desulfurizer mainly comprises zinc oxide with the mass content of more than 95% according to the industrial standard HG/T2508-sodium chloride 2012, and the desulfurization principle is that the zinc oxide reacts with the hydrogen sulfide to generate the zinc sulfide. Therefore, the main component of the waste zinc oxide desulfurizer is zinc sulfide, the main active component of the methyl mercaptan removing catalyst is still zinc sulfide, and the zinc sulfide catalyzes the reaction of methyl mercaptan and oxygen to convert the methyl mercaptan into hydrogen sulfide. Meanwhile, the mercaptan removal catalyst also contains a co-catalysis component prepared by taking zinc salt, manganese salt and potassium salt as raw materials, and the co-catalysis component not only can coordinate with zinc sulfide for catalysis, but also can react with hydrogen sulfide so as to remove the hydrogen sulfide from gas.
The invention promotes the catalytic reaction of methyl mercaptan and oxygen to convert into hydrogen sulfide by controlling the molar ratio of oxygen to methyl mercaptan in the mixed gas formed by carbon dioxide gas containing methyl mercaptan and air. When the molar ratio of oxygen to methyl mercaptan in the mixed gas exceeds 3: 1, reacting (2) oxygen and methyl mercaptan under the action of a methyl mercaptan removing catalyst, wherein the reaction formula of the reaction (2) is as follows: 3O2(g)+CH4S(g)＝SO2(g)+CO2(g)+2H2O (g), i.e. conversion of methyl mercaptan to SO2The gas is continuously left in the carbon dioxide gas and cannot be removed; when the molar ratio of oxygen to methyl mercaptan in the mixed gas is lower than 0.5: 1, the oxygen and the methyl mercaptan are subjected to a complex reaction (3) under the action of a methyl mercaptan removing catalyst, and finally a large amount of CS is generated2And a small amount of a mixture of methyl sulfide and dimethyl disulfide, i.e. conversion of methyl mercaptan to CS2The gas continues to remain in the carbon dioxide gas and cannot be removed. Therefore, comprehensively considered, the molar ratio of the oxygen to the methyl mercaptan in the mixed gas is controlled to be (0.6-2.5): 1, only reaction (1) is ensured to be generated between the methyl mercaptan and the oxygen under the action of the methyl mercaptan removing catalyst, and the reaction (2) and the reaction (3) are avoided, SO that the methyl mercaptan is converted into hydrogen sulfide and then absorbed and removed by the methyl mercaptan removing catalyst, and SO is avoided2Gas and CS2The generation of impurity gases such as gas and the like greatly improves the removal effect of methyl mercaptan in carbon dioxide gas.
The process for removing methyl mercaptan from carbon dioxide gas is characterized in that the volume content of methyl mercaptan in carbon dioxide gas in the first step is 100ppm to 2000 ppm. In actual industrial production, after natural gas is subjected to a decarbonization process, the volume content of methyl mercaptan in the obtained carbon dioxide gas is usually 100 ppm-2000 ppm, so that the process disclosed by the invention is particularly suitable for removing methyl mercaptan from carbon dioxide in the natural gas industry, and is wide in application range and high in practical value.
The process for removing methyl mercaptan from carbon dioxide gas is characterized in that the molar ratio of oxygen to methyl mercaptan in the mixed gas in the first step is (0.8-1.8): 1. oxygen and methyl mercaptan in the mixed gas are controlled within the range, the catalytic reaction is further ensured to be smoothly carried out towards the reaction (1), the reactions (2) and (3) are avoided, the generation of other impurity gases is reduced, and the deep removal of the methyl mercaptan in the carbon dioxide gas is facilitated.
The process for removing methyl mercaptan from carbon dioxide gas is characterized in that in the second step, the zinc salt is zinc nitrate or basic zinc carbonate, the manganese salt is potassium permanganate or manganese nitrate, and the potassium salt is potassium hydroxide or potassium nitrate. The raw materials for preparing the mercaptan removing catalyst are wide in source and easy to obtain, and the preparation of the mercaptan removing catalyst is facilitated.
The process for removing methyl mercaptan from carbon dioxide gas is characterized in that the binder in the second step is activated clay, aluminum oxide, bentonite or attapulgite. The binder is the most commonly used binder in the catalyst industry, is easy to obtain, has low cost and stable performance, and is beneficial to the preparation of the mercaptan removing catalyst.
The process for removing methyl mercaptan from carbon dioxide gas is characterized in that the preparation process of the methyl mercaptan removing catalyst in the second step is as follows: respectively grinding the waste zinc oxide desulfurizer, zinc salt, manganese salt, potassium salt and binder until the particle size and the mesh number are more than 200 meshes, uniformly mixing, extruding and forming, drying at 80-120 ℃ for 3-5 h, and roasting at 350-550 ℃ for 3-5 h to obtain the mercaptan-removing catalyst. The waste zinc oxide desulfurizer, the zinc salt, the manganese salt, the potassium salt and the binder are ground, extruded into strips and molded, and roasted after being dried to obtain the mercaptan removal catalyst, wherein the main component of zinc sulfide of the waste zinc oxide desulfurizer has good high temperature resistance, and the preparation process including roasting does not influence the high temperature resistance, so that the activity of the mercaptan removal catalyst is ensured; meanwhile, zinc oxide formed after roasting of the zinc salt is a desulfurization component with good performance and can react with hydrogen sulfide which is a conversion product of methyl mercaptan to generate zinc sulfide, so that hydrogen sulfide is removed, various manganese series substances formed after roasting of the manganese salt can effectively promote the decomposition of the methyl mercaptan to generate the hydrogen sulfide and can also react with the hydrogen sulfide to generate manganese sulfide so as to remove the hydrogen sulfide, and potassium hydroxide in potassium salt or potassium oxide obtained by roasting of potassium nitrate has good organic sulfur hydrolysis capacity and can also react with the hydrogen sulfide so as to remove the hydrogen sulfide. In addition, the zinc salt, the manganese salt and the potassium salt are decomposed in the roasting process, so that a pore channel is formed, the number of the pore channels in the mercaptan removing catalyst is increased, the specific surface area and the porosity of the catalyst are further increased, and the activity of the mercaptan removing catalyst is further improved.
In addition, the zinc oxide desulfurizer is generally prepared by adopting active zinc oxide, and the active zinc oxide is characterized in that the structural particles are in a nanometer level, has the dual characteristics of nanometer materials and traditional zinc oxide, and has the characteristics of large specific surface area and high chemical activity compared with the traditional zinc oxide product. The zinc sulfide in the waste zinc oxide desulfurizer is generated by the slow reaction of active zinc oxide and hydrogen sulfide, so that the waste zinc oxide desulfurizer also has related special properties. The waste zinc oxide desulfurizer is crushed again, added with relevant cocatalyst components and reshaped for use, so that the catalytic performance of zinc sulfide can be fully exerted, unused zinc oxide in the desulfurizer can be exposed again and fully utilized, the hydrogen sulfide of a conversion product of methyl mercaptan is removed in a synergistic manner, the resource utilization rate is improved, and solid waste which is difficult to treat is recycled and reduced.
Compared with the prior art, the invention has the following advantages:
1. the invention mixes the carbon dioxide gas containing methyl mercaptan with air, reacts in the presence of the methyl mercaptan removing catalyst, the methyl mercaptan is converted into hydrogen sulfide by controlling the molar ratio of the methyl mercaptan to the oxygen, and the hydrogen sulfide is absorbed and removed by the methyl mercaptan removing catalyst, thereby realizing the removal of the methyl mercaptan in the carbon dioxide gas, avoiding SO2Gas and CS2The gas generation greatly improves the effect of removing methyl mercaptan in the carbon dioxide gas.
2. The invention adopts the waste zinc oxide desulfurizer to prepare the mercaptan removal catalyst, utilizes the main component of the waste zinc oxide desulfurizer to catalyze the reaction of methyl mercaptan and oxygen, converts the methyl mercaptan into hydrogen sulfide, is supplemented with the cocatalyst component prepared by taking zinc salt, manganese salt and potassium salt as raw materials, and reacts with the hydrogen sulfide to remove the hydrogen sulfide from the gas in a synergetic way, thereby realizing the reutilization of the waste zinc oxide desulfurizer and saving the cost of the catalyst raw materials.
3. The catalytic reaction process of the invention is a gas-solid reaction, the operation is simple and stable, the process flow is short, only air is required to be added in proportion, no solvent is required to be introduced, no waste liquid is generated, the requirement on equipment is low, the energy consumption is low, the cost is low, and the invention is environment-friendly.
4. The process can reduce the sulfur content in the carbon dioxide containing the methyl mercaptan with the volume content of 100 ppm-2000 ppm to be less than 0.1ppm, so that the carbon dioxide obtained by the process reaches the environmental protection emission standard, can be further used or sold as a chemical product, can also be directly discharged into the atmosphere, further reduces the treatment cost of the carbon dioxide containing the methyl mercaptan, and is suitable for treating the carbon dioxide gas enriched after decarbonization in natural gas.
5. The preparation method of the mercaptan removing catalyst is simple, the raw material source is wide, the industrial production of the catalyst is facilitated, the waste zinc oxide desulfurizer is fully utilized, the resource utilization rate is improved, and the recycling and reduction of solid wastes which are difficult to treat are realized.
The technical solution of the present invention is further described in detail by the accompanying drawings and examples.
Drawings
FIG. 1 is a process flow diagram for the removal of methyl mercaptan from carbon dioxide gas according to the present invention.
Detailed Description
As shown in FIG. 1, the process flow for removing methyl mercaptan from carbon dioxide gas of the present invention comprises: introducing the carbon dioxide gas containing the methyl mercaptan and air into a gas distribution system, uniformly mixing to obtain mixed gas, introducing the mixed gas into a reaction system, reacting in the presence of a methyl mercaptan removing catalyst, and removing the methyl mercaptan to obtain the carbon dioxide gas.
Example 1
The embodiment comprises the following steps:
step one, introducing carbon dioxide gas with the volume content of methyl mercaptan of 500ppm into a gas distribution system and uniformly mixing the carbon dioxide gas with air to obtain mixed gas; the molar ratio of oxygen to methyl mercaptan in the mixed gas is 1.8: 1;
step two, introducing the mixed gas obtained in the step one into a reaction system, and performing a mercaptan removal reaction in the presence of a mercaptan removal catalyst to obtain carbon dioxide gas; the pressure of the mercaptan removal reaction is 4.0MPa, the temperature is 300 ℃, and the space velocity of the mixed gas is 1000h-1(ii) a The mercaptan removing catalyst is prepared from a waste zinc oxide desulfurizer, zinc nitrate, potassium permanganate, potassium hydroxide and activated clay, wherein the waste zinc oxide desulfurizer is a zinc oxide desulfurizer subjected to desulfurization reaction, and the mercaptan removing catalyst is prepared by the following steps: respectively grinding 30kg of waste zinc oxide desulfurizer, 12.5kg of zinc nitrate, 25kg of potassium permanganate, 12.5kg of potassium hydroxide and 20kg of activated clay until the particle size and the mesh number are more than 200 meshes, uniformly mixing, extruding and forming, drying at 110 ℃ for 4h, and roasting at 500 ℃ for 4h to obtain a mercaptan removal catalyst; the sulfur content in the carbon dioxide gas was 0.1ppm by volume.
Example 2
The embodiment comprises the following steps:
step one, introducing carbon dioxide gas with the volume content of methyl mercaptan of 1000ppm into a gas distribution system and uniformly mixing the carbon dioxide gas with air to obtain mixed gas; the molar ratio of oxygen to methyl mercaptan in the mixed gas is 0.8: 1;
step two, introducing the mixed gas obtained in the step one into a reaction system, and performing a mercaptan removal reaction in the presence of a mercaptan removal catalyst to obtain carbon dioxide gas; the pressure of the mercaptan removal reaction is 3.0MPa, the temperature is 300 ℃, and the space velocity of the mixed gas is 800h-1(ii) a The mercaptan removing catalyst is prepared from a waste zinc oxide desulfurizer, basic zinc carbonate, manganese nitrate, potassium hydroxide and attapulgite, wherein the waste zinc oxide desulfurizer is a zinc oxide desulfurizer subjected to desulfurization reaction, and the mercaptan removing catalyst is prepared by the following steps: respectively grinding 50kg of waste zinc oxide desulfurizer, 5kg of basic zinc carbonate, 20kg of manganese nitrate, 5kg of potassium hydroxide and 20kg of attapulgite until the particle sizes and the meshes are more than 200 meshes, uniformly mixing, extruding and forming, drying at 80 ℃ for 4h, and roasting at 350 ℃ for 5h to obtain a mercaptan removal catalyst; the sulfur content in the carbon dioxide gas was 0.08ppm by volume.
Example 3
The embodiment comprises the following steps:
step one, introducing carbon dioxide gas with the volume content of methyl mercaptan of 100ppm into a gas distribution system and uniformly mixing the carbon dioxide gas with air to obtain mixed gas; the molar ratio of oxygen to methyl mercaptan in the mixed gas is 0.6: 1;
step two, introducing the mixed gas obtained in the step one into a reaction system, and performing a mercaptan removal reaction in the presence of a mercaptan removal catalyst to obtain carbon dioxide gas; the pressure of the mercaptan removal reaction is 0.1MPa, the temperature is 150 ℃, and the space velocity of the mixed gas is 500h-1(ii) a The mercaptan removing catalyst is prepared from a waste zinc oxide desulfurizer, zinc nitrate, potassium permanganate, potassium nitrate and bentonite, wherein the waste zinc oxide desulfurizer is a zinc oxide desulfurizer subjected to desulfurization reaction, and the mercaptan removing catalyst is prepared by the following steps: respectively grinding 80kg of waste zinc oxide desulfurizer, 1.14kg of zinc nitrate, 5.71kg of potassium permanganate, 1.14kg of potassium nitrate and 12kg of bentonite until the particle size and the mesh number are more than 200 meshes, uniformly mixing, extrudingDrying the formed strips at 110 ℃ for 3h, and roasting the strips at 550 ℃ for 3h to obtain the mercaptan-removing catalyst; the sulfur content in the carbon dioxide gas was 0.1ppm by volume.
Example 4
The embodiment comprises the following steps:
step one, introducing carbon dioxide gas with the volume content of methyl mercaptan of 1000ppm into a gas distribution system and uniformly mixing the carbon dioxide gas with air to obtain mixed gas; the molar ratio of oxygen to methyl mercaptan in the mixed gas is 1.5: 1;
step two, introducing the mixed gas obtained in the step one into a reaction system, and performing a mercaptan removal reaction in the presence of a mercaptan removal catalyst to obtain carbon dioxide gas; the pressure of the mercaptan removal reaction is 3.0MPa, the temperature is 300 ℃, and the space velocity of the mixed gas is 1500h-1(ii) a The mercaptan removing catalyst is prepared from a waste zinc oxide desulfurizer, basic zinc carbonate, potassium permanganate, potassium hydroxide and activated clay, wherein the waste zinc oxide desulfurizer is a zinc oxide desulfurizer subjected to desulfurization reaction, and the mercaptan removing catalyst is prepared by the following steps: respectively grinding 70kg of waste zinc oxide desulfurizer, 3.38kg of basic zinc carbonate, 20.25kg of potassium permanganate, 3.38kg of potassium hydroxide and 3kg of activated clay until the particle size and the mesh number are more than 200 meshes, uniformly mixing, extruding and forming, drying at 110 ℃ for 5h, and roasting at 500 ℃ for 4h to obtain a mercaptan removal catalyst; the sulfur content in the carbon dioxide gas was 0.1ppm by volume.
Example 5
The embodiment comprises the following steps:
step one, introducing carbon dioxide gas with the volume content of methyl mercaptan of 2000ppm into a gas distribution system and uniformly mixing the carbon dioxide gas with air to obtain mixed gas; the molar ratio of oxygen to methyl mercaptan in the mixed gas is 2.5: 1;
step two, introducing the mixed gas obtained in the step one into a reaction system, and performing a mercaptan removal reaction in the presence of a mercaptan removal catalyst to obtain carbon dioxide gas; the pressure of the mercaptan removal reaction is 5.0MPa, the temperature is 350 ℃, and the space velocity of the mixed gas is 500h-1(ii) a The demethylationThe mercaptan catalyst is prepared from a waste zinc oxide desulfurizer, basic zinc carbonate, potassium permanganate, potassium hydroxide and aluminum oxide, wherein the waste zinc oxide desulfurizer is a zinc oxide desulfurizer subjected to desulfurization reaction, and the preparation process of the mercaptan removing catalyst is as follows: respectively grinding 70kg of waste zinc oxide desulfurizer, 3.38kg of basic zinc carbonate, 13.33kg of potassium permanganate, 3.38kg of potassium hydroxide and 10kg of aluminum oxide until the particle sizes and the meshes are more than 200 meshes, uniformly mixing, extruding and forming, drying at 100 ℃ for 4h, and roasting at 500 ℃ for 4h to obtain a mercaptan removal catalyst; the sulfur content in the carbon dioxide gas was 0.1ppm by volume.
Example 6
The embodiment comprises the following steps:
step one, introducing carbon dioxide gas with the volume content of methyl mercaptan of 1000ppm into a gas distribution system and uniformly mixing the carbon dioxide gas with air to obtain mixed gas; the molar ratio of oxygen to methyl mercaptan in the mixed gas is 1.5: 1;
step two, introducing the mixed gas obtained in the step one into a reaction system, and performing a mercaptan removal reaction in the presence of a mercaptan removal catalyst to obtain carbon dioxide gas; the pressure of the mercaptan removal reaction is 3.0MPa, the temperature is 300 ℃, and the space velocity of the mixed gas is 3000h-1(ii) a The mercaptan removing catalyst is prepared from a waste zinc oxide desulfurizer, basic zinc carbonate, potassium permanganate, potassium hydroxide and activated clay, wherein the waste zinc oxide desulfurizer is a zinc oxide desulfurizer subjected to desulfurization reaction, and the mercaptan removing catalyst is prepared by the following steps: respectively grinding 70kg of waste zinc oxide desulfurizer, 4kg of basic zinc carbonate, 12kg of potassium permanganate, 4kg of potassium hydroxide and 10kg of activated clay until the particle sizes and the meshes are more than 200 meshes, uniformly mixing, extruding and forming, drying at 120 ℃ for 4h, and roasting at 500 ℃ for 4h to obtain a mercaptan removal catalyst; the sulfur content in the carbon dioxide gas was 0.1ppm by volume.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention still belong to the protection scope of the technical solution of the invention.
Claims (5)
1. A process for removing methyl mercaptan from carbon dioxide gas is characterized by comprising the following steps:
step one, introducing carbon dioxide gas containing methyl mercaptan into a gas distribution system and uniformly mixing the carbon dioxide gas with air to obtain mixed gas; the molar ratio of oxygen to methyl mercaptan in the mixed gas is (0.6-2.5): 1;
step two, introducing the mixed gas obtained in the step one into a reaction system, and performing a mercaptan removal reaction in the presence of a mercaptan removal catalyst to obtain carbon dioxide gas; the pressure of the mercaptan removing reaction is 0.1MPa to 5.0MPa, the temperature is 150 ℃ to 350 ℃, and the space velocity of the mixed gas is 500h-1～3000h-1(ii) a The mercaptan removing catalyst is prepared from a waste zinc oxide desulfurizer, zinc salt, manganese salt, potassium salt and a binder, wherein the mass percent of the waste zinc oxide desulfurizer is 30-80%, the total mass percent of the zinc salt, the manganese salt and the potassium salt is 8-50%, the mass percent of the binder is 3-20%, and the waste zinc oxide desulfurizer is a zinc oxide desulfurizer after desulfurization reaction; the volume content of sulfur in the carbon dioxide gas is not more than 0.1 ppm;
the preparation process of the methyl mercaptan removal catalyst comprises the following steps: respectively grinding the waste zinc oxide desulfurizer, zinc salt, manganese salt, potassium salt and binder until the particle size and the mesh number are more than 200 meshes, uniformly mixing, extruding and forming, drying at 80-120 ℃ for 3-5 h, and roasting at 350-550 ℃ for 3-5 h to obtain the mercaptan-removing catalyst.
2. The process for removing methyl mercaptan from carbon dioxide gas as recited in claim 1, wherein the volume content of methyl mercaptan in carbon dioxide gas in the first step is 100ppm to 2000 ppm.
3. The process for removing methyl mercaptan from carbon dioxide gas according to claim 1, wherein the molar ratio of oxygen to methyl mercaptan in the mixed gas in the first step is (0.8-1.8): 1.
4. the process for removing methyl mercaptan from carbon dioxide gas as claimed in claim 1, wherein in step two, the zinc salt is zinc nitrate or basic zinc carbonate, the manganese salt is potassium permanganate or manganese nitrate, and the potassium salt is potassium nitrate.
5. The process of claim 1, wherein the binder in step two is activated clay, alumina, bentonite or attapulgite.
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