CN110201540A - The technique of methyl mercaptan in a kind of carbon dioxide removal gas - Google Patents
The technique of methyl mercaptan in a kind of carbon dioxide removal gas Download PDFInfo
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- CN110201540A CN110201540A CN201910627673.2A CN201910627673A CN110201540A CN 110201540 A CN110201540 A CN 110201540A CN 201910627673 A CN201910627673 A CN 201910627673A CN 110201540 A CN110201540 A CN 110201540A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
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- C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
- C10L3/10—Working-up natural gas or synthetic natural gas
- C10L3/101—Removal of contaminants
- C10L3/102—Removal of contaminants of acid contaminants
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention discloses a kind of techniques of methyl mercaptan in carbon dioxide removal gas, the technique includes: one, the carbon dioxide gas containing methyl mercaptan and air is mixed to obtain to mixed gas, and the molar ratio of oxygen and methyl mercaptan is (0.6~2.5) in mixed gas: 1；Two, the volume content that mixed gas is reacted to obtain under the effect of piptonychia mercaptan catalyst sulphur is no more than 0.1ppm carbon dioxide gas, which is prepared by useless Zinc oxide desulfurizer, zinc salt, manganese salt, sylvite and binder.The present invention mixes the carbon dioxide gas containing methyl mercaptan with air, it is reacted under the effect of piptonychia mercaptan catalyst, by the molar ratio for controlling methyl mercaptan and oxygen, make methyl mercaptan be converted into hydrogen sulfide to be absorbed by piptonychia mercaptan catalyst again, to realize the removing of methyl mercaptan in carbon dioxide gas, the generation for avoiding foreign gas substantially increases the removal effect of methyl mercaptan in carbon dioxide gas.
Description
Technical field
The invention belongs to gas phase technical field of desulfurization, and in particular to the work of methyl mercaptan in a kind of carbon dioxide removal gas
Skill.
Background technique
Natural gas will be used wider and wider as ideal clean domestic fuel.In recent years, China's natural gas is exploited
Amount rises year by year, develops large quantities of high yield gas fields in succession, but the CO in the natural gas produced2Content height differs,
In in III class natural gas carbon dioxide content mean value be 26%, carbon dioxide content is then higher in IV class natural gas, therefore, it is necessary to
Carbonization treatment is carried out to natural gas, carbon dioxide content, which is brought down below 3%, could be used as civil natural gas.However due to decarburization
Technique limits, and the carbon dioxide gas being enriched with after carbonization treatment often has accumulated a large amount of methyl mercaptans.Only it is stripped of these first sulphur
Alcohol, carbon dioxide can be only achieved environmental emission standard.
Currently, the research that methyl mercaptan removes in relevant carbon dioxide gas is seldom, only a small amount of related patents and text
The method for being all made of solvent absorption or wet oxidation process is offered, not only process flow is long, complicated for operation, and equipment investment is big, energy
Consumption is high, and waste water needs to handle again, generates secondary pollution.It is increasingly strict with carbon dioxide gas discharge standard, it is low
Methyl mercaptan in the carbon dioxide removal gas of cost not only can solve methyl mercaptan discharge bring environmental problem, can also be promoted
The economic benefit and social benefit of enterprise.
Fang Jianchao et al. (gas chemical industry, 2013 volume 38,9-12 pages) uses TS-1 molecular sieve and hydrogen peroxide solution
Carry out methyl mercaptan in carbon dioxide removal gas.This method needs to be added a large amount of hydrogen peroxide solution, and rear extended meeting generation largely contains
Sulphur waste water, and there is also abrasion and separation problems in hydrogen peroxide solution for molecular sieve.
Chinese patent CN203139886U discloses a kind of device of chlorine dioxide removal methyl mercaptan foul gas, the device
It is reacted in foul smell reactor using chlorine dioxide and methyl mercaptan foul gas, then is absorbed through alkali adsorption tower and tail gas absorber,
To achieve the purpose that deodorization.This method can generate a large amount of Alkali absorption waste liquid, and chlorine dioxide is also with intense stimulus
The high poisonous gas of property stink.
Summary of the invention
Technical problem to be solved by the present invention lies in view of the above shortcomings of the prior art, provide a kind of removing dioxy
The technique for changing methyl mercaptan in carbon gas.The technique mixes the carbon dioxide gas containing methyl mercaptan with air, urges in piptonychia mercaptan
It is reacted under agent effect, by controlling the molar ratio of methyl mercaptan and oxygen, methyl mercaptan is made to be converted into hydrogen sulfide again by piptonychia
Mercaptan catalyst absorbs, to realize the removing of methyl mercaptan in carbon dioxide gas, avoids the generation of foreign gas, mentions significantly
The removal effect of methyl mercaptan in high carbon dioxide gas.
In order to solve the above technical problems, the technical solution adopted by the present invention is that: first sulphur in a kind of carbon dioxide removal gas
The technique of alcohol, which is characterized in that the technique the following steps are included:
It mixes with air uniformly, is mixed Step 1: the carbon dioxide gas containing methyl mercaptan is passed through in air distribution system
Close gas；The molar ratio of oxygen and methyl mercaptan is (0.6~2.5) in the mixed gas: 1；
Step 2: mixed gas obtained in step 1 is passed through in reaction system, existing for piptonychia mercaptan catalyst
Under the conditions of carry out piptonychia thiol reaction, obtain carbon dioxide gas；The pressure of the piptonychia thiol reaction be 0.1MPa~
5.0MPa, temperature are 150 DEG C~350 DEG C, and the air speed of mixed gas is 500h-1~3000h-1；The piptonychia mercaptan catalyst by
Useless Zinc oxide desulfurizer, zinc salt, manganese salt, sylvite and binder are prepared, wherein the mass percent of useless Zinc oxide desulfurizer
It is 30%~80%, the gross mass percentage of zinc salt, manganese salt and sylvite is 8%~50%, and the mass percent of binder is 3%
~20%, the useless Zinc oxide desulfurizer is the Zinc oxide desulfurizer after desulphurization reaction；Sulphur in the carbon dioxide gas
Volume content be lower than 0.1ppm.
Technique of the invention is divided into two step of distribution and piptonychia thiol reaction, first by the carbon dioxide gas containing methyl mercaptan
It mixes with air uniformly, is reacted (1) under the conditions of then passing to reaction system existing for the piptonychia mercaptan catalyst, reacted
(1) reaction equation are as follows: 3O2(g)+2CH4S (g)=2H2S(g)+2CO2(g)+2H2O (g), i.e. methyl mercaptan in carbon dioxide gas
Catalysis occurs under the effect of piptonychia mercaptan catalyst with the oxygen in air to react, is converted into hydrogen sulfide, hydrogen sulfide is again by piptonychia
Mercaptan catalyst absorbing and removing, to realize the removing of methyl mercaptan in carbon dioxide gas.
Piptonychia mercaptan catalyst of the invention is prepared by useless Zinc oxide desulfurizer, and the Zinc oxide desulfurizer that gives up is industrial gas
Body field of purification Zinc oxide desulfurizer removes the product in gas after hydrogen sulfide impurities, according to professional standard HG/T 2508-2012
Zinc oxide desulfurizer, the main component of Zinc oxide desulfurizer are the zinc oxide of 95% or more mass content, and desulfurization principle is oxidation
Zinc is reacted with hydrogen sulfide generates zinc sulphide.Therefore, the main component of useless Zinc oxide desulfurizer is zinc sulphide, piptonychia mercaptan catalyst
Main active component be still zinc sulphide, zinc sulphide catalysis methyl mercaptan is reacted with oxygen, and methyl mercaptan is converted to hydrogen sulfide.Together
When, piptonychia mercaptan catalyst of the invention is also containing zinc salt, manganese salt, the co-catalysis component that sylvite is raw material preparation, the co-catalysis
Component can not only cooperate with zinc sulphide to carry out catalytic action, and can react with hydrogen sulfide to by hydrogen sulfide from gas
Middle removing.
The present invention passes through oxygen and first in carbon dioxide gas of the control containing methyl mercaptan and the mixed gas of air formation
The molar ratio of mercaptan promotes methyl mercaptan to carry out being catalyzed to react with oxygen being converted into hydrogen sulfide.When oxygen in mixed gas and first sulphur
When the molar ratio of alcohol is more than 3:1, oxygen and methyl mercaptan react (2) under the action of piptonychia mercaptan catalyst, reaction (2)
Reaction equation are as follows: 3O2(g)+CH4S (g)=SO2(g)+CO2(g)+2H2O (g), i.e. methyl mercaptan are converted into SO2Gas continues to stay in two
In carbon oxide gas, it can not remove；When the molar ratio of oxygen in mixed gas and methyl mercaptan is lower than 0.5:1, oxygen and first sulphur
Complicated reaction (3) occurs under the action of piptonychia mercaptan catalyst for alcohol, ultimately generates a large amount of CS2And a small amount of first sulphur
The mixed gas of ether and dimethyl disulfide, i.e. methyl mercaptan are converted into CS2Gas continues to stay in carbon dioxide gas, nothing
Method removing.Therefore, comprehensively consider, it is (0.6~2.5) that the present invention, which controls the molar ratio of oxygen and methyl mercaptan in mixed gas: 1,
Ensure that under the action of piptonychia mercaptan catalyst, only react (1) between methyl mercaptan and oxygen, avoid reaction (2) and
The generation for reacting (3), so that methyl mercaptan be made to be converted into hydrogen sulfide, then by piptonychia mercaptan catalyst absorbing and removing, avoids SO2Gas
Body and CS2The generation of the foreign gases such as gas substantially increases the removal effect of methyl mercaptan in carbon dioxide gas.
The technique of methyl mercaptan in a kind of above-mentioned carbon dioxide removal gas, which is characterized in that dioxy described in step 1
The volume content for changing methyl mercaptan in carbon gas is 100ppm~2000ppm.In actual industrial production, natural gas is through decarbonization process
Afterwards, the methyl mercaptan volume content in the carbon dioxide gas obtained is usually 100ppm~2000ppm, therefore technique of the invention
It is especially suitable for the piptonychia mercaptan of carbon dioxide in Gas Industry, has a wide range of application, practical value is high.
The technique of methyl mercaptan in a kind of above-mentioned carbon dioxide removal gas, which is characterized in that mixed described in step 1
The molar ratio of oxygen and methyl mercaptan is (0.8~1.8) in gas: 1.Oxygen and methyl mercaptan are in this range in control mixed gas
It is interior, it further ensures catalysis reaction and is gone on smoothly towards the direction of reaction (1), avoid reacting (2) and react (3), subtract
The generation for having lacked other impurities gas is conducive to the deep removal to the methyl mercaptan in carbon dioxide gas.
The technique of methyl mercaptan in a kind of above-mentioned carbon dioxide removal gas, which is characterized in that zinc salt described in step 2
For zinc nitrate or basic zinc carbonate, manganese salt is potassium permanganate or manganese nitrate, and sylvite is potassium hydroxide or potassium nitrate.Piptonychia of the present invention
Mercaptan catalyst to prepare raw material sources extensive, be easy to get, be conducive to the preparation of piptonychia mercaptan catalyst.
The technique of methyl mercaptan in a kind of above-mentioned carbon dioxide removal gas, which is characterized in that bonded described in step 2
Agent is atlapulgite, aluminum oxide, bentonite or attapulgite.Above-mentioned binder is the most common bonding of catalyst industry
Agent is obtained and is easy, and low in cost and performance is stablized, and is conducive to the preparation of piptonychia mercaptan catalyst.
The technique of methyl mercaptan in a kind of above-mentioned carbon dioxide removal gas, which is characterized in that piptonychia described in step 2
The preparation process of mercaptan catalyst are as follows: useless Zinc oxide desulfurizer, zinc salt, manganese salt, sylvite and binder are ground to partial size respectively
Mesh number is 200 mesh or more and mixes, in 80 DEG C~120 DEG C dry 3h~5h after extruded moulding, then at 350 DEG C~550 DEG C
3h~5h is roasted, piptonychia mercaptan catalyst is obtained.The present invention grinds useless Zinc oxide desulfurizer, zinc salt, manganese salt, sylvite and binder
Extruded moulding after mill obtains piptonychia mercaptan catalyst through roasting after drying, the main component zinc sulphide tool for the Zinc oxide desulfurizer that gives up
There is good high temperature resistance, the preparation process including roasting does not have an impact it, ensure that piptonychia mercaptan catalyst
Activity；Meanwhile zinc salt be fired after the zinc oxide that is formed be a kind of desulfurization component of good performance, can be with the conversion of methyl mercaptan
The reaction of product hydrogen sulfide generates zinc sulphide, so that the various manganese systems objects that manganese salt is formed after being fired can have by hydrogen sulfide stripping
It imitates and promotes methyl mercaptan decomposition generation hydrogen sulfide, can also be reacted with hydrogen sulfide and generate manganese sulfide thus by hydrogen sulfide stripping, potassium
Potassium hydroxide in salt all has good tempreture organic sulphur hydrolysis ability by the potassium oxide itself that potassium nitrate roasts, while
It can be reacted with hydrogen sulfide thus by hydrogen sulfide stripping.In addition, zinc salt, manganese salt, sylvite are decomposed in roasting process, thus
Duct is formed, improves the quantity in duct in piptonychia mercaptan catalyst, and then improve the specific surface area and porosity of catalyst,
And then improve the activity of piptonychia mercaptan catalyst.
In addition, Zinc oxide desulfurizer generally uses activated zinc oxide to prepare, the outstanding feature of activated zinc oxide is its knot
Structure particle be nanoscale, have both the double grading of nano material and conventional oxidation zinc, compared with conventional oxidation zinc product, have than
The feature that surface area is big, chemical activity is high.Zinc sulphide in useless Zinc oxide desulfurizer is slowly anti-with hydrogen sulfide by activated zinc oxide
It should generate, thus be likewise supplied with relevant property.Useless Zinc oxide desulfurizer is crushed again and correlation is added and helped by the present invention
Catalyst component, molding uses again, can not only give full play to the catalytic performance of zinc sulphide, and can by inside desulfurizing agent not
The zinc oxide used is exposed again and is made full use of, the converted product hydrogen sulfide of cooperation-removal methyl mercaptan, improves resource utilization,
By reluctant reclamation of solid wastes and minimizing.
Compared with the prior art, the present invention has the following advantages:
1, the present invention mixes the carbon dioxide gas containing methyl mercaptan and air, the item existing for piptonychia mercaptan catalyst
It is reacted under part, by controlling the molar ratio of methyl mercaptan and oxygen, so that methyl mercaptan is converted into hydrogen sulfide, hydrogen sulfide is again by piptonychia
Mercaptan catalyst absorbing and removing avoids SO to realize the removing of methyl mercaptan in carbon dioxide gas2Gas and CS2Gas
It generates, substantially increases the removal effect of methyl mercaptan in carbon dioxide gas.
2, the present invention prepares piptonychia mercaptan catalyst using useless Zinc oxide desulfurizer, utilizes the main of useless Zinc oxide desulfurizer
Vulcanizing zinc catalysis methyl mercaptan is reacted with oxygen, methyl mercaptan is converted to hydrogen sulfide, while being aided with zinc salt, manganese salt, sylvite and being
The co-catalysis component of raw material preparation, react to cooperate with hydrogen sulfide removes hydrogen sulfide from gas, realizes useless zinc oxide
The recycling of desulfurizing agent has saved catalyst cost of material.
3, catalytic reaction process of the invention is gas-solid phase reaction, and stabilization easy to operate, process flow is short, is only needed in proportion
It is incorporated air, without introducing any solvent, does not also generate any waste liquid, it is low for equipment requirements, energy consumption is small, it is at low cost, it is right
It is environmental-friendly.
4, technique of the invention can contain volume content containing methyl mercaptan for the sulphur in the carbon dioxide of 100ppm~2000ppm
Amount decreases below 0.1ppm, and therefore, the carbon dioxide obtained through the technique reaches environmental emission standard, both can be used as chemical industry
Product is further used or is sold, and can also be discharged directly into atmosphere, further reduced the carbon dioxide containing methyl mercaptan
Processing cost, suitable for the improvement for the carbon dioxide gas being enriched with after decarburization natural gas.
5, piptonychia mercaptan catalyst preparation method of the invention is simple, and raw material sources are extensive, are conducive to the work of the catalyst
Industry metaplasia produces, while realizing and making full use of to useless Zinc oxide desulfurizer, improves resource utilization, and it is useless to realize difficult solid
The recycling and minimizing of object.
Technical solution of the present invention is described in further detail below by drawings and examples.
Detailed description of the invention
Fig. 1 is the process flow chart of methyl mercaptan in carbon dioxide removal gas of the present invention.
Specific embodiment
As shown in Figure 1, in carbon dioxide removal gas of the present invention methyl mercaptan process flow are as follows: by the dioxy containing methyl mercaptan
Change after carbon gas is passed through in air distribution system with air and be uniformly mixed, obtains mixed gas, mixed gas is then passed through reaction
It in system, is reacted under the conditions of existing for the piptonychia mercaptan catalyst, removes methyl mercaptan, obtain carbon dioxide gas.
Embodiment 1
The present embodiment the following steps are included:
It is mixed Step 1: the carbon dioxide gas that the volume content of methyl mercaptan is 500ppm is passed through in air distribution system with air
It closes uniformly, obtains mixed gas；The molar ratio of oxygen and methyl mercaptan is 1.8:1 in the mixed gas；
Step 2: mixed gas obtained in step 1 is passed through in reaction system, existing for piptonychia mercaptan catalyst
Under the conditions of carry out piptonychia thiol reaction, obtain carbon dioxide gas；The pressure of the piptonychia thiol reaction is 4.0MPa, and temperature is
300 DEG C, the air speed of mixed gas is 1000h-1；The piptonychia mercaptan catalyst is by the Zinc oxide desulfurizer, zinc nitrate, permanganic acid of giving up
Potassium, potassium hydroxide and atlapulgite are prepared, and the useless Zinc oxide desulfurizer is the Zinc oxide desulfurizer after desulphurization reaction,
The preparation process of the piptonychia mercaptan catalyst are as follows: 30kg gives up Zinc oxide desulfurizer, 12.5kg zinc nitrate, 25kg permanganic acid
Potassium, 12.5kg potassium hydroxide and 20kg atlapulgite are ground to partial size mesh number respectively and are 200 mesh or more and mix, through extrusion at
In 110 DEG C of dry 4h after type, then in 500 DEG C of roasting 4h, obtain piptonychia mercaptan catalyst；Sulphur in the carbon dioxide gas
Volume content is 0.1ppm.
Embodiment 2
The present embodiment the following steps are included:
Step 1: the carbon dioxide gas that the volume content of methyl mercaptan is 1000ppm is passed through in air distribution system and air
It is uniformly mixed, obtains mixed gas；The molar ratio of oxygen and methyl mercaptan is 0.8:1 in the mixed gas；
Step 2: mixed gas obtained in step 1 is passed through in reaction system, existing for piptonychia mercaptan catalyst
Under the conditions of carry out piptonychia thiol reaction, obtain carbon dioxide gas；The pressure of the piptonychia thiol reaction is 3.0MPa, and temperature is
300 DEG C, the air speed of mixed gas is 800h-1；The piptonychia mercaptan catalyst is by the Zinc oxide desulfurizer, basic zinc carbonate, nitre of giving up
Sour manganese, potassium hydroxide and attapulgite are prepared, and the useless Zinc oxide desulfurizer is the zinc oxide desulfurization after desulphurization reaction
Agent, the preparation process of the piptonychia mercaptan catalyst are as follows: 50kg gives up Zinc oxide desulfurizer, 5kg basic zinc carbonate, 20kg nitric acid
Manganese, 5kg potassium hydroxide and 20kg attapulgite are ground to partial size mesh number respectively and are 200 mesh or more and mix, through extruded moulding
Afterwards in 80 DEG C of dry 4h, then in 350 DEG C of roasting 5h, obtain piptonychia mercaptan catalyst；The body of sulphur in the carbon dioxide gas
Product content is 0.08ppm.
Embodiment 3
The present embodiment the following steps are included:
It is mixed Step 1: the carbon dioxide gas that the volume content of methyl mercaptan is 100ppm is passed through in air distribution system with air
It closes uniformly, obtains mixed gas；The molar ratio of oxygen and methyl mercaptan is 0.6:1 in the mixed gas；
Step 2: mixed gas obtained in step 1 is passed through in reaction system, existing for piptonychia mercaptan catalyst
Under the conditions of carry out piptonychia thiol reaction, obtain carbon dioxide gas；The pressure of the piptonychia thiol reaction is 0.1MPa, and temperature is
150 DEG C, the air speed of mixed gas is 500h-1；The piptonychia mercaptan catalyst is by the Zinc oxide desulfurizer, zinc nitrate, permanganic acid of giving up
Potassium, potassium nitrate and bentonite are prepared, and the useless Zinc oxide desulfurizer is the Zinc oxide desulfurizer after desulphurization reaction, described
The preparation process of piptonychia mercaptan catalyst are as follows: by 80kg give up Zinc oxide desulfurizer, 1.14kg zinc nitrate, 5.71kg potassium permanganate,
1.14kg potassium nitrate and 12kg bentonite are ground to partial size mesh number respectively and are 200 mesh or more and mix, after extruded moulding
110 DEG C of dry 3h, then in 550 DEG C of roasting 3h, obtain piptonychia mercaptan catalyst；The volume of sulphur in the carbon dioxide gas contains
Amount is 0.1ppm.
Embodiment 4
The present embodiment the following steps are included:
Step 1: the carbon dioxide gas that the volume content of methyl mercaptan is 1000ppm is passed through in air distribution system and air
It is uniformly mixed, obtains mixed gas；The molar ratio of oxygen and methyl mercaptan is 1.5:1 in the mixed gas；
Step 2: mixed gas obtained in step 1 is passed through in reaction system, existing for piptonychia mercaptan catalyst
Under the conditions of carry out piptonychia thiol reaction, obtain carbon dioxide gas；The pressure of the piptonychia thiol reaction is 3.0MPa, and temperature is
300 DEG C, the air speed of mixed gas is 1500h-1；The piptonychia mercaptan catalyst is by the Zinc oxide desulfurizer, basic zinc carbonate, height of giving up
Potassium manganate, potassium hydroxide and atlapulgite are prepared, and the useless Zinc oxide desulfurizer is that the zinc oxide after desulphurization reaction is de-
Sulphur agent, the preparation process of the piptonychia mercaptan catalyst are as follows: by 70kg give up Zinc oxide desulfurizer, 3.38kg basic zinc carbonate,
20.25kg potassium permanganate, 3.38kg potassium hydroxide and 3kg atlapulgite be ground to respectively partial size mesh number be 200 mesh or more simultaneously
It mixes, in 110 DEG C of dry 5h after extruded moulding, then in 500 DEG C of roasting 4h, obtains piptonychia mercaptan catalyst；The titanium dioxide
The volume content of sulphur in carbon gas is 0.1ppm.
Embodiment 5
The present embodiment the following steps are included:
Step 1: the carbon dioxide gas that the volume content of methyl mercaptan is 2000ppm is passed through in air distribution system and air
It is uniformly mixed, obtains mixed gas；The molar ratio of oxygen and methyl mercaptan is 2.5:1 in the mixed gas；
Step 2: mixed gas obtained in step 1 is passed through in reaction system, existing for piptonychia mercaptan catalyst
Under the conditions of carry out piptonychia thiol reaction, obtain carbon dioxide gas；The pressure of the piptonychia thiol reaction is 5.0MPa, and temperature is
350 DEG C, the air speed of mixed gas is 500h-1；The piptonychia mercaptan catalyst is by the Zinc oxide desulfurizer, basic zinc carbonate, height of giving up
Potassium manganate, potassium hydroxide and aluminum oxide are prepared, and the useless Zinc oxide desulfurizer is the zinc oxide after desulphurization reaction
Desulfurizing agent, the preparation process of the piptonychia mercaptan catalyst are as follows: by 70kg give up Zinc oxide desulfurizer, 3.38kg basic zinc carbonate,
It is 200 mesh or more that 13.33kg potassium permanganate, 3.38kg potassium hydroxide and 10kg aluminum oxide are ground to partial size mesh number respectively
And mix, in 100 DEG C of dry 4h after extruded moulding, then in 500 DEG C of roasting 4h, obtain piptonychia mercaptan catalyst；The dioxy
The volume content for changing the sulphur in carbon gas is 0.1ppm.
Embodiment 6
The present embodiment the following steps are included:
Step 1: the carbon dioxide gas that the volume content of methyl mercaptan is 1000ppm is passed through in air distribution system and air
It is uniformly mixed, obtains mixed gas；The molar ratio of oxygen and methyl mercaptan is 1.5:1 in the mixed gas；
Step 2: mixed gas obtained in step 1 is passed through in reaction system, existing for piptonychia mercaptan catalyst
Under the conditions of carry out piptonychia thiol reaction, obtain carbon dioxide gas；The pressure of the piptonychia thiol reaction is 3.0MPa, and temperature is
300 DEG C, the air speed of mixed gas is 3000h-1；The piptonychia mercaptan catalyst is by the Zinc oxide desulfurizer, basic zinc carbonate, height of giving up
Potassium manganate, potassium hydroxide and atlapulgite are prepared, and the useless Zinc oxide desulfurizer is that the zinc oxide after desulphurization reaction is de-
Sulphur agent, the preparation process of the piptonychia mercaptan catalyst are as follows: 70kg gives up Zinc oxide desulfurizer, 4kg basic zinc carbonate, 12kg high
Potassium manganate, 4kg potassium hydroxide and 10kg atlapulgite are ground to partial size mesh number respectively and are 200 mesh or more and mix, through extrusion
In 120 DEG C of dry 4h after molding, then in 500 DEG C of roasting 4h, obtain piptonychia mercaptan catalyst；Sulphur in the carbon dioxide gas
Volume content be 0.1ppm.
The above is only presently preferred embodiments of the present invention, is not intended to limit the invention in any way.It is all according to invention skill
Art any simple modification, change and equivalence change substantially to the above embodiments, still fall within technical solution of the present invention
Protection scope.
Claims (6)
1. the technique of methyl mercaptan in a kind of carbon dioxide removal gas, which is characterized in that the technique the following steps are included:
It is mixed with air uniformly Step 1: the carbon dioxide gas containing methyl mercaptan is passed through in air distribution system, obtains gaseous mixture
Body；The molar ratio of oxygen and methyl mercaptan is (0.6~2.5) in the mixed gas: 1；
Step 2: mixed gas obtained in step 1 is passed through in reaction system, the condition existing for piptonychia mercaptan catalyst
Lower progress piptonychia thiol reaction, obtains carbon dioxide gas；The pressure of the piptonychia thiol reaction is 0.1MPa~5.0MPa, temperature
Degree is 150 DEG C~350 DEG C, and the air speed of mixed gas is 500h-1~3000h-1；The piptonychia mercaptan catalyst is by the zinc oxide that gives up
Desulfurizing agent, zinc salt, manganese salt, sylvite and binder are prepared, wherein and the mass percent of useless Zinc oxide desulfurizer is 30%~
80%, the gross mass percentage of zinc salt, manganese salt and sylvite is 8%~50%, and the mass percent of binder is 3%~20%,
The useless Zinc oxide desulfurizer is the Zinc oxide desulfurizer after desulphurization reaction；The volume of sulphur in the carbon dioxide gas contains
Amount is no more than 0.1ppm.
2. the technique of methyl mercaptan in a kind of carbon dioxide removal gas according to claim 1, which is characterized in that step 1
Described in carbon dioxide gas the volume content of methyl mercaptan be 100ppm~2000ppm.
3. the technique of methyl mercaptan in a kind of carbon dioxide removal gas according to claim 1, which is characterized in that step 1
Described in mixed gas the molar ratio of oxygen and methyl mercaptan be (0.8~1.8): 1.
4. the technique of methyl mercaptan in a kind of carbon dioxide removal gas according to claim 1, which is characterized in that step 2
Described in zinc salt be zinc nitrate or basic zinc carbonate, manganese salt be potassium permanganate or manganese nitrate, sylvite be potassium hydroxide or potassium nitrate.
5. the technique of methyl mercaptan in a kind of carbon dioxide removal gas according to claim 1, which is characterized in that step 2
Described in binder be atlapulgite, aluminum oxide, bentonite or attapulgite.
6. the technique of methyl mercaptan in a kind of carbon dioxide removal gas according to claim 1, which is characterized in that step 2
Described in piptonychia mercaptan catalyst preparation process are as follows: by useless Zinc oxide desulfurizer, zinc salt, manganese salt, sylvite and binder distinguish
It is ground to partial size mesh number to be 200 mesh or more and mix, in 80 DEG C~120 DEG C dry 3h~5h after extruded moulding, then 350
DEG C~550 DEG C of roasting 3h~5h, obtain piptonychia mercaptan catalyst.
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