CN103691399A - Preparation method of high-performance carbon molecular sieve for separating carbon dioxide/methane - Google Patents
Preparation method of high-performance carbon molecular sieve for separating carbon dioxide/methane Download PDFInfo
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- CN103691399A CN103691399A CN201310697479.4A CN201310697479A CN103691399A CN 103691399 A CN103691399 A CN 103691399A CN 201310697479 A CN201310697479 A CN 201310697479A CN 103691399 A CN103691399 A CN 103691399A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/20—Capture or disposal of greenhouse gases of methane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
Abstract
The invention provides a preparation method of a carbon molecular sieve has high adsorptive selectivity and high adsorption capacity for CO2/CH4 by using agricultural wastes as a raw material. The preparation method specifically comprises the steps of forming, carbonizing, activating and modifying. Main pore diameters of the obtained carbon molecular sieve are distributed between 0.3nm and 0.4nm, the specific surface area of the obtained carbon molecular sieve reaches 2400-2800m<2>.g<-1>, the carbon molecular sieve is high in CO2 adsorption capacity of 75-85mL.g<-1> at a normal temperature and normal pressure, and the equilibrium adsorption selectivity coefficient alpha (CO2/CH4) of carbon dioxide and methane reaches a range of 65-73. According to the preparation method, the adsorption capacity of the carbon molecular sieve is increased, and the gas separation coefficient of the carbon molecular sieve and the CO2/CH4 is increased by using a modifying method; the preparation method has wide application prospect in a gas separation technology.
Description
Technical field
The invention belongs to comprehensive utilization of energy field, relate to a kind of preparation method of the high-performance carbon molecular sieve for separating of carbon dioxide/methane, the particularly high value utilization of agricultural wastes, and the preparation method of high-performance carbon molecular sieve.
Background technology
Along with the scarcity of fossil energy and increasingly sharpening of environmental pollution pressure, how to utilize clean energy resource to replace the fuel such as gasoline, coal to become one and be badly in need of the problem solving.Methane/carbon dioxide mixture is extensively present in the resources such as coal bed gas, casing-head gas, garbage loading embeading vapour and biogas.As a kind of efficient, clear energy sources, if methane therefrom can be separated and concentrated utilization, can not only produce huge economic benefit, and protection of the environment is had to significant contribution.In addition CO,
2as " potential carbon resource ", the research that many countries are also correlated with always and fully utilize.Pressure swing adsorption (PSA) is in recent years at the gas separation of industrial new emergence, and the performance of adsorbent is the key that determines its separating effect, has also directly determined the economy of gas separation.Because carbon molecular sieve has a large amount of microcellular structures and the good feature of chemical stability, be commonly used for adsorbent adsorbing separation mist, if carbon molecular sieve is by a large number for nitrogen production by air separation technology.
The preparation of carbon molecular sieve mainly contains two kinds at present, and a kind of is that fabric or the macromolecule with a fixed structure makes by corresponding activating process, and a kind of is first to prepare active carbon, and then uses different hole-blocking agents to carry out gas phase or liquid phase carbon deposition tune hole.As Chinese patent " CN1303735A ", a kind of molecular sieve carbon fabric for methane and carbon dioxide separation and preparation method thereof is disclosed.It is raw material that the method be take organic fiber or fabric, through charing and steam activation, obtain product, but the surface area that compares is lower, and Selective Separation coefficient is little; Chinese patent " CN103086354A " discloses the concentrated purification CH of a kind of coal bed gas
4with carbon molecular sieve and preparation method thereof, take phenolic resin waste as raw material, through tune holes such as overmolding, charing and benzene, toluene, make carbon molecular sieve, for separating of methane and nitrogen.When benzene, toluene etc. are used as the agent of tune hole, often can be to CH
4/ N
2or CH
4/ CO
2obtain selective carbon molecular sieve preferably, but can cause adsorption capacity reduce and can cause certain harm to environment simultaneously.
In recent years, along with industrial expansion, the raw materials such as coal, timber and organic polymer of preparing molecular sieve through being commonly used for are consumed excessively, cause cost further to improve, and agricultural wastes are often burned as a kind of reproducible carbon source or low value is utilized, cause the waste of resource, therefore with agricultural wastes, as the raw material of preparing carbon molecular sieve, will there is very large competitive advantage.，
Summary of the invention
The present invention is directed at present for CO
2/ CH
4the separated problem existing with carbon molecular sieve, provides a kind of agricultural wastes that can make to obtain the preparation method that high value is utilized, and obtains carbon dioxide/methane to have the carbon molecular sieve of high-adsorption-capacity and high adsorptive selectivity.
For separating of a preparation method for the high-performance carbon molecular sieve of carbon dioxide/methane, its concrete preparation process is as follows:
(1) moulding: raw fibre is crushed to 1-2mm length, mixes and kneading with mass ratio 1-2:1 with binding agent, be then squeezed into column type;
(2) charing: by raw material 300 ℃ of-500 ℃ of charing 30min-1h in inert atmosphere pipe type stove, temperature programming speed is 5-10 ℃/min, naturally cools to room temperature;
(3) activation: product after above-mentioned charing is being contained to K
+alkaline solution in soak 2-4h, then open ports is placed in vacuum drying chamber 100-120 ℃ oven dry; Sample being inserted to sealing again but staying foraminate system is in semiclosed system, under still air atmosphere, Muffle furnace or tube furnace Program are warming up to 400-500 ℃ of constant temperature 0.5-1h, continue to be afterwards warming up to 700-800 ℃ of constant temperature 0.5-1h, heating rate is 5-10 ℃/min, after naturally cooling to room temperature, take out, and be washed with water to neutrality;
(4) modification: will soak 2-4h under the said goods room temperature in containing the solution of organic amine, then 80-100 ℃ of oven dry in vacuum drying chamber; Sample after drying is placed in to micro-wave oven, and under nitrogen atmosphere, temperature programming is to 400-500 ℃ of constant temperature microwave treatment 0.5-1h, and heating rate is 5-10 ℃/min; Then continue temperature programming to 800-1000 ℃ of constant temperature microwave treatment 0.5-1h, heating rate is 5-10 ℃/min, naturally cools to afterwards room temperature, obtains final carbon molecular sieve product.
Wherein, raw material described in step (1) be carbon content at more than 80% agricultural wastes, described carbon content is corncob, tobacco rod, coconut husk or walnut shell at more than 80% agricultural wastes; Binding agent used is one or both mixing in liquid phenolic resin, coal tar, pitch, molasses, humic acid; In step (3), contain K
+alkaline solution be K
2cO
3or KOH solution, concentration is 20%-30%,, containing K
+alkaline solution in also contain ethanol or the vinyl alcohol of 0.5-1%; Activation is to carry out in still air atmosphere, semiclosed system; In step (4), By Amine Solutions used is diethanol amine or acrylamide or the mixture of the two; Modification in step (4) all divides two temperature sections to carry out in micro-wave oven.
With the product that this technique obtains, have the advantages that pore-size distribution is narrow, specific area is high, specific area reaches 2400-2800m
2g
-1, the pore volume between 0.3-0.4nm accounts for the 55%-65% of total pore volume, has at normal temperatures and pressures very high CO
2adsorption capacity, reaches 75-85mLg
-1, the equilibrium adsorption selectivity factor α (CO to carbon dioxide and methane
2/ CH
4) reach between 65-73, can be used for pressure swing adsorption/separation of methane and carbon dioxide.
The present invention be take agricultural wastes as raw material, provides a kind of to CO
2/ CH
4the preparation method with the carbon molecular sieve of high adsorptive selectivity and high-adsorption-capacity.The method has avoided gas phase or liquid deposition to adjust hole, has improved the adsorption capacity of carbon molecular sieve, has reduced environmental pollution, has improved carbon molecular sieve to CO by the method for modification simultaneously
2/ CH
4gas separation coefficient, in gas separation, will have broad application prospects.
Should compare with the preparation method of other report or conventional carbon molecular sieve for separating of preparation method of the carbon molecular sieve of carbon dioxide/methane, have following advantage:
(1) in the preparation method of the carbon molecular sieve of this separating carbon dioxide/methane by after the raw material molding bonded after agricultural wastes fragmentation, first charing is removed the non-carbon of major part by decomposition, in product, generate more rich initial hole simultaneously.Again by the aqueous slkali soaking containing potassium, make K afterwards
+deng as much as possible, diffuse into carbonization product inside, be beneficial to improve the efficiency of activation and generate uniform hole.
(2), in the preparation method of the carbon molecular sieve of this separating carbon dioxide/methane, activation is carried out in still air atmosphere, semiclosed system.With traditional activating and compare under inert atmosphere, this process does not need to pass into inert atmosphere, and preparation technology and device are simpler, and has reduced the cost that nitrogen in traditional handicraft is done atmosphere.In semiclosed system, carry out, be i.e. during sample activation, on container, add a cover, but blow-by.When priming reaction occurs, because constantly have gas to emit, make the air outside system can not enter system, thereby avoid oxidation; In high-temperature activation reaction, it is to form the key factor enrich micropore that K becomes that steam shuttles back and forth in carbon structure inside, semitight system makes temporarily in system to keep a higher K vapour pressure, make K gas in carbon structure to walk path elongated slack-off, thereby form abundanter hole.
(3) product after activation is processed after soaking in By Amine Solutions under inert atmosphere, high temperature again, because organic amine is the material with amido, after high-temperature process, can introduce aobvious alkaline amido on the surface of carbon molecular sieve, its absorption to aobvious acid carbon dioxide is had more selectively, thereby further improve the separation of carbon dioxide/methane.Further the high-temperature process in micro-wave oven, shrinks the hole that charcoal mesoporous is larger, utilizes the advantage of micro-wave oven homogeneous heating, makes more homogeneous of micropore hole.
Exactly because this preparation method is different from the preparation method of traditional carbon molecular sieve, with and these advantages of having make the carbon molecular sieve that the method is prepared there is high-adsorption-capacity and carbon dioxide/methane is had to high adsorptive selectivity separation.In addition, the agricultural wastes of take are prepared high-performance carbon molecular sieve as raw material, can be turned waste into wealth, and can reduce the cost of carbon molecular sieve.
The specific embodiment
Embodiment mono-
After corncob is dry, be crushed to about 1cm length, mix and kneading with mass ratio 1:1 with binding agent, be then squeezed into φ 0.5cm * 1mm column type.Be placed in the lower 500 ℃ of charing 1h of blanket of nitrogen, temperature programming speed is 5 ℃/min, naturally cooling after by above-mentioned carbonization product at 25%K
2cO
3and soak after 4h in the alkaline solution of a small amount of ethanol, open ports is 120 ℃ of oven dry in vacuum drying chamber, then inserting sealing but staying foraminate crucible is in semiclosed system, obstructed atmosphere is that under still air atmosphere, Muffle furnace or tube furnace Program are warming up to 600 ℃ of constant temperature 1h, continue to be afterwards warming up to 800 ℃ of constant temperature 45min, heating rate is 5 ℃/min, then naturally cools to room temperature, takes out and be washed with water to neutrality.Under product room temperature after activation, in the solution of diethanol amine, soak 4h, after drying in vacuum drying chamber, sample is placed in to micro-wave oven, temperature programming to 500 ℃ constant temperature microwave treatment 1h under blanket of nitrogen, heating rate is 5 ℃/min; Then continue temperature programming to 1000 ℃ constant temperature microwave treatment 1h, heating rate is 5 ℃/min, naturally cools to afterwards room temperature, obtains final carbon molecular sieve product.Resulting product specific area is 2580m
2g
1, the pore volume between 0.3-0.4nm accounts for 56.4%, under normal temperature and pressure to CO
2adsorption capacity be 80.1mLg
-1, the equilibrium adsorption selectivity factor α (CO to carbon dioxide/methane
2/ CH
4) be 70.8.
Embodiment bis-
After tobacco rod is dry, be crushed to about 1cm length, mix and kneading with mass ratio 1.5:1 with binding agent, be then squeezed into φ 0.5cm * 1mm column type.Be placed in the lower 400 ℃ of charing 1h of blanket of nitrogen, temperature programming speed is 5 ℃/min, naturally cooling after by above-mentioned carbonization product at 30%K
2cO
3and soak after 4h in the alkaline solution of a small amount of ethanol, open ports is 120 ℃ of oven dry in vacuum drying chamber, then the same inserting in semiclosed system, under still air atmosphere, Muffle furnace or tube furnace Program are warming up to 600 ℃ of constant temperature 1h, continue to be afterwards warming up to 800 ℃ of constant temperature 45min, heating rate is 5 ℃/min, then naturally cools to room temperature, takes out and be washed with water to neutrality.Under product room temperature after activation, in the solution of diethanol amine, soak 4h, after oven dry, sample is placed in to micro-wave oven, temperature programming to 500 ℃ constant temperature microwave treatment 1h under blanket of nitrogen, heating rate is 5 ℃/min; Then continue temperature programming to 1000 ℃ constant temperature microwave treatment 1h, heating rate is 5 ℃/min, naturally cools to afterwards room temperature, obtains final carbon molecular sieve product.Resulting product specific area is 2400m
2g
1, the pore volume between 0.3-0.4nm accounts for 61.1%, under normal temperature and pressure to CO
2adsorption capacity be 75.3mLg
-1, the equilibrium adsorption selectivity factor α (CO to carbon dioxide/methane
2/ CH
4) be 71.5.
Embodiment tri-
After coconut husk is dry, be crushed to about 1cm length, mix and kneading with mass ratio 1.5:1 with binding agent, be then squeezed into φ 0.5cm * 1mm column type.Be placed in the lower 500 ℃ of charing 1h of blanket of nitrogen, temperature programming speed is 5 ℃/min, naturally cooling after by above-mentioned carbonization product at 30%K
2cO
3and soak after 4h in the alkaline solution of a small amount of ethanol, open ports is 120 ℃ of oven dry in vacuum drying chamber, then the same inserting in semiclosed system, under still air atmosphere, Muffle furnace or tube furnace Program are warming up to 500 ℃ of constant temperature 1h, continue to be afterwards warming up to 750 ℃ of constant temperature 1h, heating rate is 5 ℃/min, then naturally cools to room temperature, takes out and be washed with water to neutrality.Under product room temperature after activation, in the solution of diethanol amine, soak 4h, after oven dry, sample is placed in to micro-wave oven, temperature programming to 400 ℃ constant temperature microwave treatment 1h under blanket of nitrogen, heating rate is 5 ℃/min; Then continue temperature programming to 1000 ℃ constant temperature microwave treatment 1h, heating rate is 5 ℃/min, naturally cools to afterwards room temperature, obtains final carbon molecular sieve product.Resulting product specific area is 2510m
2g
1, the pore volume between 0.3-0.4nm accounts for 62.5%, under normal temperature and pressure to CO
2adsorption capacity be 79.6mLg
-1, the equilibrium adsorption selectivity factor α (CO to carbon dioxide/methane
2/ CH
4) be 67.2.
Embodiment tetra-
After corncob is dry, be crushed to about 1cm length, mix and kneading with mass ratio 2:1 with binding agent, be then squeezed into φ 0.5cm * 1mm column type.Be placed in the lower 400 ℃ of charing 45min of blanket of nitrogen, temperature programming speed is 8 ℃/min, naturally after cooling, above-mentioned carbonization product is soaked after 4h in the alkaline solution of 25%KOH and a small amount of ethanol, open ports is 120 ℃ of oven dry in vacuum drying chamber, then the same inserting in semiclosed system, under still air atmosphere, Muffle furnace or tube furnace Program are warming up to 500 ℃ of constant temperature 1h, continue to be afterwards warming up to 750 ℃ of constant temperature 1h, heating rate is 8 ℃/min, then naturally cool to room temperature, take out and be washed with water to neutrality.Under product room temperature after activation, in the solution of acrylamide, soak 4h, after oven dry, sample is placed in to micro-wave oven, temperature programming to 500 ℃ constant temperature microwave treatment 1h under blanket of nitrogen, heating rate is 5 ℃/min; Then continue temperature programming to 900 ℃ constant temperature microwave treatment 45min, heating rate is 5 ℃/min, naturally cools to afterwards room temperature, obtains final carbon molecular sieve product.Resulting product specific area is 2650m
2g
1, the pore volume between 0.3-0.4nm accounts for 60.5%, under normal temperature and pressure to CO
2adsorption capacity be 81.5mLg
-1, the equilibrium adsorption selectivity factor α (CO to carbon dioxide/methane
2/ CH
4) be 66.3.
Embodiment five
After coconut husk is dry, be crushed to about 1cm length, mix and kneading with mass ratio 2:1 with binding agent, be then squeezed into φ 0.5cm * 1mm column type.Be placed in the lower 500 ℃ of charing 1h of blanket of nitrogen, temperature programming speed is 5 ℃/min, naturally after cooling, above-mentioned carbonization product is soaked after 4h in the alkaline solution of 30%KOH and a small amount of ethanol, open ports is 120 ℃ of oven dry in vacuum drying chamber, then the same inserting in semiclosed system, under still air atmosphere, Muffle furnace or tube furnace Program are warming up to 500 ℃ of constant temperature 1h, continue to be afterwards warming up to 800 ℃ of constant temperature 45min, heating rate is 5 ℃/min, then naturally cool to room temperature, take out and be washed with water to neutrality.Under product room temperature after activation, in the solution of acrylamide, soak 4h, after oven dry, sample is placed in to micro-wave oven, temperature programming to 400 ℃ constant temperature microwave treatment 1h under blanket of nitrogen, heating rate is 5 ℃/min; Then continue temperature programming to 1000 ℃ constant temperature microwave treatment 1h, heating rate is 5 ℃/min, naturally cools to afterwards room temperature, obtains final carbon molecular sieve product.Resulting product specific area is 2986m
2g
1, the pore volume between 0.3-0.4nm accounts for 64.5%, under normal temperature and pressure to CO
2adsorption capacity be 85.4mLg
-1, the equilibrium adsorption selectivity factor α (CO to carbon dioxide/methane
2/ CH
4) be 72.5.
Embodiment six
After walnut shell is dry, be crushed to about 1cm length, mix and kneading with mass ratio 2:1 with binding agent, be then squeezed into φ 0.5cm * 1mm column type.Be placed in the lower 400 ℃ of charing 1h of blanket of nitrogen, temperature programming speed is 10 ℃/min, naturally cooling after by above-mentioned carbonization product at 30%K
2cO
3and soak after 4h in the alkaline solution of a small amount of vinyl alcohol, open ports is 120 ℃ of oven dry in vacuum drying chamber, then the same inserting in semiclosed system, under still air atmosphere, Muffle furnace or tube furnace Program are warming up to 600 ℃ of constant temperature 1h, continue to be afterwards warming up to 700 ℃ of constant temperature 1h, heating rate is 10 ℃/min, then naturally cools to room temperature, takes out and be washed with water to neutrality.Under product room temperature after activation, in the solution of diethanol amine, soak 4h, after oven dry, sample is placed in to micro-wave oven, temperature programming to 500 ℃ constant temperature microwave treatment 1h under blanket of nitrogen, heating rate is 5 ℃/min; Then continue temperature programming to 900 ℃ constant temperature microwave treatment 1h, heating rate is 5 ℃/min, naturally cools to afterwards room temperature, obtains final carbon molecular sieve product.Resulting product specific area is 2700m
2g
1, the pore volume between 0.3-0.4nm accounts for 58.3%, under normal temperature and pressure to CO
2adsorption capacity be 83.6mLg
-1, to the equilibrium adsorption selectivity factor of carbon dioxide/methane, be 64.6.
Comparative example one
After corncob is dry, be crushed to about 1cm length, mix and kneading with mass ratio 1:1 with binding agent, be then squeezed into φ 0.5cm * 1mm column type.Be placed in horizontal pipe furnace, 500 ℃ of charing 1h under blanket of nitrogen, use steam activation 1h for 800 ℃, are washed with water to neutrality after naturally cooling again.Resulting product specific area is 895m
2g
1, the pore volume between 0.3-0.4nm accounts for 48%, under normal temperature and pressure to CO
2adsorption capacity be 38.1mLg
-1, the equilibrium adsorption selectivity factor α (CO to carbon dioxide/methane
2/ CH
4) be 5.8.
Comparative example two
After corncob is dry, be crushed to about 1cm length, mix and kneading with mass ratio 1:1 with binding agent, be then squeezed into φ 0.5cm * 1mm column type.Be placed in the lower 600 ℃ of charing 1h of blanket of nitrogen, in horizontal pipe furnace, use steam activation 1h for 800 ℃, be washed with water to again neutrality after naturally cooling.Under product room temperature after activation, in the solution of diethanol amine, soak 4h, after oven dry, with in embodiment like that in micro-wave oven under blanket of nitrogen 500 ℃ process 1h, then at 900 ℃ of microwave treatment 45min.Resulting product specific area is 810m
2g
1, the pore volume between 0.3-0.4nm accounts for 49%, under normal temperature and pressure to CO
2adsorption capacity be 35.1mLg
-1, the equilibrium adsorption selectivity factor α (CO to carbon dioxide/methane
2/ CH
4) be 32.1.
Comparative example three
After corncob is dry, be crushed to about 1cm length, mix and kneading with mass ratio 1:1 with binding agent, be then squeezed into φ 0.5cm * 1mm column type.Be placed in the lower 600 ℃ of charing 1h of blanket of nitrogen, gained carbonization product is soaked after 4h in the alkaline solution of 25%KOH, 120 ℃ of oven dry in vacuum drying chamber, then 800 ℃ of activation 1h under inert atmosphere in tube furnace, are washed with water to neutrality after naturally cooling.Resulting product specific area is 2014m
2g
1, the pore volume between 0.3-0.4nm accounts for 45%, under normal temperature and pressure to CO
2adsorption capacity be 55.1mLg
-1, the equilibrium adsorption selectivity factor α (CO to carbon dioxide/methane
2/ CH
4) be 13.5.
By the comparison to embodiment and comparative example product property parameter, can obviously find out that the carbon molecular sieve being prepared by technique of the present invention is not only to CO
2adsorption capacity very high, and to CO
2and CH
4there is very high equilibrium adsorption selectivity factor.With By Amine Solutions and in micro-wave oven modification obviously improved carbon molecular sieve to CO
2and CH
4equilibrium adsorption selectivity factor; In semiclosed system, compare with traditional activating process under inert atmosphere with activation in still air atmosphere, the former resulting product is to CO
2adsorption capacity obviously improve.
Claims (5)
1. for separating of the preparation method of the high-performance carbon molecular sieve of carbon dioxide/methane, its concrete preparation process is as follows:
(1) moulding: raw fibre is crushed to 1-2mm length, mixes and kneading with mass ratio 1-2:1 with binding agent, be then squeezed into column type; Raw material be carbon content at more than 80% agricultural wastes, binding agent is one or both mixing in liquid phenolic resin, coal tar, pitch, molasses, humic acid;
(2) charing: by raw material 300 ℃ of-500 ℃ of charing 30min-1h in inert atmosphere pipe type stove, temperature programming speed is 5-10 ℃/min, naturally cools to room temperature;
(3) activation: product after above-mentioned charing is being contained to K
+alkaline solution in soak 2-4h, then open ports is placed in vacuum drying chamber 100-120 ℃ oven dry; Again the product after drying being inserted to sealing but stayed foraminate system is in semiclosed system, under still air atmosphere, Muffle furnace or tube furnace Program are warming up to 400-500 ℃ of constant temperature 0.5-1h, continue to be afterwards warming up to 700-800 ℃ of constant temperature 0.5-1h, heating rate is 5-10 ℃/min, after naturally cooling to room temperature, take out, and be washed with water to neutrality;
(4) modification: will soak 2-4h under the product room temperature after water washing in containing the solution of organic amine, then 80-100 ℃ of oven dry in vacuum drying chamber; Sample after drying is placed in to micro-wave oven, and under nitrogen atmosphere, temperature programming is to 400-500 ℃ of constant temperature microwave treatment 0.5-1h, and heating rate is 5-10 ℃/min; Then continue temperature programming to 800-1000 ℃ of constant temperature microwave treatment 0.5-1h, heating rate is 5-10 ℃/min, naturally cools to afterwards room temperature, obtains final carbon molecular sieve product.
2. the preparation method of the high-performance carbon molecular sieve for separating of carbon dioxide/methane as claimed in claim 1, is characterized in that, described carbon content is corncob, tobacco rod, coconut husk or walnut shell at more than 80% agricultural wastes.
3. the preparation method of the high-performance carbon molecular sieve for separating of carbon dioxide/methane as claimed in claim 1, is characterized in that, containing K
+alkaline solution be K
2cO
3or KOH solution, concentration is 20%-30%.
4. preparation method as claimed in claim 1, is characterized in that, containing K
+alkaline solution in also contain ethanol or the vinyl alcohol of 0.5-1%.
5. the preparation method of the high-performance carbon molecular sieve for separating of carbon dioxide/methane as claimed in claim 1, is characterized in that, in step (4), By Amine Solutions used is diethanol amine or acrylamide or the mixture of the two.
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| CN113083229A (en) * | 2021-03-30 | 2021-07-09 | 郑州大学 | Method for preparing carbon molecular sieve by using carbon material adsorbing carbonaceous substance |
| CN114682233A (en) * | 2022-03-17 | 2022-07-01 | 青岛华世洁环保科技有限公司 | Core-shell type carbon molecular sieve and preparation method and application thereof |
| CN115893410A (en) * | 2022-12-12 | 2023-04-04 | 榆林学院 | Semi-coke-based activated carbon and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008094710A (en) * | 2006-09-14 | 2008-04-24 | New Industry Research Organization | Method for producing molecular sieve carbon, and molecular sieve carbon |
| CN101596445A (en) * | 2009-06-05 | 2009-12-09 | 安徽理工大学 | A kind of preparation method of carbon molecular sieve adsorbent |
| CN102728320A (en) * | 2012-07-20 | 2012-10-17 | 清华大学深圳研究生院 | Preparation method for modified porous bamboo charcoal materials used for separating carbon dioxide and methane |
| CN102728331A (en) * | 2012-07-20 | 2012-10-17 | 清华大学深圳研究生院 | Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane |
-
2013
- 2013-12-18 CN CN201310697479.4A patent/CN103691399B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008094710A (en) * | 2006-09-14 | 2008-04-24 | New Industry Research Organization | Method for producing molecular sieve carbon, and molecular sieve carbon |
| CN101596445A (en) * | 2009-06-05 | 2009-12-09 | 安徽理工大学 | A kind of preparation method of carbon molecular sieve adsorbent |
| CN102728320A (en) * | 2012-07-20 | 2012-10-17 | 清华大学深圳研究生院 | Preparation method for modified porous bamboo charcoal materials used for separating carbon dioxide and methane |
| CN102728331A (en) * | 2012-07-20 | 2012-10-17 | 清华大学深圳研究生院 | Preparation method of metal-organic framework material for adsorbing separation of carbon dioxide/ methane |
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| CN105084357A (en) * | 2015-08-14 | 2015-11-25 | 湖州新奥利吸附材料有限公司 | Preparing method for carbon molecular sieve |
| CN105084343A (en) * | 2015-08-14 | 2015-11-25 | 湖州新奥利吸附材料有限公司 | Preparation method for low-cost carbon molecular sieve |
| CN105935584A (en) * | 2016-05-26 | 2016-09-14 | 湖州民强炭业有限公司 | Palm tree palm fiber CMSCH4 concentrate methane carbon molecular sieve |
| CN107055507A (en) * | 2017-04-28 | 2017-08-18 | 无锡德碳科技股份有限公司 | A kind of preparation method of carbon molecular sieve |
| CN108057419A (en) * | 2017-12-19 | 2018-05-22 | 太原理工大学 | A kind of methane nitrogen separation carbon adsorbent and preparation method thereof |
| CN109453745A (en) * | 2018-12-28 | 2019-03-12 | 苏州班顺工业气体设备有限公司 | High strength carbon molecular sieve and preparation method thereof |
| CN111729643A (en) * | 2020-07-02 | 2020-10-02 | 煤炭科学技术研究院有限公司 | Modified coconut shell-based adsorbent for separating methane/carbon dioxide and preparation method thereof |
| CN111748390A (en) * | 2020-07-02 | 2020-10-09 | 煤炭科学技术研究院有限公司 | Produced gas CO2Separation and purification process |
| CN113083229A (en) * | 2021-03-30 | 2021-07-09 | 郑州大学 | Method for preparing carbon molecular sieve by using carbon material adsorbing carbonaceous substance |
| CN114682233A (en) * | 2022-03-17 | 2022-07-01 | 青岛华世洁环保科技有限公司 | Core-shell type carbon molecular sieve and preparation method and application thereof |
| CN114682233B (en) * | 2022-03-17 | 2024-02-13 | 青岛华世洁环保科技有限公司 | Core-shell type carbon molecular sieve and preparation method and application thereof |
| CN115893410A (en) * | 2022-12-12 | 2023-04-04 | 榆林学院 | Semi-coke-based activated carbon and preparation method thereof |
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