CN101935032A - Preparation method and use of carbon molecular sieve - Google Patents
Preparation method and use of carbon molecular sieve Download PDFInfo
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- CN101935032A CN101935032A CN 201010273277 CN201010273277A CN101935032A CN 101935032 A CN101935032 A CN 101935032A CN 201010273277 CN201010273277 CN 201010273277 CN 201010273277 A CN201010273277 A CN 201010273277A CN 101935032 A CN101935032 A CN 101935032A
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- molecular sieve
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Abstract
The invention relates to a preparation method and use of a carbon molecular sieve. The preparation method comprises the following steps: preparing a conventional carbon molecular sieve; and expanding the pores in the conventional carbon molecular sieve by using a secondary activation technique and modifying the conventional carbon molecular sieve by adjusting the pores. The new carbon molecular sieve is prepared by using coal, coconut shell or phenolic resin, and the like as raw materials, by the conventional production steps of crushing, forming, carbonizing, steam activating, hydrocarbon settling and shrinking and the like and by secondary activation with KOH or CO2 as an activator. The activation temperature is between 550 and 850 DEG C; and the ignition loss rate of the product is kept be between 0.1 and 30 percent. In aspect of use, the carbon molecular sieve can be used for absorbing nitrogen molecules and can also be used for absorbing and separating methane and nitrogen in seam gas under a variable pressure while achieving an adsorption dynamic separation effect and allowing high-concentration methane gas to be collected at the exit of an adsorption tower directly; and thus, the methane in the seam gas can be used efficiently.
Description
Technical field
The invention belongs to the material field, the production method that relates to the carbon molecular sieve of direct purification methane from coal-seam gas, novel carbon molecular sieve after the modification that obtains according to this production method shows the preferential selectivity of nitrogen adsorption, in pressure swing adsorption technique is used, coal-seam gas is by being filled with the fixed bed of carbon molecular sieve after the modification, nitrogen is by preferentially adsorbed, and methane directly appears from bed, thereby realizes the enrichment of methane gas.
Background technology
Along with the raising of people, attach great importance to the development and use of coal-seam gas in recent years both at home and abroad to mine safety, environmental protection consciousness.Coal-seam gas is as a kind of high-efficiency cleaning energy, and the outer foreign matter content of deacration is less relatively, is CH through pretreated coal-seam gas compositions such as desulfurization, dryings
4, N
2And O
2, with CH
4/ air or CH
4/ N
2Expression that is to say that the separation of coal-seam gas comes down to CH after the preliminary cleaning
4With N
2Between separation.
At present, the main both at home and abroad concentrated methane technology of coal-seam gas has membrane sepn, low temperature fractionation, transformation absorption (PSA) etc.With respect to other technology, PSA is applied to CH in the coal-seam gas
4And N
2Separation have energy consumption and running cost is low, flexible and convenient operation, normal temperature advantages such as operation continuously down.Transformation absorption be utilize sorbent material to micropore in the kinetic effect of the adsorption strength of each component of gaseous mixture, external diffusion in absorbent particles or the absorbent particles to the difference of each component molecule steric effect, circulation change with pressure serves as to separate impellent, and one or more components are concentrated or purifying.PSA realizes one of isolating major technique of industrialization gas adsorption at present, has been widely used in fields such as petrochemical complex, iron and steel, metallurgy.
The sorbent material that the absorption of coal-seam gas transformation is adopted mainly contains gac, carbon molecular sieve, clinoptilolite etc.
Gac is a kind of sorbent material of high-specific surface area, has flourishing gap structure and very big specific surface area, is widely used in fields such as all gases purification and high-energy-density gas storage.Gac transformation fractionation by adsorption N
2And CH
4Be based on the equilibrium adsorption separation principle, CH
4Be heavy constituent, must rely on desorb to obtain.Owing to contain a certain amount of light constituent in the stripping gas, so CH
4Purity is not high.Adopting gac is that sorbent material is separating N
2And CH
4Though obtain certain achievement, CH
4Concentrated effect is not very desirable, mainly is because CH
4/ N
2Equilibrium separation factor is not high.Can improve CH though improve cycle index
4Concentration, but consumed power charge, engineering is used uneconomical.
The clinoptilolite molecular sieve is a kind of natural ionic polar adsorbent, and pore texture is regular, the polarization of duct surface elevation.It is at CH
4-N
2Show N in the kinetics sepn process
2Preferential selectivity, show great application potential.Adopt ion-exchange to carry out modification, improve it N to the clinoptilolite molecular sieve
2Adsorption selectivity, improve CH
4-N
2Separating effect.But the application of clinoptilolite at present is based on powder particle, the purge process complexity, and all there is a series of problem in aspects such as moulding, bed filling, and being applied to the operation of industrialization transformation fractionation by adsorption also needs to do a lot of work.
Carbon molecular sieve is a kind of non-polar adsorbent, and its pore size approaches the gas molecule size, is widely used in fractionation by adsorption, field of purification, present sorbent material mainly as transformation absorption nitrogen production by air separation.The characteristics of conventional carbon molecular sieve are adsorption of oxygen, enrichment nitrogen, can isolate highly purified nitrogen from air, but existing aperture size is difficult to effectively methane in the coal-seam gas and nitrogen separation be come.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of carbon molecular sieve that adopts the re-activation method to produce direct purification methane from coal-seam gas, and the carbon molecular sieve that this production method makes can solve existing sorbent material is difficult to high efficiency separation methane-nitrogen in pressure swing adsorption technique problem.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of preparation method of carbon molecular sieve may further comprise the steps:
(1) prepares conventional carbon molecular sieve;
(2) adopt the re-activation technology that conventional carbon molecular sieve is carried out reaming, it is carried out modification by transferring the hole.
Further: the employed raw material of the conventional carbon molecular sieve of preparation is rich raw material of wood-charcoal material in the step (1).
Described rich raw material of wood-charcoal material is selected from coal, resol or coconut husk, but is not limited to above-mentioned listed rich raw material of wood-charcoal material.
The re-activation process adopts activator to carry out the carbon molecular sieve adjustment and control of pore diameter in the step (2), and activation temperature is at 550～850 ℃, and product burns the mistake rate and is controlled between 0.1%～30%.
It is that activator carries out re-activation that the conventional carbon molecular sieve that obtains in the step (1) is adopted KOH: adopt 10～30% (weight ratio) KOH aqueous solution that the conventional carbon molecular sieve of step (1) gained is flooded, dipping time is 2 hours;
Activation is cooled off under the environment of rare gas element after finishing, and feeding water vapour promptly obtains carbon molecular sieve to remove sedimentary K.
Or, the conventional carbon molecular sieve that obtains in the step (1) is adopted CO
2For activator carries out re-activation: the conventional carbon molecular sieve of step (1) gained is placed in the tube furnace reactor, introduce purity greater than 99.9% CO by rare gas element
2, its introducing amount consumes 200ml CO by the conventional carbon molecular sieve of every gram
2Calculate, activation temperature is controlled between 550～850 ℃, and soak time is 1～10 hour, and product burns the mistake rate and is controlled between 0.1%～30%;
After activation finished, cooling promptly obtained carbon molecular sieve under the environment of rare gas element.
The present invention adopts chemical activating agent KOH or physically activated dose of CO
2For activator carries out re-activation, but be not limited to above-mentioned listed activator.
The purposes of the carbon molecular sieve that above-mentioned method makes aspect the absorption nitrogen molecule.Described carbon molecular sieve is used for the separation of methane-nitrogen.Described carbon molecular sieve is used for from the direct purification methane of coal-seam gas.
Specifically, a kind of carbon molecular sieve that adopts the re-activation method to produce direct purification methane from coal-seam gas, it may further comprise the steps:
(1) according to the technology of preparing of existing carbon molecular sieve, by the raw material of wood-charcoal material being pulverized, after moulding, charing, activation, deposition of carbon handle, being made conventional carbon molecular sieve.For example, choose raw material of wood-charcoal material that hard coal, coconut husk or resol etc. are used to make conventional carbon molecular sieve as raw material, the raw material of wood-charcoal material is pulverized, it is standby that the raw material of wood-charcoal material after the pulverizing is crossed 200 mesh sieves; Then, add coal tar wet goods tackiness agent and carry out extruded moulding; Moulding is placed on carries out charing in the tubular reactor, charing is carried out in greater than 99.9% nitrogen in purity, carbonization temperature between 400 ℃～700 ℃, carbonization time 1 hour, the control temperature rise rate is 5 ℃ of min
-1, remove volatilizable composition wherein; Carry out steam activation after charing is finished, the steam activation process temperature is at 800 ℃～1000 ℃, and soak time is 45 minutes, activator water vapour with the contacting of raw material of wood-charcoal material in make its microvoid structure flourishing more, have higher specific surface; At last, adopt chemical Vapor deposition process to carry out deposition of carbon, under 700 ℃～900 ℃ conditions, the consumption calculating that consumes the 50ml benzene vapor by every gram raw material of wood-charcoal material feeds benzene vapor in reactor, the residence time is half an hour, the partial thermal decomposition carbon laydown that the benzene thermo-cracking produces is to the macropore ingress of raw material of wood-charcoal material, thereby makes the aperture obtain modulation, obtains conventional carbon molecular sieve.
In addition, the conventional carbon molecular sieve in the above-mentioned steps (1) also can directly obtain from market channel.
(2) the conventional carbon molecular sieve that obtains in the above-mentioned steps (1) being adopted KOH is that activator carries out re-activation: adopt 10～30% (weight ratio) KOH aqueous solution that the conventional carbon molecular sieve of step (1) gained is flooded, dipping time is 2 hours.Select for use KOH as activator, the process of dipping is reactivation process, and activation is cooled off under the environment of rare gas element after finishing, and feeds water vapour to remove sedimentary K; Can obtain can be from coal-seam gas the direct carbon molecular sieve of purification methane.
Above-mentioned steps (2) also can be: the conventional carbon molecular sieve that obtains in the above-mentioned steps (1) is adopted CO
2For activator carries out re-activation: the conventional carbon molecular sieve of step (1) gained is placed in the tube furnace reactor, introduce purity greater than 99.9% CO by rare gas element
2, its introducing amount consumes 200ml CO by the conventional carbon molecular sieve of every gram
2Calculate, activation temperature is controlled between 550～850 ℃, and soak time is 1～10 hour, product burns the mistake rate and is controlled between 0.1%～30%, after activation finishes, under the environment of rare gas element, cool off, can obtain can be from coal-seam gas the direct carbon molecular sieve of purification methane.
Adopt chemical activating agent KOH or physically activated dose of CO in the step of the present invention (2)
2Conventional carbon molecular sieve is carried out re-activation, reaming, transfer the hole that it is carried out modification by precision.With respect to the aperture adjustment effect of deposition process, the regulation and control of the precision of the easier realization carbon molecular sieve of re-activation aperture size.Through the carbon molecular sieve behind the re-activation, show the performance of preferentially adsorbed nitrogen, thereby in the process of coal-seam gas transformation absorption, realize the purpose of direct enrich methane.
Certainly, also can adopt other chemistry applicatory or physically activated dose (as water vapour etc.) that conventional carbon molecular sieve is carried out activation treatment, also can obtain the carbon molecular sieve after the modification, reach from coal-seam gas the directly purpose of purification methane.
The present invention adopts re-activation production to be used for separation of methane-nitrogen mixed system and the carbon molecular sieve of the methane of can directly purifying, utilize the kinetics of adsorption difference of methane, nitrogen to separate, the nitrogen rate of diffusion is greater than methane, carbon molecular sieve shows the preferential selectivity of nitrogen in the adsorption step of transformation absorption, thereby realizes the purpose of direct purification methane.
Carbon molecular sieve aperture behind the re-activation is greater than the conventional empty carbon molecular sieve aperture of dividing usefulness, and according to the difference of methane, nitrogen adsorption kinetic diameter, the carbon molecular sieve behind the re-activation more helps the absorption of nitrogen molecule.
Adopt the carbon molecular sieve behind the re-activation to carry out the transformation adsorption operations as sorbent material, it shows the preferential selectivity of nitrogen adsorption, utilizes this sorbent material to carry out the transformation fractionation by adsorption of methane-nitrogen, the purpose of the methane of can realizing directly purifying.
Embodiment
Now in conjunction with the embodiments the present invention is described in further details.
Embodiment 1:
A kind of carbon molecular sieve that adopts the re-activation method to produce direct purification methane from coal-seam gas may further comprise the steps:
(1) choose hard coal (or coconut husk or resol) and as raw material, raw material is pulverized, it is standby that the raw material after the pulverizing is crossed 200 mesh sieves; Then, add coal tar and carry out extruded moulding; Moulding is placed on carries out charing in the tubular reactor, charing is carried out in greater than 99.9% nitrogen in purity, carbonization temperature between 400 ℃～700 ℃, carbonization time 1 hour, the control temperature rise rate is 5 ℃ of min
-1, remove volatilizable composition wherein; Carry out steam activation after charing is finished, the steam activation process temperature is at 800 ℃～1000 ℃, and soak time is 45 minutes; At last, under 700 ℃～900 ℃ conditions, calculate by the consumption of every gram raw material consumption 50ml benzene vapor and feed benzene vapor in reactor, the residence time obtains conventional carbon molecular sieve after being half an hour.
(2) adopt the aqueous solution dipping of 10%KOH after 2 hours to the conventional carbon molecular sieve that obtains in the above-mentioned steps (1), it is 0.1% that product burns the mistake rate, after activation finishes, under the environment of rare gas element, cool off, and feed water vapour to remove sedimentary K, can obtain can be from coal-seam gas the direct carbon molecular sieve of purification methane.
The carbon molecular sieve that makes by above-mentioned steps is used for containing nitrogen 54.73%, the gas mixture of methane 45.27% carries out the operation of transformation fractionation by adsorption, carbon molecular sieve shows the preferential selectivity of nitrogen in adsorption step, the methane content that the adsorption tower enrichment obtains can be more than 99.0%, and the methane yield is higher than 70%.
Embodiment 2:
A kind of carbon molecular sieve that adopts the re-activation method to produce direct purification methane from coal-seam gas may further comprise the steps:
(1) choose hard coal (or coconut husk or resol) and as raw material, raw material is pulverized, it is standby that the raw material after the pulverizing is crossed 200 mesh sieves; Then, add coal tar and carry out extruded moulding; Moulding is placed on carries out charing in the tubular reactor, charing is carried out in greater than 99.9% nitrogen in purity, carbonization temperature between 400 ℃～700 ℃, carbonization time 1 hour, the control temperature rise rate is 5 ℃ of min
-1, remove volatilizable composition wherein; Carry out steam activation after charing is finished, the steam activation process temperature is at 800 ℃～1000 ℃, and soak time is 45 minutes; At last, under 700 ℃～900 ℃ conditions, calculate by the consumption of every gram raw material consumption 50ml benzene vapor and feed benzene vapor in reactor, the residence time obtains conventional carbon molecular sieve after being half an hour.
(2) the conventional carbon molecular sieve of step (1) gained is placed in the tube furnace reactor, introduce purity greater than 99.9% CO by rare gas element
2, its introducing amount consumes 200ml CO by the conventional carbon molecular sieve of every gram
2Calculate, activation temperature is controlled between 550～850 ℃, and it is 30% that product burns the mistake rate, and activation is cooled off under the environment of rare gas element after finishing, can obtain can be from coal-seam gas the direct carbon molecular sieve of purification methane.
The carbon molecular sieve that makes by above-mentioned steps is used for containing methane 20.17%, the gas mixture of nitrogen 79.83% carries out the operation of transformation fractionation by adsorption, carbon molecular sieve shows the preferential selectivity of nitrogen in adsorption step, the methane content that the adsorption tower enrichment obtains is more than 99.0%, and the methane yield is higher than 56%.
Above-mentioned description to embodiment is can understand and apply the invention for the ease of those skilled in the art.The person skilled in the art obviously can easily make various modifications to these embodiment, and needn't pass through performing creative labour being applied in the General Principle of this explanation among other embodiment.Therefore, the invention is not restricted to the embodiment here, those skilled in the art should be within protection scope of the present invention for improvement and modification that the present invention makes according to announcement of the present invention.
Claims (9)
1. the preparation method of a carbon molecular sieve may further comprise the steps:
(1) prepares conventional carbon molecular sieve;
(2) adopt the re-activation technology that conventional carbon molecular sieve is carried out reaming, it is carried out modification by transferring the hole.
2. method according to claim 1 is characterized in that:
The employed raw material of the conventional carbon molecular sieve of preparation is rich raw material of wood-charcoal material in the step (1).
3. method according to claim 2 is characterized in that:
Described rich raw material of wood-charcoal material is selected from coal, resol or coconut husk.
4. method according to claim 1 is characterized in that:
The re-activation process adopts activator to carry out the carbon molecular sieve adjustment and control of pore diameter in the step (2), and activation temperature is at 550～850 ℃, and product burns the mistake rate and is controlled between 0.1%～30%.
5. method according to claim 1 is characterized in that:
It is that activator carries out re-activation that the conventional carbon molecular sieve that obtains in the step (1) is adopted KOH: adopt 10～30% (weight ratio) KOH aqueous solution that the conventional carbon molecular sieve of step (1) gained is flooded, dipping time is 2 hours;
Activation is cooled off under the environment of rare gas element after finishing, and feeding water vapour promptly obtains carbon molecular sieve to remove sedimentary K.
6. method according to claim 1 is characterized in that:
The conventional carbon molecular sieve that obtains in the step (1) is adopted CO
2For activator carries out re-activation: the conventional carbon molecular sieve of step (1) gained is placed in the tube furnace reactor, introduce purity greater than 99.9% CO by rare gas element
2, its introducing amount consumes 200ml CO by the conventional carbon molecular sieve of every gram
2Calculate, activation temperature is controlled between 550～850 ℃, and soak time is 1～10 hour, and product burns the mistake rate and is controlled between 0.1%～30%;
After activation finished, cooling promptly obtained carbon molecular sieve under the environment of rare gas element.
7. the carbon molecular sieve that arbitrary described method makes in the claim 1 to 6 is in the purposes of absorption aspect the nitrogen molecule.
8. purposes according to claim 7 is characterized in that: described carbon molecular sieve is used for the separation of methane-nitrogen.
9. purposes according to claim 8 is characterized in that: described carbon molecular sieve is used for from the direct purification methane of coal-seam gas.
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| CN102502579A (en) * | 2011-10-28 | 2012-06-20 | 湖州强马分子筛有限公司 | Production method for shell-based carbon molecular sieve |
| CN104801273A (en) * | 2015-04-22 | 2015-07-29 | 煤炭科学技术研究院有限公司 | Adsorbent for coalbed methane concentration as well as preparation method and application thereof |
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| CN105188885A (en) * | 2013-05-10 | 2015-12-23 | 大阳日酸株式会社 | Method for separation of methane and nitrogen |
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