CN105289508A - Dedicated adsorbent for pressure swing adsorption of concentrated methane and preparation method thereof - Google Patents
Dedicated adsorbent for pressure swing adsorption of concentrated methane and preparation method thereof Download PDFInfo
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- CN105289508A CN105289508A CN201510802692.6A CN201510802692A CN105289508A CN 105289508 A CN105289508 A CN 105289508A CN 201510802692 A CN201510802692 A CN 201510802692A CN 105289508 A CN105289508 A CN 105289508A
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Abstract
The invention discloses a dedicated adsorbent for pressure swing adsorption of concentrated methane and a preparation method thereof. The preparation method is characterized by comprising the following steps: taking an X-type molecular sieve as the raw material, at first, burning the X-type molecular sieve at a high temperature to remove the adsorbed impurities, then modifying the molecular sieve by an ionic liquid to obtain an IL-X molecular sieve, and finally drying and activating the IL-X molecular sieve to obtain the methane dedicated adsorbent. The CH4/N2 separation coefficient of the methane dedicated adsorbent is more than 4.8, the CH4/O2 separation coefficient is more than 5.4, and thus the adsorbent can be used as a high efficient adsorbent for pressure swing adsorption and separation of methane. The used X-type molecular sieve is a matured product in the market, the production cost is low, at the same time, the preparation method of methane adsorbent is simple, the cost is low, and the adsorbent is advantageously used for separating methane from low-concentration methane gas.
Description
Technical field
The present invention relates to a kind of Special adsorbent for pressure-changed adsorption concentrating methane and preparation method, this Special adsorbent is applicable to the methane in pressure-changed adsorption concentrating coal mine gas, belongs to sorbent material technical field.
Background technology
Methane, as the green energy resource of clean and effective, plays important impetus in China's energy structure optimizing.Feature that China's primary energy structure has " the oil-poor weak breath of rich coal ", resource consumption (accounts for more than 70%) based on coal.With coal mining by a large amount of for by-product coal bed gas (being commonly called as gas), wherein buried depth 2000m is with shallow coal bed gas geological resources about 36.8 trillion m
3, suitable with conventional gas reserves.According to statistics, China's coal-mine gas pumping amount 17,000,000,000 m in 2014
3, wherein down-hole extraction 13,300,000,000 m
3, and in the gas of more than 70% down-hole extraction methane concentration lower than 30vol%, have even lower than 5vol%.Because methane concentration is low, utilize difficulty to cause greatly gas utilization rate only about 30%, a large amount of low concentration gas is directly emptying, causes the huge wasting of resources and environmental pollution.Comparatively outstanding for the Utilizing question of this low concentration gas at present, also very urgent to the demand of concentrate technology.If by the in addition enrichment of these emptying gas, concentrate, strong supplementing can will be formed to conventional gas, and avoid the problem of environmental pollution that causes because a large amount of low concentration gas is emptying simultaneously.
Main direction of studying both at home and abroad for coal mine light concentration mash gas separating and concentrating has: cryogenic separation, pressure-variable adsorption separation, UF membrane, solvent absorption, synthesized hydrate etc., it is wherein comparatively industrial it is possible that deep cooling is separated with pressure-variable adsorption, although and cryogenic separation technology maturation, but complex process, equipment investment is large, energy consumption is high, operation easier is large, higher to the stability requirement of raw material, particularly corresponding secure context can not get effective guarantee.Therefore, pressure-variable adsorption is separated into the most applicable process, be also that the energy consumption of generally acknowledging at present is low, flow process is simple, easy to operate, invest one of low gas separating method.The key of pressure swing adsorption is to develop large to methane adsorption amount and has the adsorbent of high selectivity.
At present, the research work for methane adsorbent mainly concentrates on active carbon and zeolite molecular sieve, improves separating property by carrying out modification to it.Compared with molecular sieve, active carbon has higher specific area and pore volume, comparatively large to methane adsorption amount, becomes research emphasis both domestic and external.But due to activated carbon pore size wider distribution, based on equilibrium separation effect, active carbon is all not high to the adsorption selectivity of methane, general CH
4/ N
2separation is all lower than 3.4.Therefore using active carbon as adsorbent, the effect of methane in pressure-changed adsorption concentrating coal mine light concentration mash gas is adopted not to be desirable especially.
Zeolite molecular sieve, because having unique pore passage structure and single-minded pore-size distribution, obtains a wide range of applications at gas separaion and purification field.Because the kinetic diameter difference of methane (0.38nm), nitrogen (0.364nm), oxygen (0.346nm) is very little, these three kinds of gases can enter in the duct of most of zeolite molecular sieve in theory, cause the CH of zeolite molecular sieve
4/ N
2and CH
4/ O
2separation is lower, even lower than the CH of active carbon
4/ N
2and CH
4/ O
2separation, thus studied less.Chinese patent CN102513058A discloses a kind of the modified natural foresite and the preparation method that are used as methane adsorbent, the CH of methane adsorbent disclosed in it
4/ N
2separation is slightly larger than 3.A kind of CH is reported in document [Ind.Eng.Chem.Res., 2014,53,6807-6814.]
4/ N
2separation is the modified zeolite molecular sieve adsorbent of 3.84.The CH of methane adsorbent disclosed in existing documents and materials
4/ N
2separation is not all more than 4.
Ionic liquid (IonicLiquid, IL) refers at room temperature or be in a liquid state close to room temperature, the complete salt be made up of zwitterion, also referred to as low temperature molten salt.Ionic liquid is generally made up of organic cation and inorganic anion, due to the special performance (high thermal stability, high polarity, low-steam pressure etc.) that ionic liquid has, be widely used in the every field of chemical research, such as: solvent, extractant, absorbent and template etc.Up to now, the research of ionic liquid at room temperature achieves breakthrough.In gas absorption field, document [Acc.Chem.Res., 2007,40,1208-1216] compared for CH
4, C
2h
6, CO
2, N
2, O
2deng the absorption property of gas in different ionic liquid.Document [J.Mem.Sci., 2009,327,41-48] reports and ionic liquid is made film, is used for separation of C O
2/ CH
4, CO
2/ N
2mist.By the Common advantages of bound zeolite molecular sieve and ionic liquid, choose specific ionic liquid, and be introduced in molecular sieve, just can obtain that there is high CH
4/ N
2the modified molecules sieve adsorbant of separation, for the methane in concentrate coal mine light concentration mash gas, will have broad application prospects.
Summary of the invention
The object of the invention is to propose a kind of novel methane Special adsorbent and the preparation method with high adsorptive selectivity energy.
The methane Special adsorbent that the present invention proposes, is a kind of zeolite molecular sieve by ion liquid modified process, is raw material, obtains IL-X molecular sieve after ion liquid modified with X-type molecular sieve.
Methane Special adsorbent of the present invention, its skeleton structure keeps complete, and pore size is adjusted, CH
4/ N
2separation be greater than 4.8, CH
4/ O
2separation be greater than 5.4, can be used as the superior adsorbent of methane in pressure-changed adsorption concentrating coal mine light concentration mash gas.
The preparation method of methane Special adsorbent of the present invention, concrete steps are as follows:
Take X-type molecular sieve as raw material, first through high-temperature calcination removing absorption impurity, then obtain IL-X molecular sieve through ion liquid modified process, then drying, activation after obtain methane Special adsorbent.
Described X-type molecular sieve, silica alumina ratio is 1.0-1.5, can be 10X, 13X, LSX etc.
Described X-type molecular sieve can be pulverous, also can be shaping X-type molecular sieve.
Described high-temperature calcination, temperature is 550-650 DEG C.
Described ionic liquid, can be but be not limited to 1-ethyl-3-methylimidazole bromine salt ([emim] Br), 1-ethyl-3-methylimidazole villaumite ([emim] Cl), 1-ethyl-3-methylimidazole hexafluorophosphate ([emim] PF
6), 1-ethyl-3-methylimidazole nitrate ([emim] NO
3), 1,3-methylimidazole bromine salt ([mmim] Br), 1,3-methylimidazole tetrafluoroborate ([mmim] BF
4) etc. glyoxaline ion liquid.
The described method obtaining IL-X molecular sieve through ion liquid modified process is specially: configuration concentration is the ionic liquid aqueous solution of 1-10wt%, be that the ratio of 1:5-1:15 processes 1-8 time at 40-100 DEG C with solid-to-liquid ratio by X-type molecular sieve, each processing time is 1-4 hour.
Described activation, activation method can be that heating vacuumizes activation, and also can be that gas-heated purges activation, activation temperature be 80-350 DEG C.
The CH of the methane Special adsorbent obtained by the present invention
4/ N
2separation is greater than 4.8, CH
4/ O
2separation is greater than 5.4, can as the high-efficiency adsorbent of pressure swing adsorption/separation of methane.
The present invention's X-type molecular sieve used is market ripe, and production cost is low, and the method simultaneously preparing methane adsorbent is simple, and cost is lower, has application potential widely at low-concentration methane gas separation of methane.
Accompanying drawing explanation
Fig. 1 is that the methane Special adsorbent of embodiment 1 preparation is at the adsorption isotherm to methane, nitrogen and oxygen;
Fig. 2 is methane Special adsorbent adsorptive selectivity at various pressures prepared by embodiment 1.
Detailed description of the invention
Below by specific embodiment, the present invention is described in further detail.
Table 1 embodiment 1-7 intermediate ion liquid modifying treatment conditions table.
。
For embodiment 1, first X-type molecular sieve is calcined under 630 DEG C of conditions the impurity of removing absorption in 2 hours, ionic liquid [emim] the Br aqueous solution of preparation 3%, X-type molecular sieve is processed 6 times at 80 DEG C with solid-to-liquid ratio 1:10, each process 3 hours, spends deionized water 3 times after having processed, then at 80 DEG C dry 2 hours, at 180 DEG C, vacuumize activation 2 hours again, IL-X methane Special adsorbent of the present invention can be obtained.At 25 DEG C, during P=0.1MPa, the CH of methane Special adsorbent
4/ N
2separation is 4.88, CH
4/ O
2separation be 5.46.The methane Special adsorbent prepared of the present embodiment is to the adsorption isotherm of methane, nitrogen and oxygen as shown in Figure 1; Fig. 2 is methane Special adsorbent adsorptive selectivity at various pressures prepared by the present embodiment.
Equally, after also having done process the same manner as in Example 1 according to the treatment conditions of table 1 to all the other embodiment 2-7, the methane Special adsorbent performance that it obtains and the performance that embodiment 1 obtains there is no significant difference.Therefore do not do deposited stating at this.
Claims (10)
1. the preparation method for the Special adsorbent of pressure-changed adsorption concentrating methane, it is characterized in that, the method take X-type molecular sieve as raw material, first through the impurity of high-temperature calcination removing absorption, then obtain IL-X molecular sieve through ion liquid modified process, then drying, activation after obtain methane Special adsorbent.
2. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 1, is characterized in that, the silica alumina ratio of described X-type molecular sieve is 1.0-1.5.
3. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 1, is characterized in that, described X-type molecular sieve is 10X type molecular sieve, 13X type molecular sieve or LSX type molecular sieve.
4. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 1 or 3, is characterized in that, described X-type molecular sieve is Powdered or shaping X-type molecular sieve.
5. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 1, is characterized in that, described ionic liquid is glyoxaline ion liquid.
6. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 5, it is characterized in that, described ionic liquid is 1-ethyl-3-methylimidazole bromine salt ([emim] Br), 1-ethyl-3-methylimidazole villaumite ([emim] Cl), 1-ethyl-3-methylimidazole hexafluorophosphate ([emim] PF
6), 1-ethyl-3-methylimidazole nitrate ([emim] NO
3), 1,3-methylimidazole bromine salt ([mmim] Br), 1,3-methylimidazole tetrafluoroborate ([mmim] BF
4).
7. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 1 or 5 or 6, it is characterized in that, the described method obtaining IL-X molecular sieve through ion liquid modified process is specially: configuration concentration is the ionic liquid aqueous solution of 1-10wt%, be that the ratio of 1:5-1:15 processes 1-8 time at 40-100 DEG C with solid-to-liquid ratio by X-type molecular sieve, each processing time is 1-4 hour.
8. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 1, is characterized in that, its calcining heat of described high-temperature calcination is 550-650 DEG C.
9. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 1, is characterized in that, described activation method is that heating vacuumizes activation or gas-heated purges activation.
10. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 1 or 9, is characterized in that, described activation temperature is 80-350 DEG C.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688870A (en) * | 2016-03-31 | 2016-06-22 | 烟台智本知识产权运营管理有限公司 | Preparation method of X-type molecular sieve/LDHs composite adsorbent for separating methane and nitrogen through pressure swing adsorption |
| CN108007812A (en) * | 2017-11-28 | 2018-05-08 | 西安石油大学 | A kind of methane adsorption capacity mechanism study method based on ultimate analysis of coal |
| CN110354637A (en) * | 2019-07-30 | 2019-10-22 | 盖氏科技 | A kind of method of the easy adsorbed gas of pressure swing adsorption method enrichment |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011068642A2 (en) * | 2009-12-02 | 2011-06-09 | Uop Llc | Use of calcium exchanged x-type zeolite for improvement of refinery off-gas pressure swing adsorption |
| CN102350304A (en) * | 2011-10-28 | 2012-02-15 | 上海偲达弗材料科技有限公司 | Preparation method of hollow fiber molecular sieve adsorbent material |
-
2015
- 2015-11-19 CN CN201510802692.6A patent/CN105289508B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011068642A2 (en) * | 2009-12-02 | 2011-06-09 | Uop Llc | Use of calcium exchanged x-type zeolite for improvement of refinery off-gas pressure swing adsorption |
| CN102350304A (en) * | 2011-10-28 | 2012-02-15 | 上海偲达弗材料科技有限公司 | Preparation method of hollow fiber molecular sieve adsorbent material |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105688870A (en) * | 2016-03-31 | 2016-06-22 | 烟台智本知识产权运营管理有限公司 | Preparation method of X-type molecular sieve/LDHs composite adsorbent for separating methane and nitrogen through pressure swing adsorption |
| CN107551994A (en) * | 2016-03-31 | 2018-01-09 | 烟台智本知识产权运营管理有限公司 | A kind of preparation method of the X-type molecular sieve of adsorbing separation methane nitrogen/LDHs compound adsorbents |
| CN108007812A (en) * | 2017-11-28 | 2018-05-08 | 西安石油大学 | A kind of methane adsorption capacity mechanism study method based on ultimate analysis of coal |
| CN110354637A (en) * | 2019-07-30 | 2019-10-22 | 盖氏科技 | A kind of method of the easy adsorbed gas of pressure swing adsorption method enrichment |
| CN110354637B (en) * | 2019-07-30 | 2021-12-10 | 盖氏科技 | Method for enriching easily-adsorbed gas by pressure swing adsorption method |
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