CN105289508B - A kind of Special adsorbent and preparation method for pressure-changed adsorption concentrating methane - Google Patents
A kind of Special adsorbent and preparation method for pressure-changed adsorption concentrating methane Download PDFInfo
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Abstract
A kind of Special adsorbent and preparation method for pressure-changed adsorption concentrating methane, it is characterized in that using X-type molecular sieve as raw material, the impurity that high-temperature calcination removes absorption is first passed around, then obtains IL X molecular sieves through ion liquid modified processing, then methane Special adsorbent is obtained after drying, activation.The CH of the methane Special adsorbent4/N2Separation is more than 4.8, CH4/O2Separation is more than 5.4, can be as the high-efficiency adsorbent of pressure swing adsorption/separation of methane.X-type molecular sieve used in the present invention is market ripe, and production cost is low, while the method for preparing methane adsorbent is simple, and cost is relatively low, has very extensive application potential in low-concentration methane gas separation of methane.
Description
Technical field
The present invention relates to a kind of Special adsorbent and preparation method for pressure-changed adsorption concentrating methane, the Special adsorbent
Methane suitable for pressure-changed adsorption concentrating coal mine gas, belong to sorbent material technical field.
Background technology
Green energy resource of the methane as clean and effective, plays important impetus in China's energy structure optimizing.China
Primary energy structure has " few gas rich in coal and poor in oil " feature, and resource consumption is based on coal（Account for more than 70%）.With coal mining
By a large amount of coal bed gas of by-product（It is commonly called as gas）, wherein buried depth 2000m is with the shallow m of coal bed gas geological resources about 36.8 trillion3, it is and normal
It is suitable to advise gas reserves.According to statistics, the m of China's coal-mine gas pumping amount 17,000,000,000 in 20143, the wherein m of underground extraction 13,300,000,0003, and
Methane concentration is less than 30vol% in the gas of more than 70% underground extraction, and some is even below 5vol%.Because methane concentration is low, sharp
Cause gas utilization rate only about 30% greatly with difficulty, a large amount of low concentration gas directly empty, and cause the huge wasting of resources and environment
Pollution.It is more prominent for the Utilizing question of the low concentration gas at present, it is also extremely urgent to the demand of concentrate technology.If it can incite somebody to action
The gas of these emptyings is enriched with, concentrate, strong supplement will be formed to conventional gas, and avoid simultaneously because of big volume low-concentration
Problem of environmental pollution caused by gas empties.
Have both at home and abroad for the main direction of studying of coal mine light concentration mash gas separating and concentrating：Cryogenic separation, pressure-variable adsorption point
From, UF membrane, solvent absorption, synthesized hydrate etc., wherein industrial more it is possible that deep cooling and pressure-variable adsorption separation, and deep
Although cold separation technology maturation, complex process, equipment investment is big, high energy consumption, operation difficulty are big, the stability requirement to raw material
Higher, particularly corresponding secure context cannot be effectively ensured.Therefore, pressure-variable adsorption is separated into most suitably used process,
It is that energy consumption generally acknowledged at present is low, flow is simple and convenient to operate, invests one of low gas separating method.Pressure swing adsorption
Key is to develop adsorbent big to methane adsorption amount and with high selectivity.
At present, the research work for methane adsorbent is concentrated mainly on activated carbon and zeolite molecular sieve, by entering to it
Row modification improves separating property.Compared with molecular sieve, activated carbon has higher specific surface area and pore volume, and methane is inhaled
Attached amount is larger, turns into research emphasis both domestic and external.But due to activated carbon pore size wider distribution, it is living based on equilibrium separation effect
Property charcoal is not high to the adsorption selectivity of methane, general CH4/N2Separation is below 3.4.Therefore suction is used as using activated carbon
Attached dose, the effect using methane in pressure-changed adsorption concentrating coal mine light concentration mash gas is not especially desirable.
Zeolite molecular sieve is because with unique pore passage structure and single-minded pore-size distribution, separating and purifying field in gas and obtain
Obtained and be widely applied.Due to methane（0.38nm）, nitrogen（0.364nm）, oxygen（0.346nm）Kinetic diameter difference very
Small, these three gases can enter in the duct of most of zeolite molecular sieve in theory, cause the CH of zeolite molecular sieve4/N2With
CH4/O2Separation is relatively low, even below the CH of activated carbon4/N2And CH4/O2Separation, it is less so as to what is be studied.China
Patent CN102513058A discloses a kind of modified natural foresite and preparation method as methane adsorbent, its disclosed first
The CH of alkane adsorbent4/N2Separation is slightly larger than 3.Reported in document [Ind.Eng.Chem.Res., 2014,53,6807-6814.]
A kind of CH in road4/N2Separation is 3.84 modified zeolite molecular sieve adsorbent.Methane adsorption disclosed in existing literature data
The CH of agent4/N2Separation is not above 4.
Ionic liquid（Ionic Liquid, IL）Refer to room temperature or be in a liquid state close to room temperature, completely by zwitterion
The salt of composition, also referred to as low temperature molten salt.Ionic liquid is typically made up of organic cation and inorganic anion, due to ionic liquid
Special performance possessed by body（High thermal stability, highly polar, low-steam pressure etc.）, it has been widely used in each of chemical research
In field, such as：Solvent, extractant, absorbent and template etc..So far, the research of ionic liquid at room temperature achieves frightened
The progress of people.In gas absorption field, document [Acc.Chem.Res., 2007,40,1208-1216] compared for CH4、C2H6、
CO2、N2、O2Deng absorption property of the gas in different ionic liquid.Document [J.Mem.Sci., 2009,327,41-48] is reported
Film is made in ionic liquid, for separating CO2/CH4、CO2/ N2Mixed gas.Pass through bound zeolite molecular sieve and ionic liquid
The Common advantages of body, specific ionic liquid is chosen, and be introduced into molecular sieve, with regard to that can obtain that there is high CH4/N2Segregative line
Several modified molecules sieve adsorbants, for the methane in concentrate coal mine light concentration mash gas, it will have broad application prospects.
The content of the invention
It is an object of the invention to propose a kind of novel methane Special adsorbent with high adsorptive selectivity energy and preparation
Method.
Methane Special adsorbent proposed by the present invention, it is a kind of zeolite molecular sieve by ion liquid modified processing, with X-type
Molecular sieve is raw material, and IL-X molecular sieves are obtained after ion liquid modified.
The methane Special adsorbent of the present invention, its skeleton structure keep complete, and pore size is adjusted, CH4/N2Point
It is more than 4.8, CH from coefficient4/O2Separation be more than 5.4, can be as methane in pressure-changed adsorption concentrating coal mine light concentration mash gas
Superior adsorbent.
The preparation method of methane Special adsorbent of the present invention, is comprised the following steps that：
Using X-type molecular sieve as raw material, the impurity that high-temperature calcination removes absorption is first passed around, then through ion liquid modified place
Reason obtains IL-X molecular sieves, then obtains methane Special adsorbent after drying, activation.
Described X-type molecular sieve, silica alumina ratio 1.0-1.5, can be 10X, 13X, LSX etc..
Described X-type molecular sieve, can be powdered or shaping X-type molecular sieve.
Described high-temperature calcination, temperature are 550-650 DEG C.
Described ionic liquid, 1- ethyl-3-methylimidazole bromides can be but not limited to（[emim]Br）, 1- ethyls-
3- methylimidazole villaumites（[emim]Cl）, 1- ethyl-3-methylimidazole hexafluorophosphates（[emim]PF6）, 1- ethyl -3- methyl
Imidazole nitrate（[emim]NO3）, 1,3- methylimidazole bromide（[mmim]Br）, 1,3- methylimidazole tetrafluoroborate
（[mmim]BF4）Deng glyoxaline ion liquid.
It is described to obtain the methods of IL-X molecular sieves through ion liquid modified handle and be specially：Configuration concentration is 1-10wt%'s
Ionic liquid aqueous solution, by X-type molecular sieve using solid-to-liquid ratio as 1:5-1:15 ratio handles 1-8 times at 40-100 DEG C, every time
Processing time is 1-4 hours.
Described activation, activation method can be that heating vacuumizes activation or the activation of gas heating and blowing, activation
Temperature is 80-350 DEG C.
The CH of methane Special adsorbent obtained by the present invention4/N2Separation is more than 4.8, CH4/O2Separation is more than
5.4, can be as the high-efficiency adsorbent of pressure swing adsorption/separation of methane.
X-type molecular sieve used in the present invention is market ripe, and production cost is low, while prepares the side of methane adsorbent
Method is simple, and cost is relatively low, has very extensive application potential in low-concentration methane gas separation of methane.
Brief description of the drawings
Fig. 1 is the methane Special adsorbent of the preparation of embodiment 1 in the adsorption isotherm to methane, nitrogen and oxygen；
Fig. 2 is the adsorptive selectivity of the methane Special adsorbent of the preparation of embodiment 1 at various pressures.
Embodiment
The present invention is described in further detail below by specific embodiment.
The embodiment 1-7 intermediate ion liquid modifying treatment conditions tables of table 1.
。
By taking embodiment 1 as an example, the 2 hours impurity for removing absorption is calcined under the conditions of 630 DEG C first by X-type molecular sieve, is matched somebody with somebody
Ionic liquid [emim] Br aqueous solution of system 3%, by X-type molecular sieve with solid-to-liquid ratio 1:10 handle 6 times at 80 DEG C, and per treatment 3
Individual hour, it is washed with deionized 3 times, is then dried 2 hours at 80 DEG C, then work is vacuumized at 180 DEG C after the completion of processing
Change 2 hours, you can obtain IL-X methane Special adsorbent of the present invention.At 25 DEG C, P=0.1MPa, methane dedicated suction
Attached dose of CH4/N2Separation is 4.88, CH4/O2Separation be 5.46.Methane Special adsorbent manufactured in the present embodiment
It is as shown in Figure 1 in the adsorption isotherm to methane, nitrogen and oxygen；Fig. 2 is that methane Special adsorbent prepared by the present embodiment exists
Adsorptive selectivity under different pressures.
Equally, after also having made processing the same manner as in Example 1 to remaining embodiment 2-7 according to the treatment conditions of table 1, it is obtained
To the obtained performance of methane Special adsorbent performance and embodiment 1 have no significant difference.Therefore do not make to apply herein and state.
Claims (4)
1. the preparation method of a kind of Special adsorbent for pressure-changed adsorption concentrating methane, it is characterised in that this method is with silicon
Aluminum ratio is the powdered of 1.0-1.5 or the 10X types molecular sieve, 13X types molecular sieve or the LSX type molecular sieves that are molded are raw material, first
The impurity of absorption is removed by high-temperature calcination, then obtains IL-X molecular sieves through ion liquid modified processing, then through drying, activation
After obtain methane Special adsorbent；Described ionic liquid is 1- ethyl-3-methylimidazole bromides（[emim]Br）, 1- ethyls-
3- methylimidazole villaumites（[emim]Cl）, 1- ethyl-3-methylimidazole hexafluorophosphates（[emim]PF6）, 1- ethyl -3- methyl
Imidazole nitrate（[emim]NO3）, 1,3- methylimidazole bromide（[mmim]Br）, 1,3- methylimidazole tetrafluoroborate
（[mmim]BF4）；It is described to obtain the methods of IL-X molecular sieves through ion liquid modified handle and be specially：Configuration concentration is 1-
10wt% ionic liquid aqueous solution, by X-type molecular sieve using solid-to-liquid ratio as 1:5-1:15 ratio handles 1-8 at 40-100 DEG C
Secondary, the time per treatment is 1-4 hours.
2. the preparation method of the Special adsorbent according to claim 1 for pressure-changed adsorption concentrating methane, its feature exist
In the temperature of the high-temperature calcination is 550-650 DEG C.
3. the preparation method of the Special adsorbent according to claim 1 for pressure-changed adsorption concentrating methane, its feature exist
In the activation method is that heating vacuumizes activation or the activation of gas heating and blowing.
4. the preparation method of the Special adsorbent for pressure-changed adsorption concentrating methane according to claim 1 or 3, its feature
It is, described activation temperature is 80-350 DEG C.
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| 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 |
| 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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