CN103933931A - Low-pressure methane-adsorbed stratified molecular sieve adsorbent and preparation method thereof - Google Patents
Low-pressure methane-adsorbed stratified molecular sieve adsorbent and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a low-pressure methane-adsorbed stratified molecular sieve adsorbent and a preparation method thereof. The adsorbent comprises the following components in parts by weight (100 parts in all): 30-90 parts of a mixture of one or any two of an MCM-49 stratified molecular sieve and an MCM-22 stratified molecular sieve and 30-50 parts of a binder such as aluminum oxide or silicon oxide, wherein the MCM-49 stratified molecular sieve and the MCM-22 stratified molecular sieve are subjected to surface modification treatment through liquid-phase deposition, and the molar ratio of SiO2 to Al2O3 is 10 to 60. The preparation method comprises the steps of adding 1-10 parts of a high-molecular compound pore-foaming agent in a forming process, uniformly mixing, and carrying out extrusion forming, wherein the activated roasting processing temperature of a formed body is 400-600 DEG C. The adsorbent is applied to low-pressure adsorption and storage processes of methane and has a high methane adsorption capacity reaching up to 160-180V/V. According to the preparation method, the problems of low methane adsorption capacity, high operation pressure and difficulty in regeneration of the adsorbent in the prior art are solved. The stratified molecular sieve adsorbent is taken as an efficient methane adsorbent and has good application prospects in the adsorption and storage of the methane.
Description
Technical field
The invention belongs to the adsorbent technical field of chemical materials, be specifically related to a kind of layer molecule sieve adsorbant and preparation method for low-pressure methane absorption.
Background technology
At present, the clean methane natural gas technology of coal system is the important directions of China's using energy source, national strategy.Coal preparing natural gas is based on the feature of domestic energy resource structure just, and by efficient utilization and the clean production natural gas that rationally transforms of coal, its energy conversion efficiency is far above coal liquefaction, coal derived DME, coal methyl alcohol processed, generating.But the how extensive effectively transport of coal preparing natural gas is in this industry development, to be badly in need of one of bottleneck problem solving.
Compare for pipe natural gas (PNG), liquefied natural gas (LNG), three kinds of conventional natural gas accumulating modes of compressed natural gas (CNG), take the mode of adsorbent adsorbed methane accumulating (ANG) to store and transport, carry out storage and the transport of natural gas by high-performance adsorbent.This kind of mode is the novel mode in natural gas accumulating, moving power consumption, the investment of building a station, safety, having unique advantage for aspects such as medium and small source of the gas and Firsthand Users.Carry out the exploitation of ANG key technology, can the clean natural gas of coal system effectively be stored and be carried on the one hand, can promote on the other hand the innovation of industry peak regulation, there is important economic benefit, social benefit.And this wherein efficiently, the preparation of adsorbent cheaply and microcellular structure, the preparation method etc. of various sorbing materials be one of subject matter of current ANG technology on the impact of absorption property.
Based on both at home and abroad result of study is in the past known, desirable Adsorption Natural Gas material should have the narrow pore-size distribution of large as far as possible Micropore volume and 1.5nm left and right, larger specific area, applicable hole surface character and good heat and mass efficiency.The test that a large amount of research of people concentrates on Carbon Materials raw material in micropore acticarbon preparation, physics and chemistry activation method, activator, activation condition, processing and forming, post-processing approach etc. is selected upper, has made the larger super micropore active carbon of Adsorption Natural Gas amount.Patent CN101003015 discloses a kind of high molecular derivatives Si-C composite material for absorbing and storing methane and preparation method thereof.The method, in alkaline distilled water, adds surfactant and organo-silicon compound, is hydrolyzed and emulsification, then obtains polymer-silicon hybridization precursor by vinylidene chloride polymerisation.By the washing of this precursor, dry after, under inert atmosphere by its progressively carbonization, its specific area of the composite obtaining 1700m
2more than/g, more than pore volume 0.90ml/g, to the adsorbance 140V/V of methane.Although this adsorbent can be under the temperate condition of 3.5MPa effective adsorbed methane, the adsorbance of methane is also lower than the Technical Economy index of 160 V/V.Patent CN1258638 discloses a kind of preparation method of active carbon of absorbing and storing methane, the method is taking petroleum coke or pitch coke as raw material, KOH is the active carbon that activator makes high-specific surface area powdery, then by powdered activated carbon and binding agent with 700-1000 DEG C of charings, recycling steam or carbon dioxide activation processing at 700-1000 DEG C, make moulding active carbon with high specific surface area.The type charcoal that the method makes volume adsorption for methane under 3.5MPa reaches 140-170V/V.This active carbon has advantages such as methane volume adsorption are larger, but raw materials petroleum coke or pitch coke change of properties are large, and preparation process step is longer, and product quality is wayward with repeatability.CN101531365 discloses a kind of preparation method of pressed active carbon for pressure swing adsorption/separation of methane/nitrogen.Although it is simple that this preparation method has technical process, cost is low, pollute little feature, and the active carbon of preparation has advantages of that methane/nitrogen separation is effective, and methane volume adsorption is less, therefore it can not be as the Special adsorbent of absorbing and storing methane.Therefore although active carbon itself has very large specific area and pore-size distribution, larger to methane adsorption capacity, in the kind of active carbon, preparation method, gas, water content etc. is very obvious on methane adsorbance and the impact such as selective.On the other hand, the intrinsic processing and forming inconvenience of absorbent charcoal material, sorption and desorption variations in temperature are large, the wider problem of pore-size distribution is difficult to solve well comprehensively, have affected the performance of its practical effect.The exploitation of high-efficiency adsorbent will be depended on research and the application of novel nano poromerics and duct thereof and finishing technology etc.
In recent years, the inorganic molecule sieve synthesis technical field with regular pore canal has had development at full speed, and multiple new construction sial or silica zeolite are synthesized and are applied to Kaolinite Preparation of Catalyst and absorbent preparation.Wherein there is the novel high-performance sorbent material of high-sequential microcellular structure, adsorption capacity powerful feature, become research and one of application focus that current new energy field is paid close attention to.Due to the special microcellular structure of zeolite molecular sieve and selective absorption effect, aspect gas absorption separation and purification, there is application quite widely.CN102513058A discloses a kind of modified natural foresite and preparation method as methane adsorbent.Taking natural STI zeolite (molecular sieve) as raw material, after ammonium salt solution exchange, obtain NH4-STI zeolite, after high-temperature vapor is processed, obtain H-STI zeolite, then exchange with magnesium ion, obtain magnesium type STI zeolite.This adsorbent natural minerals zeolite used reserves are abundant, cost of winning is low, the method of simultaneously preparing STI zeolite methane adsorbent is easy, and cost is lower, and the separation of methane/nitrogen is greater than 3, but as the Special adsorbent of absorbing and storing methane, its adsorption capacity is lower.
Layer molecule sieve adsorbant is the novel microporous inorganic material of one with the fastest developing speed in the world nearly ten years, has the characteristic of high adsorption capacity, pore structure high-sequential.Current, novel stratiform micro porous molecular sieve has been successfully applied in Effect of Catalysis In Petrochemistry agent production abroad because its unique dual duct diagram of system reveals excellent molecular diffusion performance.With other porous material as compared with aluminium oxide, silica gel, activated carbon etc., its feature is selected or modified and can carry out Effective Regulation change to duct shape and pore size, duct surface nature by organic ligand, to increase absorption affinity and the adsorption capacity to specific adsorbate.So lamellar zeolite material has obvious advantage at three major parameters of surface area, pore-size distribution, micropore quantity that determine performance of the adsorbent, for the Design & preparation of novel porous adsorbent provides a kind of new way.
In such stratiform micro porous molecular sieve, MCM-49, MCM-22 material grains size are in 1-5 um left and right, the interior micropore canals system by two cover five-ways of crystal, the interlayer hole and the 0.75nm layer endoporus that are 1.50nm form (being similar to major urban arterial highway and street), pore volume 0.5 – 0.6 ml/g, and the physico-chemical property with different its pore canal system of molecular sieve silica alumina ratio can change adjusting, and molecular screen material chemistry is with Heat stability is good and be easy to moulding.The character of this novel lamellar micro porous molecular sieve meets the requirement of desirable natural gas adsorbent preferably.After we are tentatively to molecular sieve chemical modification as the adsorbance of adsorbent methane under 3 bar low pressure at 150-170 V/V.Intend preparing Optimum Experiment by synthetic, modification, the moulding etc. of further deep extraordinary stratiform micro porous molecular sieve, more than expection adsorbent coal preparing natural gas adsorbance reaches 170 V/V, desorption gas methane concentration is more than 99%.Combine with mature pressure-variable adsorption separating technology (PSA), be expected to develop into the high-efficiency methane gas storage material that next-generation technology economy is good.
Summary of the invention
Wider for methane adsorbent pore-size distribution in the past, methane adsorbance is lower, absorption-desorption temperature changes greatly, impurity content etc. on impacts such as absorption properties obviously, and the problem such as preparation and processing and forming inconvenience.The present invention proposes that a kind of pore structure high-sequential, specific area are large, the novel lamellar molecular sieve methane adsorbent of high adsorption capacity and preparation method thereof.
A kind of layer molecule sieve adsorbant and preparation method for low-pressure methane absorption of the present invention, this adsorbent comprises following component in parts by weight:
(1) 50 ~ 90 parts, a kind of in MCM-49, MCM-22 stratiform micro porous molecular sieve or wantonly two kinds of mixtures;
(2) all the other are 10～50 parts of adhesive oxides, and its gross weight umber is 100 parts.
In the present invention, SiO2 and Al2O3 mol ratio in MCM-49, MCM-22 stratiform micro porous molecular sieve used are 10-60:1.
In the present invention, in MCM-49, MCM-22 used, wantonly two kinds of lamellar zeolites mix according to 1/10 – 10/1 weight rate, and after moulding, adsorbent of molecular sieve must be through liquid-phase silicone deposition surface modification; During liquid-phase silicone is deposition modified, select the methyl-silicone oil of commodity as modifier, the deposition of silica is 5%～15wt% (with respect to layer molecule sieve adsorbant).
In the present invention, adhesive oxides used is selected from aluminium oxide or silica.
The preparation method of the layer molecule sieve adsorbant of the low-pressure methane absorption that the present invention proposes, concrete steps are: by a kind of in MCM-49, MCM-22 stratiform micro porous molecular sieve or wantonly two kinds and adhesive oxides mixing, add again macromolecular compound pore-foaming agent to mix, then add rare nitric acid fully to mediate evenly, carry out extruded moulding, the processing of formed body calcination for activation, control sintering temperature is 400-600 DEG C.
In the present invention, macromolecular compound pore-foaming agent used is sesbania powder or polyacrylamide, is 5 wt%-10wt% of formed absorbent.
The adsorbance of layer molecule sieve adsorbant of the present invention methane under 3 bar low pressure, 25 degree is at 160-180 V/V.
The novel microporous methane adsorbent that the present invention proposes, is the dual duct of the uniqueness system layer shape micro porous molecular sieve that a kind of interlayer hole by 1.50nm and 0.75nm layer endoporus form, and specific area is 300-500 m
2/ g, pore volume is 0. 5-0.7 m
3/ g.Thereby show excellent molecular diffusion performance, therefore the rate of adsorption is high, absorption--desorption performance is good.Meanwhile, the preparation method of methane adsorbent of the present invention is easy, and production cost is lower, and Technological Economy is good, is a kind of methane gas storage material efficiently, is with a wide range of applications.
Detailed description of the invention
Below by the following example, the present invention is further illustrated.
Embodiment 1:
Adopt SiO
2/ Al
2o
3mol ratio is 20 48 grams, sodium type MCM-22 molecular sieve and 12 grams of Al
2o
3adhesive mixes, then adds 2.8 grams, pore-foaming agent field mountain valley with clumps of trees and bamboo powder to mix, and then adds the rare nitric acid of a certain amount of 3 % fully to mediate evenly, carries out extruded moulding, after airing, makes adsorbent I in 530 DEG C of roastings.
Embodiment 2:
Described in employing embodiment 1, method makes the MCM-22 molecular sieve after moulding, the molecular sieve making, with flooding containing 12% phenyl silicone oil petroleum ether solution of configuring, is left standstill after dipping, thorough to solvent evaporates, after dry, at 520 DEG C, methane adsorbent II is made in roasting, and siliceous deposits amount is 5.2%.
Embodiment 3:
Adopt SiO
2/ Al
2o
3mol ratio is 40 40 grams, Hydrogen MCM-49 molecular sieve and 20 grams of Al
2o
3adhesive mixes, then adds 5 grams of pore-foaming agent polyacrylamides to mix, and then adds the rare nitric acid of a certain amount of 3 % fully to mediate evenly, carries out extruded moulding, after airing, makes adsorbent III in 420 DEG C of roastings.
Embodiment 4:
Described in employing embodiment 1, method makes the MCM-49 molecular sieve after moulding, the molecular sieve making, with flooding containing 25% phenyl silicone oil petroleum ether solution of configuring, is left standstill after dipping, thorough to solvent evaporates, after dry, at 590 DEG C, methane adsorbent II is made in roasting, and siliceous deposits amount is 13.6%.
Embodiment 5:
Adopt SiO
2/ Al
2o
3mol ratio is 50 20 grams, Hydrogen MCM-49 molecular sieve, SiO
2/ Al
2o
3mol ratio is 12 25 grams, sodium type MCM-22 molecular sieve and 10 grams of SiO
2adhesive mixes, then adds 3 grams, pore-foaming agent field mountain valley with clumps of trees and bamboo powder to mix, and then adds the rare nitric acid of a certain amount of 3 % fully to mediate evenly, carries out extruded moulding, after airing, makes adsorbent III in 420 DEG C of roastings.
Embodiment 6:
Described in employing embodiment 1, method makes the MCM-49/MCM-22 mixed molecular sieve after moulding, the molecular sieve making is flooded with the 20% phenyl silicone oil petroleum ether solution that contains configuring, after dipping, leave standstill, thorough to solvent evaporates, after dry, at 480 DEG C, methane adsorbent II is made in roasting, and siliceous deposits amount is 11.2%.
Comparative example 7:
Adopt respectively SiO
2/ Al
2o
3mol ratio is 35 40 grams of Hydrogen ZSM-5 molecular sieves or SiO
2/ Al
2o
3mol ratio is 5 40 grams, sodium type USY molecular sieve and 10 grams of SiO
2adhesive mixes, then adds 4 grams, pore-foaming agent field mountain valley with clumps of trees and bamboo powder to mix, and then adds the rare nitric acid of a certain amount of 3 % fully to mediate evenly, carries out extruded moulding, after airing in 500 DEG C of roastings.The above-mentioned molecular sieve making is flooded with the 15% phenyl silicone oil petroleum ether solution that contains configuring, after dipping, leave standstill, thorough to solvent evaporates, roasting at 520 DEG C after being dried, make respectively methane adsorbent VII and VIII, siliceous deposits amount is respectively 8.7% and 8.9%.
Embodiment 8:
Six kinds of methane adsorbent I, II, III, IV, V, VI are made in employing, investigate it in methane adsorption capacity in constant temperature, constant voltage on methane adsorbent equipment, and desorption performance.Condition adopts: 25 DEG C of adsorption temps; Pressure 3.0Mp; 45 DEG C of desorption temperatures; Desorption vacuum 500mmHg; Evaluate initial adsorption capacity/desorption rate, 50 average adsorption capacity/desorption rates of absorption/desorption, result is as shown in the table.
MCM-49 after siliceous deposits modification, MCM-22 molecular sieve are compared with adsorbent without siliceous deposits modification as can be seen from the above table, owing to having regulated parent/hydrophobic property and the molecular sieve interlayer pass size of MCM-49, MCM-22 hole surface, the methane adsorption under room temperature, low pressure is further obviously improved; MCM-49, MCM-22 molecular sieve have good stability in use simultaneously.And compare with USY molecular sieve with the ZSM-5 of conventional pore passage structure, the effect of its adsorption capacity/desorption rate significantly improves, and has reached the Technical Economy index request of commercial Application.
Claims (8)
1. for a layer molecule sieve adsorbant for low-pressure methane absorption, it is characterized in that this adsorbent comprises following component in parts by weight:
(1) 30 ~ 90 parts, a kind of in MCM-49, MCM-22 stratiform micro porous molecular sieve or wantonly two kinds of mixtures;
(2) all the other are adhesive oxides, and its gross weight umber is 100 parts.
2. the layer molecule sieve adsorbant of low-pressure methane absorption according to claim 1, is characterized in that the SiO in described MCM-49, MCM-22 stratiform micro porous molecular sieve
2with Al
2o
3mol ratio is 10:1-60:1.
3. the layer molecule sieve adsorbant of low-pressure methane absorption according to claim 1, it is characterized in that in MCM-49, MCM-22, wantonly two kinds of lamellar zeolites mix according to 1/10 – 10/1 weight rate, after moulding, adsorbent of molecular sieve must be through liquid-phase silicone deposition surface modification.
4. the layer molecule sieve adsorbant of low-pressure methane absorption according to claim 3, it is characterized in that liquid-phase silicone in layer molecule mesh surface selects the methyl-silicone oil of commodity as modifier in deposition modified, the deposition with respect to layer molecule sieve adsorbant of silica is 5%～15wt%.
5. the layer molecule sieve adsorbant of low-pressure methane absorption according to claim 1, is characterized in that described adhesive oxides is selected from aluminium oxide or silica.
6. the preparation method of the layer molecule sieve adsorbant of a low-pressure methane absorption as claimed in claim 1, it is characterized in that a kind of in MCM-49, MCM-22 stratiform micro porous molecular sieve or wantonly two kinds and adhesive oxides mixing, add again macromolecular compound pore-foaming agent to mix, then add rare nitric acid fully to mediate evenly, carry out extruded moulding, the processing of formed body calcination for activation, control sintering temperature is 400-600 DEG C.
7. the preparation method of the layer molecule sieve adsorbant of low-pressure methane absorption according to claim 6, is characterized in that described macromolecular compound pore-foaming agent is sesbania powder or polyacrylamide, is 5 wt%-10wt% of formed absorbent.
8. the layer molecule sieve adsorbant of low-pressure methane absorption according to claim 1, is characterized in that the adsorbance of described layer molecule sieve adsorbant methane under 3 bar low pressure, 25 degree is at 160-180 V/V.
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| CN110761828A (en) * | 2019-09-23 | 2020-02-07 | 煤科集团沈阳研究院有限公司 | Gas explosion suppressant and preparation method thereof |
| CN112973623A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Application of EAB molecular sieve in separation of methane/carbon dioxide |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109550477A (en) * | 2019-01-17 | 2019-04-02 | 卓悦环保新材料（上海）有限公司 | A kind of application of titanium silicon dead catalyst and titanium silicon adsorbent |
| CN110368803A (en) * | 2019-07-22 | 2019-10-25 | 煤科集团沈阳研究院有限公司 | A kind of gas absorbent and its preparation method and application |
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| CN110761828A (en) * | 2019-09-23 | 2020-02-07 | 煤科集团沈阳研究院有限公司 | Gas explosion suppressant and preparation method thereof |
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Application publication date: 20140723 |