CN103721678A - Efficient absorbent used for purification of biogass and coalbed methane and preparation method thereof - Google Patents
Efficient absorbent used for purification of biogass and coalbed methane and preparation method thereof Download PDFInfo
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- CN103721678A CN103721678A CN201210384714.8A CN201210384714A CN103721678A CN 103721678 A CN103721678 A CN 103721678A CN 201210384714 A CN201210384714 A CN 201210384714A CN 103721678 A CN103721678 A CN 103721678A
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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
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- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
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Abstract
The invention relates to an efficient absorbent used for purification of biogass and coalbed methane and a preparation method thereof. The absorbent is prepared from raw materials such as starch, phenolic resin and coal powder. The main preparation technology comprises crushing, mixing, forming, carbonization, activation and the like. The obtained absorbent has abundant micropores and is used in separation process of methane and carbon dioxide, the separation obtained methane gas has the purity more than 97%, and the absorbent is applicable to pressure swing adsorption apparatuses.
Description
Technical field
The present invention relates to high-efficiency adsorbent and the manufacture method of biogas, coal bed gas purification.
Background technology
In recent years, the fossil fuels such as coal, oil, natural gas non-renewable, and all environmental problems such as greenhouse effects of causing of petroleum refining industry, acid rain, dust pollution, cause people's common concern, greatly promoted the research and development of the regenerative resource industries such as wind energy, solar energy, water energy, biomass energy, geothermal energy, ocean energy.Biogas is subject to common concern as a kind of biomass energy general, that easily obtain with the extensive utilization of its efficient stable, and compared with other combustion gas, its capability of antidetonance is better, is a kind of generally acknowledged clean type recyclable fuel.
Improve biogas quality, first want purifying marsh gas, remove various impurity components (removing sulfide, halide, amine etc.), then carry out CH
4purify and (remove CO
2).Purification method is divided and can be divided into wet method and dry method by absorbent state; By the principle of processing, divide, can be divided into chemical absorption method, Physical Absorption method, membrane separation process, pressure swing adsorption method and bioanalysis etc.The above several separation methods of contrast, the film using in membrane separation process needs often to change, and operating cost is higher, and pressure-variable adsorption agent and chemical absorbent can be recycled, therefore, pressure swing adsorption method and chemical absorption method are wider compared with the practical application of membrane separation technique.Pressure swing adsorption method, compared with chemical absorption method, does not have adding of other medicaments in addition, to equipment non-corrosiveness, almost without " three wastes ", produce, can not cause new environmental pollution, and operation at normal temperatures, can save heating or cooling energy consumption, reduce operating cost.In addition the product purity of pressure swing adsorption method technique is high and can flexible modulation, and can arbitrarily regulate in the larger context according to the variation of process conditions the purity of product methane.Meanwhile, pressure swing adsorption method purification facility scale is flexible, in the purification project of small-scale, especially has superiority.And whole technique is by computer control, easy to operate, device can be realized full automatic working.Visible, pressure swing adsorption method is the one preferred technique in gas purification.
In pressure swing adsorption method technique, key technology is the performance of adsorbent; In general, adsorbent has appropriate surfaces structure and pore structure, easily manufactured, generally do not react with adsorbate, easily regeneration, has good mechanical strength, and adsorbent is all widely used in various fields such as petroleum industry, gas industry, medical science, environmental protection, pharmaceuticals industries.Current adsorbent kind used is a lot, but conventional has active carbon, molecular sieve, silica gel, activated alumina and a clay etc.Conventional adsorbent has two kinds, active carbon and molecular sieve.
The microcrystal of active carbon is that the laminated structure accumulation of being arranged with hexagonal lattice by carbon atom forms, be difficult for broken, the space generating between lattice forms various shapes and big or small pore, there is abundant microcellular structure, make active carbon there is large specific area and strong absorption property, belong to apolar substance.
In microporous molecular sieve, there is the hole of many marshallings, these holes not only provide bigger serface, can also play the effect of screening molecule, the molecule that is less than aperture enters molecular sieve endoporus, the molecule larger than aperture is blocked in molecular sieve surface, thereby the shape of making and the molecule varying in size are separated, belong to polar adsorbent, polar molecule is had to strong absorption property, can carry out depth drying and purification to gas, the in the situation that of higher temperature and certain humidity, also have higher selective.
The achievement in research of acticarbon mainly contains two aspects at present, and the one, to the modification of active carbon, for example, adopt the metal ions such as calcium, copper, magnesium to do after surface modification treatment active carbon, charcoal absorption CO
2performance have clear improvement.The 2nd, the new raw material of activated carbon is manufactured in exploitation, such as coal-based and biomass-based etc.Aspect the developmental research of molecular sieve, mainly concentrate on the study on the modification of molecular sieve.
It is raw material that adsorbent of the present invention adopts phenolic resins, starch and coal, and the adsorbent obtaining has the dual-use function of active carbon and molecular sieve, has good absorption property.
Summary of the invention
The object of this invention is to provide a kind of high-efficiency adsorbent for biogas, coal bed gas purification.
Another object of the present invention is to provide the simple preparation method of one of above-mentioned adsorbent, and this adsorbent can be used for pressure-variable adsorption by suitable stride rapid and the reverse methane and carbon dioxide vacuumizing in step concentrating and separating biogas or coal bed gas.
Object of the present invention realizes by following technical proposal:
(1) needed raw material starch, phenolic resins and coal dust are crushed to below 15 μ m;
(2) add by a certain percentage kneader, add water simultaneously, machine and mix;
(3) material mixing is shaped to cylinder on forming machine;
(4) put into drier, dry 12h at 80 ℃;
(5) dried material is put into heating furnace, under nitrogen protection, with the programming rate of 10 ℃/min, be heated to 300 ℃, and then with the programming rate of 5 ℃/min, be heated to 850 ℃, constant temperature 90min.
(6) after cooling, by the good sample of carbonization, under nitrogen protection, carry out steam activation, activation temperature is 700～800 ℃, and soak time is 1～6h.
(7) after cooling, then obtain granular adsorbent after washing, being dried.
Described adsorbent raw material, phenolic resins is thermosetting resin, starch can be cornstarch, tapioca, potato starch or wheaten starch, is preferably tapioca.
After crushed, particle diameter should be controlled at 10～20 μ m to described raw material.
The quality proportioning of described raw material: starch: phenolic resins: coal dust=5%～20%: 20～60%: 20～60%, preferred value is starch: phenolic resins: coal dust=10%: 45%: 45%.
The addition of described adsorbent-shaping process water is 1～10% (quality) of material quantity, and preferred value is 3%.
After described adsorbent-shaping, the suitable column diameter that is of a size of of granular material is 1～3mm, height 2-10mm, and preferred value is Φ 2 × 4mm.
After described adsorbent-shaping, need be at 80 ℃, dry 12h; And then under nitrogen protection, carry out carbonization at 850 ℃.
After described adsorbent carbonization, need be under nitrogen protection, use steam to activate at 700-800 ℃, preferred activation temperature is 750 ℃.
On pressure-swing absorption apparatus, test the separating property of this adsorbent to methane and carbon dioxide, test condition is: adsorptive pressure 0.4Mpa, desorption pressure-0.098Mpa, adsorption column Φ 20 × 300mm, raw gas flow 40ml/min, the concentration of separation of methane is greater than 97%.
Compared with prior art, adsorbent of the present invention has following features:
(1) preparation method's technique is simple, has low, the free of contamination feature of cost.
(2) granular adsorbent of preparing has the dual-use function of active carbon and molecular sieve and good absorption property.
(3) prepare adsorbent and there is abundant micropore, for the separation process of methane, carbon dioxide, separate the methane gas purity obtaining and exceed 97%, can be used for pressure-swing absorption apparatus.
(4) adsorbent of the present invention can be processed into difformity, meets the demand of different industries.
The specific embodiment
Embodiment 1
First needed raw material tapioca, phenolic resins and coal dust are pulverized, be then sized to 10～20 μ m, by following mass fraction, prepare burden, starch: phenolic resins: coal dust=10%: 45%: 45%; Put into kneader, add the water of 3% (quality) simultaneously, mix 1h; On forming machine, be molded into Φ 2 × 4mm cylinder, put into drier, dry 12h at 80 ℃; Put into carbide furnace, under nitrogen protection, with the programming rate of 10 ℃/min, be heated to 300 ℃, and then be heated to 850 ℃ with the programming rate of 5 ℃/min, constant temperature 90min, after cooling, injects gasification furnace by water with the amount of 10ml/min, and is 0.5m by flow
3the nitrogen of/h is brought steam into activation furnace, at 750 ℃, and activation 2h; At nitrogen protection borehole cooling, obtain product.Properties of product are: the following microporosity 86% of 0.8nm, specific area: 1100m
2/ g; On pressure-swing absorption apparatus, test the separating property of this adsorbent to methane and carbon dioxide, test condition is: adsorptive pressure 0.4Mpa, desorption pressure-0.098Mpa, adsorption column Φ 20 × 300mm, raw gas flow 40ml/min, the concentration 99% of separation of methane.
Embodiment 2
First needed raw material tapioca, phenolic resins and coal dust are pulverized, be then sized to 10～20 μ m, by following mass fraction, prepare burden, starch: phenolic resins: coal dust=5%: 50%: 45%; Put into kneader, add the water of 3% (quality) simultaneously, mix 1h; On forming machine, be molded into Φ 2 × 4mm cylinder, put into drier, dry 12h at 80 ℃; Put into carbide furnace, under nitrogen protection, with the programming rate of 10 ℃/min, be heated to 300 ℃, and then be heated to 850 ℃ with the programming rate of 5 ℃/min, constant temperature 90min, after cooling, injects gasification furnace by water with the amount of 10ml/min, and is 0.5m by flow
3the nitrogen of/h is brought steam into activation furnace, at 750 ℃, and activation 2h; At nitrogen protection borehole cooling, obtain product.Properties of product are: the following microporosity 82% of 0.8nm, specific area: 960m
2/ g; On pressure-swing absorption apparatus, test the separating property of this adsorbent to methane and carbon dioxide, test condition is: adsorptive pressure 0.4Mpa, desorption pressure-0.098Mpa, adsorption column Φ 20 × 300mm, raw gas flow 40ml/min, the concentration 98% of separation of methane.
Embodiment 3
First needed raw material tapioca, phenolic resins and coal dust are pulverized, be then sized to 10～20 μ m, by following mass fraction, prepare burden, starch: phenolic resins: coal dust=20%: 40%: 40%; Put into kneader, add the water of 1% (quality) simultaneously, mix 1h; On forming machine, be molded into Φ 2 × 4mm cylinder, put into drier, dry 12h at 80 ℃; Put into carbide furnace, under nitrogen protection, with the programming rate of 10 ℃/min, be heated to 300 ℃, and then be heated to 850 ℃ with the programming rate of 5 ℃/min, constant temperature 90min, after cooling, injects gasification furnace by water with the amount of 10ml/min, and is 0.5m by flow
3the nitrogen of/h is brought steam into activation furnace, at 750 ℃, and activation 2h; At nitrogen protection borehole cooling, obtain product.Properties of product are: the following microporosity 76% of 0.8nm, specific area: 840m
2/ g; On pressure-swing absorption apparatus, test the separating property of this adsorbent to methane and carbon dioxide, test condition is: adsorptive pressure 0.4Mpa, desorption pressure-0.098Mpa, adsorption column Φ 20 × 300mm, raw gas flow 40ml/min, the concentration 96% of separation of methane.
Embodiment 4
Change tapioca into cornstarch, other condition is identical with enforcement 1.Properties of product are: the following microporosity 82% of 0.8nm, specific area: 930m
2/ g; On pressure-swing absorption apparatus, test the separating property of this adsorbent to methane and carbon dioxide, test condition is: adsorptive pressure 0.4Mpa, desorption pressure-0.098Mpa, adsorption column Φ 20 × 300mm, raw gas flow 40ml/min, the concentration 97% of separation of methane.
Embodiment 5
Change tapioca into potato starch, other condition is identical with enforcement 1.Properties of product are: the following microporosity 77% of 0.8nm, specific area: 860m
2/ g; On pressure-swing absorption apparatus, test the separating property of this adsorbent to methane and carbon dioxide, test condition is: adsorptive pressure 0.4Mpa, desorption pressure-0.098Mpa, adsorption column Φ 20 × 300mm, raw gas flow 40ml/min, the concentration 95% of separation of methane.
Claims (8)
1. for an adsorbent for biogas, coal bed gas purification, it is characterized in that its physical property is:
Shape: cylindric;
The following microporosity of microporosity: 0.8nm is greater than 70%;
Specific area: 500～1500m
2/ g.
2. adsorbent according to claim 1, is characterized in that by starch, phenolic resins and coal dust being that raw material makes.
3. adsorbent according to claim 1, is characterized in that preparation technology comprises the following steps successively:
(1) pulverize: raw material is less than to 15 μ m through being crushed to particle diameter;
(2) mix: three kinds of raw materials are mixed by a certain percentage;
(3) moulding: mixed material is through being molded into cylindrical pellet;
(4) carbonization: the cylindric material obtaining carries out carbonization under nitrogen protection;
(5) activation: after carbonization treatment, use steam activation under nitrogen protection.
4. adsorbent raw material according to claim 2, is characterized in that phenolic resins is thermosetting resin, and starch can be cornstarch, tapioca, potato starch or wheaten starch.
5. preparation technology according to claim 3, is characterized in that the mass fraction of starch, phenolic resins and coal dust is respectively: 5%～20%, 20～60%, 20～60%.
6. preparation technology according to claim 3, is characterized in that the particle diameter of raw material is controlled at 10～20 μ m.
7. preparation technology according to claim 3, is characterized in that carburizing temperature is 750～880 ℃.
8. preparation technology according to claim 3, is characterized in that activation temperature is 700～800 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115924884A (en) * | 2022-12-12 | 2023-04-07 | 宣城市中兴分子筛有限公司 | Method for extracting carbon molecular sieve for methane from biogas |
Citations (3)
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| US5688313A (en) * | 1996-06-21 | 1997-11-18 | Amcol International Corporation | Activated carbon foundry sand additives and method of casting metal for reduced VOC emissions |
| CN1258638A (en) * | 1998-12-25 | 2000-07-05 | 中国科学院山西煤炭化学研究所 | Preparation of active carbon adsorbing and storing methane |
| CN101653721A (en) * | 2009-09-15 | 2010-02-24 | 重庆大学 | Preparation method of coal-based granular activated carbon with molecular sieving effect and application thereof in pressure-transformation adsorption and separation concentrated gas |
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2012
- 2012-10-12 CN CN201210384714.8A patent/CN103721678A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5688313A (en) * | 1996-06-21 | 1997-11-18 | Amcol International Corporation | Activated carbon foundry sand additives and method of casting metal for reduced VOC emissions |
| CN1258638A (en) * | 1998-12-25 | 2000-07-05 | 中国科学院山西煤炭化学研究所 | Preparation of active carbon adsorbing and storing methane |
| CN101653721A (en) * | 2009-09-15 | 2010-02-24 | 重庆大学 | Preparation method of coal-based granular activated carbon with molecular sieving effect and application thereof in pressure-transformation adsorption and separation concentrated gas |
Non-Patent Citations (2)
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| 刘立恒等: "粘结剂对颗粒活性炭PSA分离CH4/N2性能的影响", 《材料研究学报》 * |
| 刘立恒等: "粘结剂对颗粒活性炭PSA分离CH4/N2性能的影响", 《材料研究学报》, vol. 25, no. 3, 30 June 2011 (2011-06-30) * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115924884A (en) * | 2022-12-12 | 2023-04-07 | 宣城市中兴分子筛有限公司 | Method for extracting carbon molecular sieve for methane from biogas |
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Application publication date: 20140416 |