CN1027679C - Gas separation membrane with selective adsorption properties - Google Patents
Gas separation membrane with selective adsorption properties Download PDFInfo
- Publication number
- CN1027679C CN1027679C CN 89105555 CN89105555A CN1027679C CN 1027679 C CN1027679 C CN 1027679C CN 89105555 CN89105555 CN 89105555 CN 89105555 A CN89105555 A CN 89105555A CN 1027679 C CN1027679 C CN 1027679C
- Authority
- CN
- China
- Prior art keywords
- film
- membrane
- gas separation
- mentioned
- separation membrane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 75
- 238000000926 separation method Methods 0.000 title claims abstract description 54
- 238000001179 sorption measurement Methods 0.000 title abstract description 19
- 239000003463 adsorbent Substances 0.000 claims abstract description 27
- 229910052751 metal Inorganic materials 0.000 claims abstract description 21
- 239000002184 metal Substances 0.000 claims abstract description 21
- 239000011949 solid catalyst Substances 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 11
- 229920002521 macromolecule Polymers 0.000 claims description 27
- 229920002492 poly(sulfone) Polymers 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 230000000996 additive effect Effects 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000001856 Ethyl cellulose Substances 0.000 claims description 8
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229920001249 ethyl cellulose Polymers 0.000 claims description 8
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical group [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229920001747 Cellulose diacetate Polymers 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000000843 powder Substances 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 34
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 27
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 19
- 239000002808 molecular sieve Substances 0.000 description 18
- 238000001764 infiltration Methods 0.000 description 17
- 230000008595 infiltration Effects 0.000 description 17
- 229920002301 cellulose acetate Polymers 0.000 description 14
- 238000005516 engineering process Methods 0.000 description 13
- 230000035699 permeability Effects 0.000 description 13
- 239000000428 dust Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000009792 diffusion process Methods 0.000 description 10
- 239000003292 glue Substances 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000007246 mechanism Effects 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 230000004888 barrier function Effects 0.000 description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 239000003595 mist Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 238000005266 casting Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000005304 joining Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- URAYPUMNDPQOKB-UHFFFAOYSA-N triacetin Chemical compound CC(=O)OCC(OC(C)=O)COC(C)=O URAYPUMNDPQOKB-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- 241001269238 Data Species 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 229960001760 dimethyl sulfoxide Drugs 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000001087 glyceryl triacetate Substances 0.000 description 1
- 235000013773 glyceryl triacetate Nutrition 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229960002622 triacetin Drugs 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- XTTGYFREQJCEML-UHFFFAOYSA-N tributyl phosphite Chemical compound CCCCOP(OCCCC)OCCCC XTTGYFREQJCEML-UHFFFAOYSA-N 0.000 description 1
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A gas separation membrane with selective adsorption function belongs to a mixed gas separation membrane material. The membrane material is prepared by mixing additives composed of an adsorbent, metal powder or a solid catalyst and the like with a high molecular compound, has excellent separation performance, and has a separation coefficient alpha of a porous membrane2/CO，H2/N2) > 3.74, while the permeation rate is J (H)2) At 10-4～10-3And even higher.
Description
The present invention relates to a kind of selection absorption property that has, be used for the film that mist separates, membrane material selects adsorbent, metal or metallic salt, the solid catalyst etc. of absorption property to make with high molecular polymer blend or reaction by having.
Membrane separation technique is with its efficient height, and technology is simple, and advantages such as small investment are applied to have tempting application prospect in the separation of various compounding substances increasingly extensively, and the separation that membrane separation technique is used for mist is the emphasis paid close attention to of people especially.
Problems such as the separation of mist and adjustment are the problems that industrial quarters extensively runs into.Along with industrial expansion, contain H
2, CO, CH
4Reasonable utilization Deng the industrial tail gas of composition is put in face of people day by day urgently.In the past, these tail gas or waste gas are difficult to be used economically except that being used for burning, cause the waste of resource and the pollution of environment, in recent decades, membrane separation technique is the development of membrane material particularly, for utilizing industrial tail gas that the possibility on the industry is provided, for example: from containing N
2Synthetic ammonia tailgas in separate to reclaim H
2And NH
3Deng.But in some field, the diffusion barrier The Application of Technology also has been subjected to some restrictions and difficulty.Whether these restrictions and difficulty be mainly from reasonable economically, that is, if the level of diffusion barrier technology does not reach the business accounting value of people's expectation, the application of this technology in this field will be very difficult.Undoubtedly, the separative efficiency of raising membrane material is the important channel that solves this difficult problem.
Usually, separation membrane material is divided into homogeneous membrane and perforated membrane two big classes.The infiltration mechanism of homogeneous membrane is dissolving-diffusion theory, and promptly gas at first in the absorption of film surface, dissolves then, and spreads from high side to low side in film, and last desorption comes out.In this process, what determine permeance property is the dissolution degree of gas with various molecule to membrane material, and therefore this mechanism is called as dissolving-diffusion mechanism.For perforated membrane, what determine permeance property is gas flow situation in the microporous layers, i.e. promise gloomy (Kundsen) stream, and it has determined infiltration rate and separation.That is to say that when system is under the interactional ideal case that can ignore intermolecular or molecule and hole wall etc., this film will equal the square root of the inverse of molecular weight ratio for the separation factor alpha (A/B) of mist so, promptly α (A/B)=
/
。For H
2/ CO, H
2/ N
2The desirable separation α of gaseous mixture equals
, be about 3.74.Obviously the above-mentioned theoretical treatment that perforated membrane is carried out and the agenda of film have bigger distance.Therefore, also there is not a kind of separation of perforated membrane to reach this theoretical value so far.
Find that through long term studies common polymeric membrane always is inverse relation to the permeability and the selectivity of certain gas.Promptly improve permeability, selectivity just reduces, otherwise, improving selectivity, permeability just reduces.Undoubtedly, there is the gas separation membrane of actual application value must possess high infiltration rate and high selectivity simultaneously, usually, homogeneous membrane has very high selectivity, and perforated membrane has higher infiltration rate, but be difficult to have both this 2 point with a kind of polymeric membrane, that is to say that you become a film at very difficult homogeneous membrane and perforated membrane " are done ", though you can make composite membrane to it.In order to improve traditional macromolecule permeability of the membrane and selectivity, people carry out copolymerization to two or more compound; Or blend; Or be prepared into composite membrane with ultra-thin active layer.Application with the developing membrane separation technique.
Virtuous controlled once publish an article [surface (day) 23, (1) 28(1985)] of the former paddy of Japan, proposition is used for C
1The performance objective value of the gas separation membrane of chemistry, promptly under the situation of the organic film of porous, working pressure is 50kg/cm
2More than, maximum operation (service) temperature is 150 ℃, its separating property (Capacity Ratio) H
2/ CO is 2～3, and transmission coefficient is 10
-4(cm
3Cm/cm
2CmHgsec) more than, in other words,, just has C if the performance of diffusion barrier reaches above-mentioned value under these conditions
1The possibility of chemical industry application.In addition, many remaining industrial departments, for example: synthetic ammonia PETROLEUM PROCESSING (reforming process etc.) and from natural gas, reclaiming. concentrate a large amount of hydrogen etc., all proposed corresponding requirement.
1987 United States Patent (USP) (US4,636,314) a kind of macromolecule that adds metal heteropoly acid or its salt and make in high molecular polymer and the blend film of inorganic matter are disclosed.1987 Japan Patent (JP62,202,801) a kind of metal dust that is full of adsorbable hydrogen in polymeric membrane () patent for example: palladium, platinum, nickel etc. is also disclosed.But above-mentioned patent is not all announced the chemical physical property and the master datas such as permeability and selectivity of relevant film.
1988 United States Patent (USP) (US4,740,219) disclose again a kind of in cellulose acetate, add special construction with hydrophobic grouping contain si molecular sieves Silicalite(Nature, Vol.271, Feb.9,1978, P512～516), as adsorbent.Become single phase film with solution-cast, this film is used for 02/N
2, CO
2/ H
2Separation, this film has bigger separation factor, but does not announce the master data of film seepage velocity J value in the patent, and the chemistry of film, physical property.Because concerning nonporous membrane, its separation factor alpha value will be far longer than perforated membrane.Therefore, to diffusion barrier, α value and J value have meaning of equal importance.
The objective of the invention is to utilize adsorbent. metal dust and its esters, solid catalyst is to the adsorption property (physical absorption of gas with various, chemisorbed, ADSORPTION STATE etc.), redox reaction performance and polymeric membrane are to the differential permeability of gas, a kind of gas separation membrane of selecting absorption property that has is provided, " behavior " of this film may not be subjected to " classics " film separation principle and theoretical restriction, this film is perforated membrane or nonporous membrane, is a kind of by adsorbent, metal, the single-phase mixture film of selecting the adsorbed gas function that has of catalyst etc. and macromolecular compound composition.
Another object of the present invention provides the above-mentioned method with gas separation membrane of selecting absorption property of preparation.
The 3rd purpose of the present invention is the above-mentioned film that makes to be used for membrane separator spare with practical value, for example H
2/ CO, H
2/ N
2, H
2/ CH
4, CO
2/ CH
4, O
2/ N
2Deng separation.
The present invention has the material of selecting adsorption function by adding in macromolecular compound, prepare separation membrane material.Worker of the present invention chances on, in macromolecular compound, add and have the prepared separation membrane of material of selecting adsorption function, have above-mentioned " classics " theoretical institutes inexplicable " behavior ", especially the separation factor alpha (A/B) of film (perforated membrane) is worth, surpassed the theoretical limiting value of these " classics ", and the separation factor alpha value is not only only relevant with the molecular weight of separated material, in other words, be exactly that the gas molecule of same molecular amount is when seeing through film of the present invention, have different speed, rather than " classics " theoretical said identical speed that has.This contribution of the present invention has not only improved the infiltration rate and the separation factor of gas separation membrane material greatly, and has opened up the approach for preparing the macromolecule gas separation membrane that the selection adsorption function is arranged with excellent properties.
The present invention utilizes Electronic Speculum, temperature programming adsorption/desorption technology. in-situ infrared technology, " process " of investigation gas permeation membrane material of the present invention.When proposing gas by film of the present invention, the ADSORPTION STATE that film had promotes conveyer mechanism.
As mentioned above, do not contain the perforated membrane of active additive, the principle of its separating mixed gas mainly is according to the gloomy molecular weight flooding mechanism of promise.The separation factor alpha of mist is only relevant with the molecular weight of gas molecule, promptly α (AB)=
/
。And we interpolation in the perforated membrane of certain adsorbent, find that but the α value has surpassed the limiting value of the gloomy theory of promise.Therefore, can confirm that its permeation mechanism is not only relevant with the gloomy diffuse flow of promise, and relevant with the situation of absorption, diffusion, desorption and ADSORPTION STATE, this point, we attempt to be illustrated in the following discussion.
The present invention utilizes film that macromolecular compound makes differential permeability energy and the physical and chemical performance thereof to gas with various, as: softening point, acid resistance, alkali resistance, dissolubility, viscosity, stretching, tearing strength and filming performance etc., selection can generate ADSORPTION STATE and adsorption bond strong and weak suitable metal dust, adsorbent, solid catalyst that oxidation-reduction reaction maybe can take place with separated gas molecule.Make the above-mentioned raw materials blend, fuse or be combined to one by chemistry or physical method, make macromolecule gas separation membrane with selection absorption property.
Above-mentioned metal dust is interpreted as the I in the 4th, 5,6 cycles, II, III, IV, V, VI, VII subgroup element and VIII family element in the periodic table of elements, for example: powder or its esters of Pt, Pd, Zn, Ag, Co, Ni, Nb, Fe, Cu, Cr, W, Mo etc.Adsorbent comprises various types of molecular sieves, for example: X type molecular sieve, A type molecular sieve, ZSM type molecular sieve, carbon molecular sieve etc., diatomite, silicon microballoon, aluminium oxide, and the various carriers (glazing of various models or not glazing carrier etc.) used of chromatography.Catalyst refers to the oxide catalyst that comprises above-mentioned metal or the metal/carrier catalyst that heterogeneous catalytic reaction is used, and these catalyst bases are generally SiO
2, AL
2O
3, SiO
2-Al
2O
3, ZnO, MgO and various types of molecular sieves etc.
A kind of or two or more above-mentioned adsorbent, metal dust or its esters or catalyst are in 2%～90%(weight) ratio and a kind of or two or more following organic high molecular polymer in 98%～10%(weight) ratio make through blend, fused or reaction and have the macromolecule gas separation membrane of selecting absorption property.
Above-mentioned macromolecular compound is meant organic silicon rubber, polyvinyl alcohol, cellulose acetate (two, three acetic acid), polysulfones, ethyl cellulose, polyacrylic acid, polyimides, NC Nitroncellulose etc., or the mixture of two or more above-mentioned macromolecular compound compositions.
Above-mentioned organic polymer is dissolved in the solvent with concentration in certain proportion, add (or not adding) suitable metal dust or its esters, adsorbent and solid catalyst, (temperature, mixing speed, humidity etc.) are mixed, are fused or reaction under certain conditions, obtain glue, this glue on clean smooth plate in air or in water casting film, perhaps use general film-forming apparatus film forming.Appropriate time then wears out in hot-air or hot water.
Above-mentioned glue also can be coated in to support on the ground and form composite membrane.
Above-mentioned mixing, fused or reaction condition are generally: 10～50 ℃ of temperature, mixing speed and time are with abundant mixing and reaction is advisable smoothly.
Above-mentioned membrance casting condition is, in air: temperature 5-40 ℃, relative temperature 30～90% is in the water: 0～50 ℃ of temperature, 0.1～5 minute time, the aging condition of film is in water: 50～90 ℃ of temperature, 1～8 hour time, the drying condition of film, in air: 20～80 ℃ of temperature, in a vacuum: 20～50 ℃ of temperature, 1～8 hour time.
Purpose of the present invention, can also realize by following manner:
By above-mentioned prescription and technology, adsorbent is the molecular sieve of carbon molecular sieve, sodium X type (13X) molecular sieve, calcium A type molecular sieve or other types, and macromolecular compound is ethyl cellulose, cellulose acetate or polysulfones.
Metal dust is cobalt powder or copper powder, and macromolecular compound is ethyl cellulose, cellulose acetate or polysulfones.
Adsorbent is active carbon and CuCl, and macromolecular compound is polysulfones or cellulose acetate.
Adsorbent is Pd/Al
2O
3Catalyst and CuCl, macromolecular compound are polysulfones.
Adsorbent can also select 13X(sodium X type) molecular sieve, macromolecular compound is polysulfones or cellulose acetate.
Adsorbent can also be 5A type (calcium A type) molecular sieve, and macromolecular compound is a cellulose acetate.
Adsorbent can also be to contain Na
2O, Al
2O
3Or SiO
2The equimolecular sieve, macromolecular compound is a cellulose acetate.
Solvent in the above-mentioned filming technology can be ketone, ester class, alcohols, amide-type and pyridine, oxolane, methyl-sulfoxide, dioxane etc., or the mixed liquor of two or more above-mentioned each kind solvents.
Above-mentioned support ground is meant, can make film increase the material of stretching, tearing strength, the present invention includes polyimides, polysulfones, polypropylene, polyester, nonwoven, cellulose family macromolecule etc.
The amount that joins metal dust in the above-mentioned macromolecular compound, adsorbent, solid catalyst is with 10～40%(weight) for good, wherein the ratio between metal dust, adsorbent, the solid catalyst can be regulated arbitrarily.
Adding the particle of additives such as metal dust in the film, adsorbent, solid catalyst to and be advisable with diameter 0.5～150 μ m, certainly, as not considering economic cause and changing the performance of additive, is good with fine grained.The surface area of these powder particles is 10～1500m
2/ g.The granular size of additive and distribution and specific area have direct relation, and for example mean particle size is 6 microns a reduced iron powder, and its specific surface can reach 5160m
2/ g.As the superfines of＜0.5 micron of selection, its specific surface may be bigger.As additive is porosity, and its average pore size is 1A～100 μ m.Under the prerequisite of keeping membrance casting condition and film-strength, the addition of additive can be unrestricted, but with 10～40%(weight) be good.The method that adds can directly be added in the glue, or adding also can behind the first soaked in solvent.Stirring the back powder particle can evenly or asymmetricly be distributed in the film.Powder particle also can add in film forming procedure, forms one deck additive powder bed on the surface of film.
From prior art and theory, we know that the thickness of diffusion barrier has a direct impact the transmitance of film, therefore, how to do film very thinly, to obtain bigger permeability, have become a kind of special technology.And the film made from prescription of the present invention and technology with very thick through what film was done, and does not influence the infiltration rate of film, is 1 * 10 with the thickness range of the film of above-mentioned prescription and method preparation
-3～0.5cm, we get rid of certainly, do film thinlyyer with prescription of the present invention and method, or thicker again, and adaptability of the present invention and uniqueness here just are described.
In above-mentioned filming technology, we can also select preferable condition.
In air, membrance casting condition is preferably: 20～35 ℃ of temperature, and relative humidity 40～60%, and in water: 0～35 ℃ of temperature, 0.5～4 minute time.The film that makes is worn out, the stability of film is very important, but should suits, aging under following condition is better choice: 60～90 ℃ of water temperatures, 1～3 hour time.Drying condition in the vacuum: 10～40 ℃ of temperature, 1～5 hour time.
The film made from above-mentioned prescription and method is porous or imporosity, is the single phase film with certain extension and tearing strength.
The permeability of above-mentioned film is at U.S. ASTM1434V(1975) carry out on the CS-135-241 type Permeability gauge recommended, assay method adopts modified constant voltage volumetric method, the 3400 gas chromatograph Analysis for CO, the O that produce with Varian company
2, N
2, H
2Deng component.
The performance of this film is: separating H
2/ CO, H
2/ N
2The time its separation α can be up to more than 3.0, even surpass 3.74 and reach 5.3, permeability J(H
2) [cm
3(STP)/cm
2SeccmHg]＞10
-4～10
-3
Of the present invention have a gas separation membrane of selecting absorption property, through temperature-programmed adsorption-desorption technology, in-situ infrared technology and transmission electron microscope, the determining adsorption instrument confirms that it can select to adsorb certain gas as O automatically
2, N
2, H
2, CO, CO
2, CH
4Reach gases such as rudimentary hydro carbons, and form ADSORPTION STATE on the surface, and the degree of stability of this ADSORPTION STATE, the size of adsorbance directly influences the permeability of the membrane energy.
Because film of the present invention has added " active particles " such as adsorbent, metal dust, solid catalysts, make that the surface of polymeric membrane is uneven, its existing catalytic activity application point, the adsorption activity application point is arranged again, the suction-operated of varying strength takes place between these application points and the gas molecule, and having formed ADSORPTION STATE, this ADSORPTION STATE has just played promotion conveying effect probably.
Accompanying drawing is Electronic Speculum (SEM) photo of diffusion barrier of the present invention, and macromolecular compound is a polysulfones, and additive is a solid catalyst, and wherein Fig. 1 and Fig. 2 are the surface of film, and Fig. 3 and Fig. 4 are the section (multiplication factor is respectively 1000 times and 2000 times) of film.Photo shows that there is more solid powder particle (white particle) film surface and inside.The section photo shows that the catalyst of interpolation has some and polysulfones to be bundled together, in some holes in the polysulfones porous layer.When gas with various saw through film, gas will contact with solid catalyst, adsorbent or metal dust inevitably, also just exists competitive Adsorption, diffusion, desorption, perhaps forms ADSORPTION STATE, has also just formed the peculiar penetration mechanism of film of the present invention.
The Carlo Erba 1822 type automatic absorbing analyzers that the present invention produces with Italy are measured adsorbent one polymeric membrane, and catalyst-polymeric membrane finds that their specific area and pore-size distribution and pore size are all different. And permeability of the membrane can (separation factor and infiltration rate) have direct relation with these data.
In sum, the present invention has outstanding substantive distinguishing features and significant technological progress compared with the prior art.
1, the master data of the prescription of film and film (such as specific area, pore-size distribution and pore size) shows, film has unique The Nomenclature Composition and Structure of Complexes.
2, film has excellent permeance property, shows that film possesses high selectivity (separation factor) and high infiltration rate simultaneously. Film is for separating of H2/CO、H
2/N
2During Deng gaseous mixture, J(H2) 10-4～10
-2In the scope, and α can be up to more than 3.0, even surpass 3.74 and reach 5.3.
3, owing to embedded active additive in the film, make film have simultaneously very high separation factor and infiltration rate, become possibility so that make thick film, thickness of the present invention can reach about 5mm.
For the present invention is described better, the invention will be further described by following embodiment:
Example 1
The 2g molecular sieve (contains Na
2O, Al
2O
3, SiO
2Deng) granularity is less than 0.1mm, joins in the dimethyl formamide solution of polysulfones, the mixture heating is stirred, and forms glue, is poured on the glass plate of level, and 20 ℃ of temperature, solvent flashing drying and forming-film in the air of relative temperature 50%, this film are perforated membrane.
Above-mentioned film is immersed the polysulfones solution some time, still dry under these conditions after the taking-up, become the film of post forming.After measured, the surface area of this film is 78.49m
2/ g, pore volume are 0.064cm
3/ g, pore volume are 0.064cm
3/ g, average pore radius is 16.6
, the infiltration rate J(H of film
2)＞10
-3, separation α (H
2/ CO)＞3.7, α (H
2/ N
2)＞3.0.
Example 2
Get the saturated CuCl dimethyl formamide solution of 4ml and polysulfones/dimethyl formamide solution of 16g20%, the stirring of suitably heating makes it molten entirely, adds 2gPd/Al again
2O
3Catalyst (granularity is less than 0.01mm) stirs, and leaves standstill a moment, and in the film forming on glass of level, surface area is 24.75m after measured then
2/ g, pore volume are 0.107cm
3/ g, average pore radius is 86.6A, this film is used to separate H
2/ CO, H
2/ N
2, its infiltration rate J(H
2)＞10
-3, separation factor alpha＞3.1.
Example 3
Get ethyl cellulose (ethyoxyl content 45～47%) and be dissolved in following solvent: ethanol, butanone, oxolane, pyridine, butyl acetate, dioxane, its concentration are 1～15%(weight), in film forming (under room temperature) on the flat board of level or on the polyester film, vacuum drying five hours makes nonporous membrane.But above-mentioned glue also coated is made composite membrane on backing material, for example, and nonwoven, porous polypropylene nitrile, or the porous PS membrane etc.
By above-mentioned prescription and method, in glue, add an amount of plasticizer (as: triethyl phosphate, tributyl phosphite, butyl phthalate, diethyl phthalate, butyl borate, three diglycol ethylenes, glyceryl triacetate, PEG400 etc.), can increase substantially the infiltration rate of film.
Example 4
Getting 15g concentration is 4～7%(weight) the pyridine solution of ethyl cellulose (ethyoxyl content 45～47%), add 1g cobalt powder (granularity is less than 200 orders), film forming on the glass plate of level is leached film in the water, again at 30～50 ℃ of following vacuum drying 5 hours, its seepage velocity J(H
2)＞10
-4, J(CO)＞10
-4, α (H
2/ CO)＞3.5, α (H
2/ N
2)＞3.5.
Example 5
Granularity (contains Na less than the molecular sieve of 0.10mm
2O, Al
2O
3, SiO
2Deng) 1g, joining in the dimethyl formamide solution of cellulose acetate and go, mixture suitably heats, stirs, forms glue, suitably leaves standstill, and at room temperature film forming makes perforated membrane, after tested, infiltration rate J(H
2)＞10
-2, J(CO)＞10
-3, separation factor alpha (H
2/ CO)＞3.2, α (H
2/ N
2)＞3.5.
Example 6
By example 5 prescription and preparation methods, replace cellulose acetate, the infiltration rate J(H of the perforated membrane that makes with ethyl cellulose
2)＞10
-2, α (H
2/ N
2)＞3.5.
Example 7
The adsorbent molecular sieve of carbon molecular sieve, sodium X type (13X) molecular sieve or other types, granularity is less than 0.10mm, molten the going of dimethyl formamide that joins the pyridine solution of ethyl cellulose or cellulose acetate, polysulfones gone in the liquid, mixture heats, stirs, leaves standstill, on the glass plate, on the metal film tool or on the polyester film, solvent flashing under 20～30 ℃ of air of temperature, dry under vacuum or the room temperature, make perforated membrane.
Change above-mentioned each molecular sieve analog into all kinds of solid catalysts,, also can be made into the perforated membrane of excellent performance as metal/carrier, metal oxide etc.
Example 8
1 gram molecule sieve (siliceous, granularity is less than 0.1mm) adds dimethyl formamide 9 grams, stirs 3 hours, the dimethyl formamide solution that adds cellulose acetate, stir, remove bubble, be poured over (27 ℃ of temperature on the smooth clean water flat glass plate, air pressure 630mmHg), striking film forming 2-3 minute dropped in the water 2-3 minute immediately, again this film drop in 85 ℃ the hot water 1 hour aging, take out the back film is blotted, and air dry is promptly under the smooth condition of film.This film J(H
2)=4.40 * 10
-4, J(N
2)=9.09～9.27 * 10
-5, α (H
2/ N
2)=4.84～5.25.
Example 9
Granularity is less than copper powder (crossing with hydrogen reducing in advance) 1 gram of 0.05mm, joining the dimethyl formamide of polysulfones or cellulose acetate goes in molten, mixture suitably heats, stir, form glue, suitably leave standstill, film forming at room temperature, aging in hot-air or hot water, make gas separation membrane, after tested infiltration rate J(H
2) be 5.2 * 10
-4, α (H
2/ CO)=3.8, α (H
2/ N
2)=3.6.
Example 10
Getting CuCl solution is soaked in the active carbon, dry again, activation, make the active carbon that contains CuCl,, join in the dimethyl formamide solution of polysulfones or cellulose acetate and go this active carbon 1 gram, suitably heating, stir, form glue, remove bubble, under the room temperature on the clean glass plate of level film forming, air dry.The infiltration rate of this film is: J(H
2)=2.32 * 10
-2, J(N
2)=6.37 * 10
-3, J(CO)=6.35 * 10
-3, J(CO
2)=4.91 * 10
-3, separation factor is: α (H
2/ N
2)=3.64, α (H
2/ CO)=3.65.
The infiltration rate unit that this paper mentions is: cm
3(STP)/cm
2SeccmHg.
Best enforcement just is example 1, example 8, example 9, example 10.
Claims (7)
1, has the macromolecule gas separation membrane of selecting absorption property, the following macromolecular compound that it is characterized in that the additive be made up of one or more following metallic salts, adsorbent, the solid catalyst of 2%-90% (weight) and 98%-10% is through blend, and fused or reaction is made;
Above-mentioned metallic salt comprises nitrate and the chloride of Co, Cu, Cr;
Above-mentioned solid catalyst is meant Fe-Cr-Zn, P-Mo-Bi oxide catalyst and Pt/Al
2O
3, Pd/Al
2O
3, Pd-Pt/Al
2O
3Metal/carrier catalyst;
Above-mentioned adsorbent is the active carbon that soaked above-mentioned slaine;
Above-mentioned macromolecular compound is cellulose diacetate, polysulfones, ethyl cellulose.
2, gas separation membrane as claimed in claim 1 is characterized in that adsorbent is CuCl, and solid catalyst is Pd/Al
2O
3, Pt/Al
2O
3, macromolecular compound is a polysulfones.
3, gas separation membrane as claimed in claim 1 is characterized in that metallic salt is Cu(NO
3)
2, solid catalyst is Pt/Al
2O
3, macromolecular compound is a cellulose diacetate.
4, gas separation membrane as claimed in claim 1 is characterized in that solid catalyst is Fe-Cr-Zn or P-Mo-Bi oxide catalyst, and macromolecular compound is a polysulfones.
5, gas separation membrane as claimed in claim 1, the particle that it is characterized in that adsorbent, solid catalyst is 0.5-150 μ m or thinner, surface area is 10-1500m
2/ g or bigger, average pore size is 1A-100 μ m.
6, as gas separation membrane as described in the claim 5, it is characterized in that thickness is 1 * 10
-3-0.5cm.
7,, it is characterized in that film is perforated membrane or nonporous membrane as claim 5 or 6 described gas separation membranes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105555 CN1027679C (en) | 1989-08-10 | 1989-08-10 | Gas separation membrane with selective adsorption properties |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89105555 CN1027679C (en) | 1989-08-10 | 1989-08-10 | Gas separation membrane with selective adsorption properties |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1040152A CN1040152A (en) | 1990-03-07 |
| CN1027679C true CN1027679C (en) | 1995-02-22 |
Family
ID=4856259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89105555 Expired - Fee Related CN1027679C (en) | 1989-08-10 | 1989-08-10 | Gas separation membrane with selective adsorption properties |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1027679C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368355C (en) * | 2005-08-15 | 2008-02-13 | 中国石油化工股份有限公司 | Method for raising yield of ethene, propylene |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5672388A (en) * | 1994-07-08 | 1997-09-30 | Exxon Research & Engineering Company | Membrane reparation and poer size reduction using interfacial ozone assisted chemical vapor deposition |
| US5824617A (en) * | 1994-07-08 | 1998-10-20 | Exxon Research & Engineering Company | Low alkaline inverted in-situ crystallized zeolite membrane |
| US5871650A (en) * | 1994-07-08 | 1999-02-16 | Exxon Research And Engineering Company | Supported zeolite membranes with controlled crystal width and preferred orientation grown on a growth enhancing layer |
| CN1309461C (en) * | 2004-01-13 | 2007-04-11 | 中国科学院生态环境研究中心 | Acetyl cellulose/Fe-Al oxide composite membrane, and its preparing method and use |
| CN101518719B (en) * | 2008-02-29 | 2012-02-01 | 中国科学院过程工程研究所 | Preparation method of organic-inorganic hybrid pervaporation preferential alcohol permeation membrane |
| CN102883795B (en) * | 2010-01-22 | 2015-01-07 | 小利兰斯坦福大学理事会 | Nitrogen-permeable membranes and uses thereof |
| CN103665531A (en) * | 2013-11-11 | 2014-03-26 | 深圳职业技术学院 | Plastic porous material and preparation method thereof |
| CN105457501B (en) * | 2015-12-19 | 2018-01-05 | 杭州水处理技术研究开发中心有限公司 | A kind of preparation method of efficient gas seperation film |
| CN109173752B (en) * | 2018-09-10 | 2021-10-01 | 杭州博大净化设备有限公司 | Mixed matrix membrane for gas separation and preparation method thereof |
| CN109529641B (en) * | 2019-01-11 | 2021-04-20 | 天津工业大学 | Polyimide-photosensitive cobalt organic framework hybrid membrane preparation and gas separation application |
| CN114749145B (en) * | 2022-04-28 | 2023-07-18 | 东北石油大学 | Molecular sieve for adsorbing and separating nitrogen and methane and its preparation method |
| CN117695869B (en) * | 2024-02-02 | 2024-04-19 | 天津工业大学 | Iron-based alloy hollow fiber membrane for hydrogen separation and preparation method thereof |
-
1989
- 1989-08-10 CN CN 89105555 patent/CN1027679C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100368355C (en) * | 2005-08-15 | 2008-02-13 | 中国石油化工股份有限公司 | Method for raising yield of ethene, propylene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1040152A (en) | 1990-03-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1027679C (en) | Gas separation membrane with selective adsorption properties | |
| EP1372832B1 (en) | Flexible and porous membranes and adsorbents, and method for the production thereof | |
| EP0607185B1 (en) | Particle-loaded nonwoven fibrous article for separations and purifications | |
| JP2716879B2 (en) | Composite polytetrafluoroethylene articles with controlled porosity and control methods therefor | |
| EP1468718B1 (en) | Air filter unit with several filtering media | |
| US8337601B2 (en) | Air filter sheet, process for manufacturing same, and air filter | |
| CN103958027A (en) | Methods of applying a sorbent coating on a substrate, a support, and/or a substrate coated with a support | |
| CN104689708B (en) | One removes formaldehyde air purifying filter core and preparation method thereof based on inclined hole aluminum honeycomb panel | |
| CN1218422A (en) | Regenrable catalyzed trap and apparatus, and method of using the same | |
| KR101402604B1 (en) | Metal-Complexed carbon Menmbrane and method for preparing the same | |
| CN107952289A (en) | A kind of filter screen with purifying formaldehyde and preparation method thereof | |
| CN1011201B (en) | Alkali-resistant ultrafiltration membrane | |
| CN112705179A (en) | Hierarchical different-pore covalent organic framework material and preparation method and application thereof | |
| CN109626389B (en) | Hollow molecular sieve with microsphere structure and preparation method thereof | |
| CN1027680C (en) | Catalytic-polymeric gas separation membrane | |
| CN114618232B (en) | Glass fiber air filtering material and application thereof | |
| CN109663564A (en) | A kind of gas adsorption material and preparation method thereof | |
| CN109248653A (en) | A kind of gas adsorption material and preparation method thereof | |
| CN118477486A (en) | PTFE folding type backflushing filter element with high dirt holding capacity and low flow resistance and preparation method thereof | |
| CN110624398B (en) | Air purification composite material | |
| CN113368705B (en) | Preparation method and application of functionalized bilayer molecularly imprinted nanofiber composite membrane based on dual synergistic imprinting strategy | |
| JP4315337B2 (en) | Non-particulate organic porous material having optical resolution and method for producing the same | |
| CN114522545A (en) | Load type imprinted membrane for selectively removing diclofenac sodium and preparation method thereof | |
| CN108176188B (en) | Application method of molecular sieve combination in waste gas purification and molecular sieve combination | |
| CN114177787A (en) | Self-supporting nanofiber anion exchange chromatographic membrane and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |