CN1837035A - Process for preparing nano hybrid carbon film - Google Patents

Process for preparing nano hybrid carbon film Download PDF

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CN1837035A
CN1837035A CN 200510200871 CN200510200871A CN1837035A CN 1837035 A CN1837035 A CN 1837035A CN 200510200871 CN200510200871 CN 200510200871 CN 200510200871 A CN200510200871 A CN 200510200871A CN 1837035 A CN1837035 A CN 1837035A
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preparation
carbon film
hybrid carbon
nano
gas
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CN100384722C (en
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王同华
刘庆龄
邱介山
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Dalian University of Technology
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Dalian University of Technology
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Abstract

The invention belongs to new material technique realm, and relates to the method for preparation of a nano hybridization char film, especially referring to the Method for preparation of char compound with abionano particle, metal grain or metal salt, organic additive and so on. The character lies in in the processs of char film prodromal body, according to adds some abio-nano partical, metal grain or metal salt, organic additive and so on, utilizing hybridization species' feeding effect for gas, consequently improving char film gas flux, at the same time not depress the selectivity. the effect and benefit of this invention is settling the complex technique, hard to improve the gas's flux in high gas selectivity condition of char film preparation technique in existence, providing a method for preparation of a nano hybridization char film which is convenient to manipulate, easy to control.

Description

A kind of preparation method of nano hybrid carbon film
Technical field
The invention belongs to new material technology field, relate to a kind of preparation method of novel nano hybrid carbon film, particularly relate to the method that charcoal and inorganic nano-particle, metallic particles or blending hydridization such as metal-salt, organic additive prepare compound carbon membrane.
Background technology
Since nineteen eighty-three Koresh and Soffer successfully prepare the gas delivery carbon membrane of walking in small steps, many novel carbon membrane persursor materials and technology of preparing have been continued to bring out out.People such as Suda and Haraya utilizes Kapton type Kapton direct charing under vacuum condition of Dupont public affairs to prepare O 2/ N 2Selectivity is up to 36 carbon membrane (J.Phys.Chem.B 1997,101,3988.).Employing ultrasonic deposition such as Shiflett become embrane method to deposit poly furfuryl alcohol on porous stainless steel, and charing makes the nanoporous level and supports carbon membrane under the helium protection, to O 2/ N 2Has good separating effect (Science 1999,285,1902.).Fuertes is coated in the inwall of vitrified pipe supporter with the Dipping technology with phenolic resin, under vacuum in 700 ℃ of charings, prepared Molecular sieve carbon membranes (Journal of Membrane Science 2000,177:9).Youn Kook Kim etc. introduces polyimide with the carboxylic acid group, thus the pore structure of utilizing carboxylic acid group's decomposition in the pyrolytic process to improve carbon membrane improve carbon membrane gas separating property (Journal of Membrane Science 2004,235:139).People such as Pei Shi Tin adopt methods such as presoma being carried out the non-solvent solution impregnation to improve the carbon membrane gas separating property, find to utilize by the presoma behind the non-solvent alcohol solution dipping because solution has swelling action to the polyimide chain, thus improved its to the selectivity of divided gas flow but reduced gas flux (
Industrial?&?Engineering?Chemistry?Research，2004?43：6476)。
Although above-mentioned certain methods can be improved the gas permeability of carbon membrane,, obtain high gas flux under than higher selectivity and remain more scabrous problem for the carbon membrane of above-mentioned preparation.
Summary of the invention
The purpose of this invention is to provide a kind of easy and simple to handle, the preparation method of the nano hybrid carbon film that is easy to control.Solve existing complicated process of preparation in the existing carbon membrane technology of preparing, the problem that gas flux reduces under highly selective.
A kind of novel nano hybrid carbon film preparation method's provided by the present invention technical scheme comprises:
(1) mixing solutions preparation.With inorganic nano-particle ZSM-5,4A, carbon molecular sieve, SiO 2, TiO 2, metallic particles Ag, Cu, Pt, Pd, Au or metal-salt AgNO 3, CuNO 3, methods such as employing blend, sol-gel such as organic additive polyoxyethylene glycol, polyvinylpyrrolidone disperse or dissolve solvent such as N,N-dimethylacetamide, n-formyl sarcolysine base pyrrolidone, n-formyl sarcolysine yl acetamide, dimethyl sulfoxide (DMSO), in the chloroform etc., hotchpotch is dispersed in the solvent through stirring.
(2) above-mentioned solution is dropwise joined polymers soln such as polyamic acid, various polyimide, polyetherimide, polyethersulfone ketone, poly furfuryl alcohol, phenolic resin polyvinylidene chloride, in polyvinylidene difluoride (PVDF), polyacrylonitrile, various Mierocrystalline cellulose, polysulfones, the polyethersulfone etc., and stir simultaneously, till the mixing solutions that forms homogeneous, or adopt original position synthetic method that above-mentioned hotchpotch is incorporated in the polymkeric substance; The mass content of hotchpotch is controlled at 3%～50% usually; For inorganic nano-particle, metallic particles or metal-salt, the organic additives etc. that can make interpolation are easy to be dispersed in the polymkeric substance; thereby it is very high to the dispersion requirement of additive in solvent; should adopt suitable churning time and special dispersing method; churning time is controlled at 1h～10h usually, adopts ultrasonic dispersing or high-speed stirring to disperse.
(3) precursor film preparation.Above-mentioned mixing solutions is adopted system film modes such as knifing, pickling process, spread coating, spraying method or ultrasonic deposition method, make flat sheet membrane or it is coated on supporter such as porous ceramic pipe or plate, porous stainless steel or plate, porous charcoal pipe or plate and the porous silicon plate etc. and make composite membrane, prepare the precursor film of hybrid carbon film through solvent evaporation, drying.
(4) hybrid carbon film preparation.The above-mentioned precursor film of making is directly put into charring furnace carries out charing,
Or charing again after putting into charring furnace after the first preoxidation again and carrying out charing or directly put into the first preoxidation of charring furnace; Under protection of inert gas,, just can prepare nano hybrid carbon film by condition of carbonization such as control carbonization heating rate, the whole temperature of charing, rare gas elementes; Usually the condition of carbonization that adopts is: temperature rise rate is 0.2 ℃～10 ℃/min, and the whole temperature of charing is 500 ℃～1000 ℃, and rare gas element is argon gas or nitrogen, and flow velocity is 10～200ml/min.
Effect of the present invention and benefit are:
(1) adopt inorganic nano-particle, metallic particles or metal-salt, organic additive etc. that carbon-film pore structure is regulated and control, technology is simple, easy handling.
(2) can prepare according to actual needs by the content of control hydridization species and have different flux and hybrid carbon film optionally.
(3) can prepare at the isolating mould material of special gas by the kind that changes additive.Realization to institute's divided gas flow " cut the garment according to the figure?.
(4) partial polymer need not to synthesize, and can directly adopt commercially available product as raw material, thereby shortens process of industrialization, is easy to realize commercially producing.
(5) significantly improve the permeation flux of gas, and the separation selectivity of gas does not reduce significantly.
Embodiment
Be described in detail the specific embodiment of the present invention and embodiment below in conjunction with technical scheme.
Embodiment 1
Get 0.6 gram exsiccant nano-ZSM-5 powder and place beaker (1), get 20g N,N-dimethylacetamide (DMAC) and pour in the beaker, stirred 1 hour ultrasonic 1 hour afterwards.Take by weighing the 20g polyamic acid again and place beaker (2), under agitation the solution in the beaker (1) was added to fall beaker (2) and continuously stirring 10 hours, adopt the knifing method to make flat sheet membrane above-mentioned mixing solutions, adopt pickling process that it is coated on supporter such as porous ceramic pipe, porous stainless steel, porous charcoal pipe and the porous silicon plate etc. and make composite membrane; Through the 10h drying, film is put into charring furnace, under argon shield, be warming up to 600 ℃ and constant temperature 2 hours with 5 ℃/min, treat that it is cooled to just can take out below 100 ℃.
The gas permeability data of the hybrid carbon film for preparing are (30 ℃ of probe temperatures):
Supporter Infiltration capacity (Barrer) Selectivity
H 2 CO 2 O 2 N 2 H 2/N 2 CO 2/N 2 O 2/N 2
Do not have 1078 884 431 30 36 29 14.4
The tubulose charcoal 998 694 351 27 37 29.5 13
Stainless steel tube 1050 874 420 34 31 25.7 12.5
Vitrified pipe 889 754 224 18.7 57 40.3 12
Silicon chip 1203 1002 520 34.7 34.7 29 15
1Barrer＝10 -10?cm 3(STP)?cm?cm -2?s -1?cm?Hg -1
Embodiment 2
Get 0.6 gram exsiccant nanometer Pt powder and place beaker (1), get 20g N,N-dimethylacetamide (DMAC) and pour in the beaker, stirred after 5 hours ultrasonic 1 hour.Take by weighing the 20g polyamic acid again and place beaker (2), under electric mixer stirs, the solution in the beaker (1) is dropwise added down beaker (2), stir after 5 hours and adopt the knifing method to make flat sheet membrane above-mentioned mixing solutions, adopt spread coating that it is coated on supporter such as porous ceramic plate, porous stainless steel plate, porous charcoal pipe and the porous silicon plate etc. and make composite membrane; Through the 8h drying, film is put into charring furnace, under argon shield, be warming up to 700 ℃ and constant temperature 1.5 hours with 1 ℃/min. treat that it is cooled to just can take out below 100 ℃.
The gas permeability data of the hybrid carbon film for preparing are (30 ℃ of probe temperatures)
Supporter Infiltration capacity (Barrer) Selectivity
H 2 CO 2 O 2 N 2 H 2/N 2 CO 2/N 2 O 2/N 2
Do not have 356 251 108 8.5 42 30 12.7
The tubulose charcoal 284 204 98 8.2 35 25 12
Stainless steel plate 306 245 101 8.2 37 30 12.3
Ceramic plate 289 225 88 8 36 28 11
Silicon chip 402 354 120 9.2 44 38 13
1Barrer＝10 -10?cm 3(STP)cm?cm -2?s -1?cm?Hg -1
Embodiment 3
Get 1.0 gram AgNO 3Solution places beaker (1), gets 15g N,N-dimethylacetamide (DMAC) and pours in the beaker, stirs after 7 hours ultrasonic 1.5 hours.Take by weighing the 18g polyamic acid again and place beaker (2), under electric mixer stirs, the solution in the beaker (1) is dropwise added down beaker (2), adopt the knifing method to make flat sheet membrane above-mentioned mixing solutions 1500 rev/mins of high-speed stirring after 3 hours, adopt the ultrasonic deposition method that it is deposited on supporter such as porous ceramic pipe, porous stainless steel, porous carbon slab and the porous silicon plate etc. and make composite membrane; Through the 7h drying, film is put into charring furnace, under argon shield, be warming up to 650 ℃ and constant temperature 2 hours with 2.5 ℃/min. treat that it is cooled to just can take out below 100 ℃.
The gas permeability data of the hybrid carbon film for preparing are (30 ℃ of probe temperatures)
Supporter Infiltration capacity (Barrer) Selectivity
H 2 CO 2 O 2 N 2 H 2/N 2 CO 2/N 2 O 2/N 2
Do not have 442 350 253 15 29 23 17
The porous carbon slab 352 224 221 15.8 22 14 14
Stainless steel tube 389 206 204 14.8 26 14 13.8
Vitrified pipe 342 281 206 15.8 22 18 13
Silicon chip 485 382 266 16.6 29 23 16
1Barrer＝10 -10?cm 3(STP)cm?cm -2?s -1?cm?Hg -1
Embodiment 4
Get the 25g tetraethoxy and place beaker (1), get in the 30ml ethanol adding beaker and stirred one hour down at 60 ℃.Get 30ml ethanol and place beaker (2), get 7.5g water and 0.83gHCl and place beaker (2) and stir.Solution in the beaker (2) is joined in the beaker (1), stir the silicon sol that 1h forms homogeneous.Take by weighing the 20g polyamic acid and place beaker (3), get the middle colloidal sol of beaker (1) and join in the beaker (3), and stir.Adopt the knifing method to make flat sheet membrane above-mentioned mixing solutions, adopt spraying method that it is coated on supporter such as porous ceramic pipe, porous stainless steel, porous charcoal pipe and the porous silicon plate etc. and make composite membrane; Through the 9h drying, film is put into charring furnace, under argon shield, be warming up to 750 ℃ and constant temperature 2 hours with 0.5 ℃/min. treat that it is cooled to just can take out below 100 ℃.
The gas permeability data of the hybrid carbon film for preparing are (30 ℃ of probe temperatures)
Supporter Infiltration capacity (Barrer) Selectivity
H 2 CO 2 O 2 N 2 H 2/N 2 CO 2/N 2 O 2/N 2
Do not have 4580 3250 1025 176 26 18 5.8
The tubulose charcoal 3584 2850 889 165 22 17 5.4
Stainless steel tube 4350 3620 1022 170 26 21 6.0
Vitrified pipe 3984 2250 998 204 20 11 4.9
Silicon chip 5580 3520 1050 169 33 21 6.2
1Barrer＝10 -10?cm 3(STP) cm?cm -2?s -1?cm?Hg -1
Embodiment 5
Get the 20g titanium ethanolate and place beaker (1), get in the 25ml ethanol adding beaker and stirred one hour down at 70 ℃.Get 20ml ethanol and place beaker (2), get 7g water and 0.6gHCl again and place beaker (2) and stir.Solution in the beaker (2) is dropwise joined in the beaker (1), and stir the colloidal sol that 1h forms homogeneous down at 65 ℃.Take by weighing the 15g polyamic acid and place beaker (3), get that a certain amount of colloidal sol joins in the beaker (3) in the beaker (1), and high-speed stirring 1h.Adopt knifing, ultrasonic deposition method to make flat sheet membrane or it is coated on supporter such as porous ceramic plate, porous stainless steel plate, porous charcoal pipe and the porous silicon plate etc. above-mentioned mixing solutions and make composite membrane; Through the 10h drying, film is put into charring furnace, under argon shield, be warming up to 750 ℃ and constant temperature 2 hours with 3 ℃/min. treat that it is cooled to just can take out below 100 ℃.
The gas permeability data of the hybrid carbon film for preparing are (30 ℃ of probe temperatures)
Supporter Infiltration capacity (Barrer) Selectivity
H 2 CO 2 O 2 N 2 H 2/N 2 CO 2/N 2 O 2/N 2
Do not have 5050 3251 1150 209 24 16 5.5
The tubulose charcoal 4850 2581 1024 205 24 13 5.0
Stainless steel plate 5120 3655 1540 266 19 14 5.8
Ceramic plate 4745 3452 1102 225 21 15 4.9
Silicon chip 5872 4454 1423 237 25 19 6.0
1Barrer＝10 -10?cm -3(STP)cm?cm -2?s -1?cm?Hg -1
Embodiment 6
The 5g polyethersulfone ketone is dissolved in the solution that is configured to 18%wt in the n-formyl sarcolysine base pyrrolidone, and the impurity in the solution is fallen in vacuum filtration through filter cloth, and standing and defoaming 20h added 1g nanometer 4A molecular sieve continuously stirring 10 hours again.Adopt the knifing method to make flat sheet membrane above-mentioned mixing solutions, adopt pickling process that it is coated on supporter such as porous ceramic pipe, porous stainless steel, porous charcoal pipe and the porous silicon plate etc. and make composite membrane; Through the 7h drying, film is put into pre-oxidation furnace, be under the 100ml/min in air flow quantity, control temperature rise rate be 1 ℃/min at 400 ℃ of preoxidation 30min, obtain the preoxidation film.Preoxidation polyethersulfone ketone film is put in the tubular type charring furnace, and the control temperature rise rate is 1 ℃/min, is under the 200ml/min at nitrogen flow, is warming up to 750 ℃ of constant temperature 60min, treats that it is cooled to just can take out below 100 ℃.
The gas permeability data of the hybrid carbon film for preparing are (30 ℃ of probe temperatures)
Supporter Infiltration capacity (Barrer) Selectivity
H 2 CO 2 O 2 N 2 H 2/N 2 CO 2/N 2 O 2/N 2
Do not have 5324 4571 541 68 78 67 8
The tubulose charcoal 4521 3584 485 59 77 61 8.2
Stainless steel tube 5541 4517 524 62 89 73 8.5
Vitrified pipe 4835 3845 561 72 67 53 7.8
Silicon chip 5985 4457 598 67 89 67 8.9
1Barrer＝10 -10?cm 3(STP)?cm?cm -2?s -1cm?Hg -1
Embodiment 7
With the 90g furfuryl alcohol, 4g iodine and 20g nanometer Cu put into the there-necked flask that prolong is housed, and stir the synthetic nanometer Cu poly furfuryl alcohol mixing solutions that contains of 5h original position; Adopt the knifing method to make flat sheet membrane above-mentioned solution, adopt pickling process that it is coated on supporter such as porous ceramic pipe, porous stainless steel, porous charcoal pipe and the porous silicon plate etc. and make composite membrane; , put it in 65 ℃ of baking ovens dry 18 hours, put it into then in the charring furnace, the temperature rise rate with 6.5 ℃/min under argon shield rises to 750 ℃, and constant temperature 1.5 hours, naturally cools to room temperature then.
The gas permeability data of the hybrid carbon film for preparing are (30 ℃ of probe temperatures)
Supporter Infiltration capacity (Barrer) Selectivity
H 2 CO 2 O 2 N 2 H 2/N 2 CO 2/N 2 O 2/N 2
Do not have 854 654 100 10 85 65 10
The tubulose charcoal 753 584 89 9 84 65 9.9
Stainless steel tube 899 702 113 12 75 59 9.4
Vitrified pipe 726 523 102 11 66 48 9.0
Silicon chip 886 772 120 11 81 70 11
1Barrer＝10 -10cm 3(STP)cm?cm -2?s -1?cm?Hg -1

Claims (10)

1. the preparation method of a nano hybrid carbon film; be in the preparation process of carbon membrane; by in presoma, introducing inorganic nano-particle, metallic particles or the hotchpotchs such as metal-salt and organic additive that gas-permeable had promoter action; and the kind of strict controlled doping thing, content, doping way and condition of carbonization; prepare nano hybrid carbon film, it is characterized in that:
(1) methods such as employing blend, colloidal sol-gel such as various inorganic nano-particles, metallic particles, metal-salt or organic additive is dispersed or dissolved in the solvent, hotchpotch is dispersed in the solvent through stirring;
(2) above-mentioned solution is dropwise joined in the various polymers solns, and stir simultaneously, till the mixing solutions that forms homogeneous, or adopt original position synthetic method that above-mentioned hotchpotch is incorporated into and make mixing solutions in the polymkeric substance;
(3) mixing solutions is adopted different system film modes make flat sheet membrane or it is coated on the different supporters and make composite membrane, prepare the precursor polymer hybridized film through solvent evaporation, drying;
(4) put into charring furnace again after the polymer hybrid film is directly put into charring furnace or first preoxidation, charing obtains hybrid carbon film under rare gas element or vacuum, or directly puts into the first preoxidation of charring furnace charing again.
2. the preparation method of a kind of nano hybrid carbon film according to claim 1 is characterized in that hotchpotch is inorganic nano-particle ZSM-5,4A, carbon molecular sieve, SiO 2, TiO 2, HTS, metallic particles such as Ag, Cu, Pt, Pd, Au, metal-salt such as AgNO3, CuNO3, organic additive such as polyoxyethylene glycol, polyvinylpyrrolidone etc. a kind of.
3. the preparation method of a kind of nano hybrid carbon film according to claim 1 is characterized in that it being that the add-on of hotchpotch is 3%～50% (quality %).
4. the preparation method of a kind of nano hybrid carbon film according to claim 1 is characterized in that introducing the employed blending mode of various hotchpotchs in presoma is a kind of of methods such as blending method, sol-gel method, in-situ synthesis.
5. the preparation method of a kind of nano hybrid carbon film according to claim 1, it is characterized in that for guaranteeing that dopant species is dispersed in the polymkeric substance uniformly, must in advance dopant species be dispersed in the solvent, should adopt suitable churning time and special dispersing method; Churning time should be controlled at 1h～10h, and dispersing method is that ultrasonic dispersing or high-speed stirring are disperseed.
6. the preparation method of a kind of nano hybrid carbon film according to claim 1 is characterized in that employed solvent is: N,N-dimethylacetamide, n-formyl sarcolysine base pyrrolidone, n-formyl sarcolysine yl acetamide, dimethyl sulfoxide (DMSO), chloroform etc. a kind of.
7. the preparation method of a kind of nano hybrid carbon film according to claim 1, it is characterized in that selected polymer precursor is: various polyimide, polyetherimide, polyethersulfone ketone, poly furfuryl alcohol, phenolic resin, polyvinylidene chloride, polyvinylidene difluoride (PVDF), polyacrylonitrile, various Mierocrystalline cellulose, polysulfones, polyethersulfone etc. a kind of.
8. the preparation method of a kind of nano hybrid carbon film according to claim 1 is characterized in that the coating method that adopts is a kind of of knifing, pickling process, spread coating, spraying method or ultrasonic deposition method.
9. the preparation method of a kind of nano hybrid carbon film according to claim 1 is characterized in that the supporter that adopts is a kind of of porous ceramic pipe or plate, porous stainless steel or plate, porous charcoal pipe or plate and porous silicon plate.
10. the preparation method of a kind of nano hybrid carbon film according to claim 1 is characterized in that being controlled at the preoxidation temperature of polymer hybrid film below 400 ℃; Carbonization process under vacuum condition, carry out or gas shield under carry out, shielding gas is a kind of of nitrogen, argon gas, gas flow rate should be controlled at 10～200ml/min; The condition of carbonization that adopts is: charing is 500 ℃～1000 ℃ of temperature eventually, and temperature rise rate is controlled at 0.1 ℃/min～10 ℃/min.
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CN105536562B (en) * 2016-01-15 2017-10-13 鲁东大学 A kind of preparation method of charcoal montmorillonite Composite film
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CN109152982A (en) * 2016-04-29 2019-01-04 陶氏环球技术有限责任公司 The improved transition metal and preparation method thereof containing Carbon Molecular Sieve Membrane
CN109152982B (en) * 2016-04-29 2021-12-28 陶氏环球技术有限责任公司 Transition metal containing carbon molecular sieve membrane and preparation method thereof
CN107603215A (en) * 2017-09-22 2018-01-19 安庆市虹泰新材料有限责任公司 A kind of preparation method of polyamide copper composite membrane
CN107983178A (en) * 2017-12-12 2018-05-04 安徽启东热能科技有限公司 One kind is used for the separated permeable membrane of lighter hydrocarbons
CN107983178B (en) * 2017-12-12 2021-06-29 安徽启东热能科技有限公司 Permeable membrane for light hydrocarbon separation
WO2021109708A1 (en) * 2019-12-07 2021-06-10 中化泉州能源科技有限责任公司 Carbon molecular sieve membrane and preparation method therefor
CN112645322A (en) * 2020-11-30 2021-04-13 河南省大潮炭能科技有限公司 Carbon soaking method for super capacitor

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