CN1036767C - Permeable hydrogen membrane and preparing process thereof - Google Patents
Permeable hydrogen membrane and preparing process thereof Download PDFInfo
- Publication number
- CN1036767C CN1036767C CN93108889A CN93108889A CN1036767C CN 1036767 C CN1036767 C CN 1036767C CN 93108889 A CN93108889 A CN 93108889A CN 93108889 A CN93108889 A CN 93108889A CN 1036767 C CN1036767 C CN 1036767C
- Authority
- CN
- China
- Prior art keywords
- membrane
- hydrogen
- permeation membrane
- hydrogen permeation
- permeable hydrogen
- 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
Images
Abstract
The present invention relates to a permeable hydrogen membrane with high-strength selectivity and a preparing process thereof. The solution of a prepolymerization monomer of polybenzimidazole pyrrolidone is uniformly coated on metal nets, and under the protection of nitrogen gas, the permeable hydrogen membrane which is reinforced by the metal nets and has with high-strength selectivity is prepared by polymerization and high-temperature solidification. The permeable hydrogen membrane and a homogenizing permeable hydrogen membrane which is not reinforced by the metal nets have the same hydrogen selectivity, and the permeable hydrogen membrane totally have great improvement in the aspects of mechanical strength, permeable hydrogen rate, membrane forming conditions, the successful rate of finished products, etc. Accordingly, the permeable hydrogen membrane of an aromatic heterocyclic organic high molecular compound can be applied in the field of membrane separation technique.
Description
The present invention relates to a kind of high-intensity selectivity hydrogen permeation membrane and preparation method thereof, or rather, the present invention is a kind of selectivity hydrogen permeation membrane that strengthens with woven wire and preparation method thereof, belongs to the field of membrane separation technique.
Polybenzimidazoles pyrrolones (Polypyrrones) is polycondensation in polar solvent by aromatics tetracarboxylic dianhydride and aromatics tetramine, and a kind of notch cuttype aromatic heterocycle polymer compound (Lu Fengcai etc., aerospace material technology, the 2nd phase that obtain through high-temperature process, 15～18 pages, 1984).The homogeneous film that makes with it is a kind of rich hydrogen film (Lu Fengcai etc., macromolecule journal, the 5th phase, 342～346 pages that hydrogen had better selective permeation.1987) because the good selectivity of this homogeneous film, the CN91217597.4 utility model patent is with its pre-separation device as selectivity hydrogen detector.Yet because the existence of following unfavorable factor, the preparation condition of this homogeneous membrane requires relatively harsher, is difficult to produce in batches:
1, can make the hydrolysis of pre-polymerization monomer and stop polycondensation reaction, the strict humidity that controls environment in the film forming procedure owing to moisture content.
2, the pre-polymerization monomer need carry out preliminary polymerization and remove desolvate (time needs 1.5～2 hours approximately) with certain thickness uniform spreading on the flat board of horizontal positioned during film forming, in this process, is subject to the interference of environmental condition.In addition, the uniformity of this finished film is also wayward, usually is thick, the intermediate thin of periphery, causes the yield of film forming very low.
3, film forming is thin more, and the permeability of hydrogen is good more, but for the finished film that guarantees to obtain has enough intensity, film again can not be too thin, therefore limited this approach of further raising membranous permeation rate.
At the practical problem of above existence, purpose of the present invention is exactly to propose a kind of film and the film build method that are matrix with this new hydrogen-rich materials, makes it can be applied to reality better.
The present invention is the pre-polymerization monomer solution with certain density polybenzimidazoles pyrrolones; under certain conditions, be coated in equably on the woven wire, after process preliminary polymerization and steaming desolventize; place in the ageing oven, high-temperature polycondensation becomes the hydrogen permeation membrane that strengthens with woven wire under protection of nitrogen gas.Because this hydrogen permeation membrane is to be matrix with the high molecular polymer that is attached on the woven wire, compares with single homogeneous membrane, its mechanical strength greatly increases.In addition, can repeatedly apply in the preparation, so the adjustable range of hydrogen permeation membrane thickness is also much wide than single homogeneous membrane, both can coat thick film, also can coat ultrathin membrane.This hydrogen permeation membrane in the preparation, just needed time of collecting process only is 1/3rd or shorter (10 to 25 minutes) of homogeneous membrane for it.When preparation hydrogen permeation membrane of the present invention, can not be subjected to the interference of ambient humidity to greatest extent.The used woven wire of the present invention has two effects, the one, as the skeleton of film, increase the finished product film strength, two provide and make the equally distributed mesh of organic macromolecule pre-polymerization physical efficiency, make the thickness of finished film even, thereby the shortcoming of peripheral thick, the intermediate thin that must take place when having avoided the homogeneous membrane film forming.
Accompanying drawing is seen in hydrogen permeation membrane preparation signal of the present invention.In the accompanying drawings, the 1st, last cylinder, the 2nd, bottom roll, the 3, the 6th, fixing last item, the 4th, pre-polymerization monomer solution, the 5th, woven wire.Preparation method's step is as follows:
1, the method for just etc. delivering according to above-mentioned Lu Feng, synthetic aromatic heterocycle polymer monomer resin.
2, use N, N '-dimethyl formamide (water content is less than 500ppm) is diluted to concentration at 3～15% (weights) with resin, and preferably the solution of 5～8% (weight) scope seals standby.
3, with commercially available woven wire (300～800 order), its material such as stainless steel, brass, nickel etc. all can, better with stainless steel, be cut into the size of length and width appropriateness, use the acetone soaking and washing, dry stand-by.
4, above-mentioned woven wire is installed in the coating apparatus of accompanying drawing signal, and adjust cylinder 1 and two fixedly last item 3 and 6 gap, degree of tightness is suitable when extremely mobile.
5, in the coating jar, add an amount of resin solution.
6, back and forth spur woven wire for several times with average rate, making the silk screen hole is that resin solution evenly is coated with.
7, dry up the woven wire that is coated with resin solution with hair-dryer.
8, the woven wire that dries up is placed in the airtight container, under nitrogen protection, is warming up to 300 ℃, kept constant temperature then 2～3 hours, make the abundant polymerizing curable film forming of aromatic heterocycle polymer monomer resin of woven wire surface coating.
9, cool the temperature to room temperature, promptly obtain the selectivity hydrogen permeation membrane that woven wire of the present invention strengthens.
In the process of above-mentioned preparation, thickness and the uniformity of the 2nd, 6,7 steps to hydrogen permeation membrane has direct influence.For guaranteeing the even of coating, the 6th, 7 liang of step wanted twice of repetitive operation in normal circumstances at least.Lower resin concentration, coating repeatedly, the process that dries up are The key factor to the hydrogen permeation membrane of making even coating.By the serviceability data of following embodiment and oxygen permeation membrane as can be seen, the selectivity hydrogen permeation membrane that woven wire of the present invention strengthens is identical with homogeneous membrane to selection performance and other performance of hydrogen, but mechanical strength and saturating hydrogen rate have significant improvement.
Embodiment 1
The pre-polymerization monomer concentration is 7.9% (weight), 325 order stainless steel cloths, and by above-mentioned preparation method's coating film forming, 6,7 liang of steps wherein repeat twice.Be installed in the hydrogen permeation membrane that makes on " the hydrogen content detector " of CN9l217597.4 utility model patent, strengthen hydrogen permeation membrane with woven wire of the present invention and replace homogeneous membrane, thermal conductivity detector (TCD) (TCD) bridge stream 112mA, 80 ℃ of temperature, nitrogen is carrier gas, flow 30ml/ branch, woven wire strengthens membrane area 4.3cm
2, 80 ℃ of temperature, sample gas are the hydrogen and the nitrogen mixed air of north, Beijing branch science gas companies preparation, hydrogen concentration is 20.9% (volume).
Quantitative response relational expression to hydrogen is: Y=0.456X
In the formula: Y is a response signal, mV;
X is the concentration expressed in percentage by volume of hydrogen.
When being sample with the liquefied gas, signal response is 0.82mV.
Under similarity condition, thickness is that the homogeneous hydrogen permeation membrane of 30 μ is Y=0.167X to the quantitative response relational expression of hydrogen
The pre-polymerization monomer concentration is 10% (weight), 325 order stainless steel cloths, and by above-mentioned preparation method's coating film forming, 6,7 liang of step triplicates wherein.On same hydrogen content detector, measure.Operating condition is all identical with embodiment 1.
Quantitative response relational expression to hydrogen is: Y=0.133X
When being sample with the liquefied gas, signal response is 0.04mV
The pre-polymerization monomer concentration is 5.4% (weight), 325 order stainless steel wire hilllocks, and by above-mentioned preparation method's coating film forming, 6,7 liang of steps wherein repeat once.Its condition determination is with embodiment 1.
Quantitative response relational expression to hydrogen is: Y=2.21X
When being sample with the liquefied gas, signal response is 0.61mV
The pre-polymerization monomer concentration is 5.4% (weight), 325 order stainless steel cloths, and by above-mentioned preparation method's coating film forming, 6,7 liang of step triplicates wherein.Its condition determination is with embodiment 1.
Quantitative response relational expression to hydrogen is: Y=0.986X
The pre-polymerization monomer concentration is 5.0% (weight), 400 order stainless steel cloths, and by above-mentioned preparation method's coating film forming, 6,7 liang of steps wherein repeat six times, and its condition determination is with embodiment 1.
Quantitative response relational expression to hydrogen is: Y=0.4X
When being sample with the liquefied gas, signal response is 0.72mV
The pre-polymerization monomer concentration is 5.0% (weight), 800 order stainless steel cloths, and by above-mentioned preparation method's coating film forming, 6,7 liang of step triplicates wherein, its condition determination is with embodiment 1.
Quantitative response relational expression to hydrogen is: Y=0.797X
When being sample with the liquefied gas, signal response is 0.91mV
In above listed examples, the quantitative response of hydrogen is concerned that the slope k among the Y=kX is relevant with the saturating hydrogen rate of hydrogen permeation membrane, saturating hydrogen rate is big more, and corresponding k value is also just big more.Response to oil liquefied gas has reflected that then hydrogen permeation membrane (is generally C to hydrocarbon gas
1～C
5Hydrocarbon) selectivity.As can be seen, give in the example except that individual cases, to the response of oil liquefied gas all less than the response of 1% hydrogen concentration gas.So just illustrated that when this hydrogen permeation membrane was used for detecting the hydrogen content of oil gas, the interference of hydrocarbon component was very little.
Claims (4)
1. one kind is the preparation method of choice of base hydrogen permeation membrane with polybenzimidazoles pyrrolones aromatic heterocycle polymer compound, it is characterized in that the pre-polymerization monomer solution is coated on the close-meshed woven wire equably, at least repeat twice, and process polycondensation and the whole poly-selectivity hydrogen permeation membrane that forms in high temperature and nitrogen with the woven wire enhancing, said pre-polymerization monomer solution is that solid content is that 3～15% (weight) aromatics tetracarboxylic dianhydride and aromatics tetramine are dissolved in the polar solvent and form, said polar solvent is N, N '-dimethyl formamide or N, N '-dimethylacetylamide.
2. according to the said hydrogen permeation membrane preparation method of claim 1, the solid content that it is characterized in that said pre-polymerization monomer solution is 5～8% (weight).
3. according to the said hydrogen permeation membrane preparation method of claim 1, it is characterized in that said dusting cover order woven wire is a stainless steel cloth, the scope of its sieve mesh is 200～1000.
4. one kind is the hydrogen permeation membrane of matrix with polybenzimidazoles pyrrolones aromatic heterocycle polymer compound, it is characterized in that it makes with the said method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93108889A CN1036767C (en) | 1993-07-29 | 1993-07-29 | Permeable hydrogen membrane and preparing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN93108889A CN1036767C (en) | 1993-07-29 | 1993-07-29 | Permeable hydrogen membrane and preparing process thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1098024A CN1098024A (en) | 1995-02-01 |
| CN1036767C true CN1036767C (en) | 1997-12-24 |
Family
ID=4987386
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93108889A Expired - Fee Related CN1036767C (en) | 1993-07-29 | 1993-07-29 | Permeable hydrogen membrane and preparing process thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1036767C (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337154A (en) * | 1979-04-04 | 1982-06-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Crosslinked composite semipermeable membrane |
| US5262056A (en) * | 1992-11-30 | 1993-11-16 | Board Of Regents, The University Of Texas System | Polyamides and polypyrrolones for fluid separation membranes |
-
1993
- 1993-07-29 CN CN93108889A patent/CN1036767C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4337154A (en) * | 1979-04-04 | 1982-06-29 | Nippon Shokubai Kagaku Kogyo Co., Ltd. | Crosslinked composite semipermeable membrane |
| US5262056A (en) * | 1992-11-30 | 1993-11-16 | Board Of Regents, The University Of Texas System | Polyamides and polypyrrolones for fluid separation membranes |
Non-Patent Citations (1)
| Title |
|---|
| 高分子学报，[5] 1987.1.1 卢凤才等 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1098024A (en) | 1995-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Effects of polymerization conditions on hydrophilic groups in aromatic polyamide thin films | |
| US3607365A (en) | Vapor phase method of coating substrates with polymeric coating | |
| CA1190100A (en) | Process for producing aromatic polyimide composite separating membrane | |
| US5851646A (en) | Prepreg, process for producing the same and printed circuit substrate/board using the same | |
| US4602922A (en) | Method of making membranes for gas separation and the composite membranes | |
| Illing et al. | Preparation and characterisation of polyaniline based membranes for gas separation | |
| US3829324A (en) | Bonding condensation polymers to polymeric base materials | |
| US5281692A (en) | Elongated object made of a copolymer of carbon monoxide and an olefinically unsaturated monomer | |
| CN105709611B (en) | A kind of poly- pyrrole throat/compound porous catalytic membrane of polyimides and preparation method thereof | |
| Feldheim et al. | Switchable gate membranes. Conducting polymer films for the selective transport of neutral solution species | |
| Takizawa et al. | Permeability of a series of alcohols through poly (γ-methyl-d-glutamate) | |
| Kitani et al. | Flexible polyaniline | |
| Trushinski et al. | Polysulfonamide thin-film composite reverse osmosis membranes | |
| CN1036767C (en) | Permeable hydrogen membrane and preparing process thereof | |
| US4454178A (en) | Poly(acetylene) films and their production | |
| CN1173828A (en) | Gas permeable fabric | |
| Bearzotti et al. | Fast humidity response of a metal halide-doped novel polymer | |
| Semenova et al. | Dependence of permeability through polyimide membranes on state of gas, vapor, liquid and supercritical fluid at high temperature | |
| CN111154433A (en) | Fluorine-containing resin mixture and copper-clad plate prepared from same | |
| Tchangai et al. | Water sorption in polyamide–imide films and its effect on dielectric loss | |
| Lai et al. | Preparation of polycarbonate/metal salt gas separation membranes | |
| CN112981615B (en) | Nano carbon fiber and preparation method and application thereof | |
| US5430073A (en) | Process for preparing polymers and mouling compounds based thereon | |
| CN112934002A (en) | Aziridine crosslinked sodium polyacrylate separation membrane and preparation method and application thereof | |
| CN112852155A (en) | Preparation method of polyimide/black phosphorus alkene flame retardant powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| 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 |