CN100358616C - Process for preparing silicon separating films with specialized selectivity to natural products - Google Patents
Process for preparing silicon separating films with specialized selectivity to natural products Download PDFInfo
- Publication number
- CN100358616C CN100358616C CNB2006100139630A CN200610013963A CN100358616C CN 100358616 C CN100358616 C CN 100358616C CN B2006100139630 A CNB2006100139630 A CN B2006100139630A CN 200610013963 A CN200610013963 A CN 200610013963A CN 100358616 C CN100358616 C CN 100358616C
- Authority
- CN
- China
- Prior art keywords
- solution
- ethanol
- hours
- natural products
- dissolved
- 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
Landscapes
- Silicon Compounds (AREA)
Abstract
The present invention discloses a method for preparing silicon separating films with specialized selectivity on natural products, which belongs to the technical field of the film preparation. The present invention has the steps that a template agent is dissolved in a solvent which contains ethanol to obtain a template agent solution; then, function monomers are added in the template agent solution; condensing back flow is carried out after the addition of a stabilizing agent; a silane predecessor is prepared after a solvent is removed; tetraethoxy silane is dissolved in an ethanol solution, and the silane predecessor is added in the ethanol solution; a sol is prepared through condensing back flow, and then, the sol is aged at room temperature; a treated Al2O3 plate is immersed in the sol, and is repeatedly dipped; then, the Al2O3 plate is sintered in a muffle furnace to elute the template agent, and the silicon separating film is obtained after the Al2O3 plate is dried. The method of the present invention has the advantages that the preparation process is simple; the prepared silicon separating film realizes the selective separation of a material on a molecular level; the molecular recognition process can be realized in an aqueous phase. The method is suitable for the separation of natural products, and has wide versatility.
Description
Technical field
The present invention relates to a kind of preparation method who natural products is had the siliceous diffusion barrier of single-minded selectivity.The technology of preparing that belongs to diffusion barrier.
Background technology
Membrane separation technique is 21st century one of the most potential unit operations, has broad application prospects.Membrane separation technique has many advantages, does not undergo phase transition as separation process, and energy consumption is low; Separation is big, but continued operation, efficient height, non-secondary pollution; Operating temperature is low, is applicable to separation, purification and the enrichment of heat-sensitive substance (fruit juice, enzyme, medicine); Device is simple, and is easy to operate etc., but also has a lot of problems in the practical application, serious such as film pollution and deterioration; The most of organic film materials especially heat endurance of hydrophilic material are relatively poor, and mechanical strength is low, chemical proof difference etc.; At present, the selectivity that membrane technology separates realizes by molecular cut off, but natural products, medicine or some chemical industry series products, molecular weight ratio is more approaching, be difficult to accurately separate with existing membrane technology, so improve the selectivity of film, film is separated reach accurate separation, be one of insoluble problem of facing of present membrane technology.Molecular engram is the technology of the preparation high-selectivity adsorbing material that grows up over nearly 20 years, it has imitated the action principle of the key and the lock of living nature, treat separation component and can carry out Selective Separation from the molecule rank, but function monomer that molecular imprinting is used and crosslinking agent majority are organic compound, and molecular engram and molecular recognition process all can not realize in polar solvent, and natural products, medicine or some chemical industry series products much all are water miscible materials, exist difficulty on using.
Summary of the invention
The object of the present invention is to provide a kind of preparation to have the method for single-minded selective diffusion barrier, prepared diffusion barrier can be realized the high selectivity of water miscible natural products is separated.
For achieving the above object, the present invention is realized by following technical proposals.With the organosilan is function monomer, is that the template agent prepares predecessor with a certain class natural products component, carries out the synergetic hydrolysis reaction with tetraethoxysilane then, forms colloidal sol, again with Al
2O
3For carrier is filmed, carry out just having obtained having single-minded optionally siliceous diffusion barrier behind the sintering.It is characterized in that comprising following concrete steps:
1.Al
2O
3The pre-treatment of carrier is earlier γ-Al
2O
3The plate surface finish is smooth, boiled 10~50 minutes in hydrochloric acid, nitric acid or the phosphoric acid solution with 0.01~0.15mol/L again, then with boiling 10~50 minutes in the NaOH of 0.01~0.15mol/L or the potassium hydroxide solution, after spending deionised water 1~6 time, placed ethanol more ultrasonic 10~50 minutes, and spent deionised water and be placed on dried for standby under the room temperature.
2. the preparation of silane precursor, the template agent is dissolved in ethanol, pyridine, be made into mass concentration in methyl-sulfoxide or the oxolane and be 0.2%~30% solution, described template agent is: rutin, Quercetin, genistein, morphine, mufangchine, unabain or andrographolide, get template solution after treating to dissolve fully, volume ratio by template solution and function monomer is 20: 1~10 adding gamma-aminopropyl-triethoxy-silanes, γ-chloro triethoxysilane or the 3-third isocyanide root triethoxysilane obtain precursor solution, the volume ratio 100: 1~10 of pressing precursor solution and stabilizing agent then adds N, N-dimethylformamide or N, N-dimethyl acetyl ammonia refluxed 10~36 hours down in 40 ℃~90 ℃.After reaction finishes, adopt rotary evaporation to remove to desolvate silane precursor.
3. the silane precursor that step 2 is made is dissolved in that to be made into mass concentration in the ethanol be 0.5%~10% solution, being 1: 5~20 to add tetraethoxysilanes with this liquor capacity ratio, regulate pH=4.5~6.1 with hydrochloric acid or acetic acid then, or regulate pH=7.9~9.2 with ammoniacal liquor or NaOH, being 100: 1~10 to add stabilizing agent N with regulating liquor capacity ratio behind the pH, N-dimethylformamide or N, N-dimethyl acetyl ammonia, under stirring state, adding volume ratio to the solution that is added with stabilizing agent is 5: 1~10 deionized waters, refluxed 8~12 hours down at 40 ℃~90 ℃ then, obtain homogeneous, stable sols.
4. the colloidal sol that step 3 is made ageing 1~6 hour under room temperature, the Al that step 1 is handled
2O
3Immersed in the colloidal solution after the ageing 6~9 seconds, dip-coating is 6~7 times repeatedly, obtains composite membrane.
5. the composite membrane that step 4 is made places Muffle furnace, and design temperature is 150~200 ℃, by the heating rate of 0.5 ℃/min~5 ℃/min, sintering 4~8 hours.
6. the composite membrane that sinters, again with mass concentration be 60%~80% ethanol, ethyl acetate, chloroform or dimethyl sulfoxide solution in the agent of 60 ℃~90 ℃ of following wash-out templates, wash-out promptly can be used for the separating natural product after 6~10 hours.
The invention has the advantages that preparation process is simple, prepared diffusion barrier mechanical strength height, the anti-pollution ability is strong, and temperature limit is wide, can on the molecule rank, realize Selective Separation to a certain material, and can realize the molecular recognition process at aqueous phase, can also be widely used in membrane bioreactor, film sensors, the chiral resolution of medicine, the lithium particle battery is specially adapted to the separating natural product, has versatility widely.
The specific embodiment
Embodiment one: the 100mg rutin is dissolved in the 10ml pyridine, the aminopropyl triethoxysilane and the 0.5ml N.N-dimethylformamide that add 0.5ml, 65 ℃ of following condensing refluxes 36 hours, after reaction finishes, pyridine is removed with rotary evaporator, promptly make the rutin predecessor, the tetraethoxysilane of 10ml is dissolved in the 50ml ethanolic solution, and add the rutin predecessor 5ml of above-mentioned preparation, add 1ml N again, N-dimethylformamide and 15ml deionized water are regulated pH=4.9 with HCL then, reflux down at 60 ℃ and to carry out synergetic hydrolysis in 10 hours and prepare Ludox, then ageing 2 hours under room temperature.Al
2O
3Plate is through polishing, after hydrochloric acid, NaOH decoction, the ethanol of 0.05mol/L are ultrasonic, immerse in the colloidal sol for preparing previously respectively again, dip-coating is 7 times repeatedly, place the Muffle furnace sintering then, the highest temperature is set at 170 ℃, heats up by 0.5 ℃/min, takes out after 6.5 hours, with 90% ethanolic solution rutin wash-out from xerogel is removed down at 60 ℃ then, drying promptly makes rutin is had single-minded selective silicon plasma membrane under room temperature.On homemade film evaluating apparatus the material liquid that contains Lu Ding 0.56mg/ml is separated, reaching the adsorption equilibrium time is 3.6 hours, is 87.2% to the selection rate of rutin.
Embodiment two: the 100mg Quercetin is dissolved in 20ml ethanol, the chloropropyl triethoxysilane and the 2.0mlN that add 5ml, the N-dimethylformamide, 70 ℃ of condensing refluxes 24 hours, after reaction finishes, oxolane sent out with the rotation steaming device remove, promptly make the Quercetin predecessor, the tetraethoxysilane of 15ml is dissolved in the 30ml ethanolic solution, and adds the Quercetin predecessor 5ml of above-mentioned preparation, add 3ml N then, N-dimethylformamide and 20ml deionized water, regulate pH=9.5 with NaOH again, reflux down at 60 ℃ then and carried out synergetic hydrolysis in 10 hours and prepare Ludox, then ageing 2.5 hours under room temperature.Al
2O
3Plate is through polishing, after hydrochloric acid, NaOH decoction, the ethanol of 0.10mol/L are ultrasonic, immerse in the colloidal sol for preparing previously respectively again, dip-coating is 6 times repeatedly, place the Muffle furnace sintering then, the highest temperature is set at 180 ℃, heats up by 1 ℃/min, takes out after 6 hours and makes composite membrane, with 80% ethyl acetate solution Quercetin wash-out from film is removed down at 80 ℃ then, drying promptly makes Quercetin is had the siliceous diffusion barrier of single-minded selectivity under room temperature.On homemade film evaluating apparatus the feed liquid that contains Quercetin 0.72mg/ml is separated, reaching the adsorption equilibrium time is 4 hours, is 81.6% to the selection rate of Quercetin.
Embodiment three: the morphine of 150mg is dissolved in the 30ml oxolane, the 3-third isocyanide root triethoxysilane and the 1.5ml N that add 10ml, N-dimethyl acetyl ammonia, 80 ℃ of condensing refluxes 12 hours, after reaction finishes, oxolane sent out with the rotation steaming device remove, promptly make the morphine predecessor, the tetraethoxysilane of 15ml is dissolved in the 30ml ethanolic solution, and adds the morphine predecessor 5ml of above-mentioned preparation, add 3ml N then, N-dimethylformamide and 20ml deionized water, regulate pH=6.5 with acetic acid again, reflux down at 60 ℃ then and carried out synergetic hydrolysis in 8 hours and prepare Ludox, then ageing 4 hours under room temperature.Al
2O
3Plate is through polishing, after hydrochloric acid, NaOH decoction, the ethanol of 0.15mol/L are ultrasonic, immerse in the colloidal sol for preparing previously respectively again, dip-coating is 6 times repeatedly, place the Muffle furnace sintering then, the highest temperature is set at 200 ℃, heats up by 2 ℃/min, takes out after 6 hours and makes composite membrane, with 80% chloroformic solution morphine wash-out from film is removed down at 80 ℃ then, drying promptly makes morphine is had the siliceous diffusion barrier of single-minded selectivity under room temperature.On homemade film evaluating apparatus the material liquid that contains morphine 0.63mg/ml is separated, reaching the adsorption equilibrium time is 4.5 hours, is 80.5% to the selection rate of morphine.
Embodiment four: the mufangchine of 80mg is dissolved in the 15ml methyl-sulfoxide, the aminopropyl triethoxysilane and the 1.5ml N that add 5ml, N-dimethyl acetyl ammonia, refluxed 20 hours down at 90 ℃, after reaction finishes, methyl-sulfoxide is removed with rotary evaporator, promptly make mufangchine compound precursor thing, the tetraethoxysilane of 8ml is dissolved in the 20ml ethanol, adds the mufangchine compound precursor thing 2ml of above-mentioned preparation, and add 0.5ml N, N-dimethylformamide and 5ml deionized water, regulate pH=4.5 with hydrochloric acid again, reflux down at 70 ℃ then and carried out synergetic hydrolysis in 10 hours and prepare Ludox, then ageing 3 hours under room temperature.Al
2O
3Plate is through polishing, immersing the front respectively after hydrochloric acid, NaOH decoction, the ethanol of 0.05mol/L are ultrasonic again prepares in the colloidal sol, dip-coating is 9 times repeatedly, place the Muffle furnace sintering then, the highest temperature is set at 200 ℃, heats up by 2 ℃/min, takes out after 8 hours and makes composite membrane, with 80% ethanolic solution mufangchine wash-out from film is removed down at 75 ℃ then, drying promptly makes mufangchine is had the siliceous diffusion barrier of single-minded selectivity under room temperature.On homemade film evaluating apparatus the material liquid that contains mufangchine 0.37mg/ml is separated, reaching the adsorption equilibrium time is 5 hours, is 86.8% to the selection rate of mufangchine.
Embodiment five: the unabain of 50mg is dissolved in the 10ml methyl-sulfoxide, the chloropropyl triethoxysilane and the 1.5ml N that add 3ml, the N-dimethylformamide, refluxed 12 hours down at 90 ℃, after reaction finishes, methyl-sulfoxide is removed with rotary evaporator, promptly make unabain compound precursor thing, the tetraethoxysilane of 10ml is dissolved in the 30ml ethanol, adds the unabain compound precursor thing 5ml of above-mentioned preparation, and add 1ml N, N-dimethylformamide and 15ml deionized water, regulate pH=8.1 with ammoniacal liquor again, reflux down at 70 ℃ then and carried out synergetic hydrolysis in 8 hours and prepare Ludox, then ageing 2 hours under room temperature.Al
2O
3Plate is through polishing, immersing the front respectively after hydrochloric acid, NaOH decoction, the ethanol of 0.11mol/L are ultrasonic again prepares in the immersion colloidal sol, dip-coating is 8 times repeatedly, use the Muffle furnace sintering then, the highest temperature is set at 170 ℃, heats up by 1 ℃/min, takes out after 8 hours and makes composite membrane, with 80% ethanolic solution unabain wash-out from film is removed down at 80 ℃ then, drying promptly makes unabain is had the siliceous diffusion barrier of single-minded selectivity under room temperature.On homemade film evaluating apparatus the material liquid that contains unabain 0.42mg/ml is separated, reaching the adsorption equilibrium time is 5 hours, is 85.9% to the selection rate of unabain.
Embodiment six: the andrographolide of 150mg is dissolved in the 30ml oxolane, the 3-third isocyanide triethoxysilane and the 2ml N that add 15ml, N-dimethyl acetyl ammonia, refluxed 24 hours down at 90 ℃, after reaction finishes, oxolane is removed with rotary evaporator, promptly make andrographolide compound precursor thing, the tetraethoxysilane of 10ml is dissolved in the 30ml ethanol, adds the andrographolide compound precursor thing 5ml of above-mentioned preparation, and add 1ml N, N-dimethylformamide and 15ml deionized water, regulate pH=5.2 with hydrochloric acid again, reflux down at 70 ℃ then and carried out synergetic hydrolysis in 30 hours and prepare Ludox, then ageing 2 hours under room temperature.Al
2O
3Plate is through polishing, after hydrochloric acid, NaOH decoction, the ethanol of 0.05mol/L are ultrasonic, immerse in the colloidal sol for preparing previously respectively again, dip-coating is 8 times repeatedly, place the Muffle furnace sintering then, the highest temperature is set at 200 ℃, heats up by 2 ℃/min, takes out after 7 hours and makes composite membrane, with 80% dimethyl sulfoxide solution andrographolide wash-out from film is removed down at 80 ℃ then, drying promptly makes andrographolide is had the siliceous diffusion barrier of single-minded selectivity under room temperature.On homemade film evaluating apparatus the material liquid that contains andrographolide 0.52mg/ml is separated, reaching the adsorption equilibrium time is 6 hours, is 87.8% to the selection rate of andrographolide.
Embodiment seven: the genistein of 100mg is dissolved in 20ml ethanol, the chloropropyl triethoxysilane and the 1ml N that add 10ml, N-dimethyl acetyl ammonia, refluxed 20 hours down at 85 ℃, after reaction finishes, ethanol is removed with rotary evaporator, promptly make genistein compound precursor thing, the tetraethoxysilane of 10ml is dissolved in the 30ml ethanol, adds the genistein compound precursor thing 5ml of above-mentioned preparation, and add 1ml N, N-dimethyl acetyl ammonia and 15ml deionized water, regulate pH=6.3 with acetic acid again, reflux down at 75 ℃ then and carried out synergetic hydrolysis in 24 hours and prepare Ludox, then ageing 2 hours under room temperature.Al
2O
3Plate is through polishing, after hydrochloric acid, NaOH decoction, the ethanol of 0.10mol/L are ultrasonic, immerse in the colloidal sol for preparing previously respectively again, dip-coating is 8 times repeatedly, then in the Muffle furnace sintering, the highest temperature is set at 180 ℃, heats up by 1.5 ℃/min, takes out after 6 hours and makes composite membrane, with 70% ethanolic solution genistein wash-out from film is removed down at 90 ℃ then, drying promptly makes genistein is had the siliceous diffusion barrier of single-minded selectivity under room temperature.On homemade film evaluating apparatus the material liquid that contains genistein 0.45mg/ml is separated, reaching the adsorption equilibrium time is 4 hours, is 88.1% to the selection rate of genistein.
Claims (1)
1. preparation method who natural products is had the siliceous diffusion barrier of single-minded selectivity, this method is function monomer with the organosilan, is that the template agent prepares predecessor with a certain class natural products component, carries out the synergetic hydrolysis reaction with tetraethoxysilane then, form colloidal sol, again with Al
2O
3For carrier is filmed, carry out just having obtained having single-minded optionally siliceous diffusion barrier behind the sintering, it is characterized in that comprising following concrete steps: natural products
1) .Al
2O
3The pre-treatment of carrier is earlier γ-Al
2O
3The plate surface finish is smooth, boiled 10~50 minutes in hydrochloric acid, nitric acid or the phosphoric acid solution with 0.01~0.15mol/L again, then with boiling 10~50 minutes in the NaOH of 0.01~0.15mol/L or the potassium hydroxide solution, after spending deionised water 1~6 time, placed ethanol more ultrasonic 10~50 minutes, and spent deionised water and be placed on dried for standby under the room temperature;
2). the preparation of silane precursor, the template agent is dissolved in ethanol, pyridine, be made into mass concentration in methyl-sulfoxide or the oxolane and be 0.2%~30% solution, described template agent is: rutin, Quercetin, genistein, morphine, mufangchine, unabain or andrographolide, get template solution after treating to dissolve fully, volume ratio by template solution and function monomer is 20: 1~10 adding gamma-aminopropyl-triethoxy-silanes, γ-chloro triethoxysilane or the 3-third isocyanide root triethoxysilane obtain precursor solution, the volume ratio 100: 1~10 of pressing precursor solution and stabilizing agent then adds N, N-dimethylformamide or N, N-dimethyl acetyl ammonia, refluxed 10~36 hours down in 40 ℃~90 ℃, after reaction finishes, adopt rotary evaporation to remove to desolvate silane precursor;
3). with step 2) silane precursor that makes is dissolved in that to be made into mass concentration in the ethanol be 0.5%~10% solution, being 1: 5~20 to add tetraethoxysilanes with this liquor capacity ratio, regulate pH=4.5~6.1 with hydrochloric acid or acetic acid then, or regulate pH=7.9~9.2 with ammoniacal liquor or NaOH, being 100: 1~10 to add stabilizing agent N with regulating liquor capacity ratio behind the pH, N-dimethylformamide or N, N-dimethyl acetyl ammonia, under stirring state, adding volume ratio to the solution that is added with stabilizing agent is 5: 1~10 deionized waters, refluxed 8~12 hours down at 40 ℃~90 ℃ then, obtain homogeneous, stable sols;
4). the colloidal sol that step 3) is made ageing 1~6 hour under room temperature, the Al that step 1) is handled
2O
3Immersed in the colloidal solution after the ageing 6~9 seconds, dip-coating is 6~7 times repeatedly, obtains composite membrane;
5). the composite membrane that step 4) is made places Muffle furnace, and design temperature is 150~200 ℃, by the heating rate of 0.5 ℃/min~5 ℃/min, sintering 4~8 hours;
6). the composite membrane that sinters, again with mass concentration be 60%~80% ethanol, ethyl acetate, chloroform or dimethyl sulfoxide solution in the agent of 60 ℃~90 ℃ of following wash-out templates, wash-out promptly can be used for the separating natural product after 6~10 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2006100139630A CN100358616C (en) | 2006-05-30 | 2006-05-30 | Process for preparing silicon separating films with specialized selectivity to natural products |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2006100139630A CN100358616C (en) | 2006-05-30 | 2006-05-30 | Process for preparing silicon separating films with specialized selectivity to natural products |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1883780A CN1883780A (en) | 2006-12-27 |
CN100358616C true CN100358616C (en) | 2008-01-02 |
Family
ID=37582158
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2006100139630A Expired - Fee Related CN100358616C (en) | 2006-05-30 | 2006-05-30 | Process for preparing silicon separating films with specialized selectivity to natural products |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100358616C (en) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101254416B (en) * | 2007-12-07 | 2010-05-19 | 厦门大学 | Preparation of gelatine- aminosilane- -anode alumina compound film with affinity |
CN101797481B (en) * | 2010-04-28 | 2013-03-20 | 哈尔滨工业大学 | Preparation method of functional shell band-shaped silica nano fibrous membrane |
CN104888495A (en) * | 2015-06-08 | 2015-09-09 | 北京理工大学 | Production method of chiral chromatographic column |
CN105597561B (en) * | 2015-12-25 | 2018-02-02 | 常州大学 | A kind of organic silicon sol preparation method and application swung based on pH |
CN108543425B (en) * | 2018-04-10 | 2020-11-24 | 常州大学 | Preparation method of separation membrane for polyphenol substances |
RU2756552C1 (en) * | 2020-08-10 | 2021-10-01 | Федеральное государственное бюджетное учреждение науки Ордена Трудового Красного Знамени Институт химии силикатов им. И.В. Гребенщикова Российской академии наук (ИХС РАН) | Method for production of bioactive membrane of osmotic-active filter for water treatment |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6306301B1 (en) * | 1996-10-31 | 2001-10-23 | University Of Kentucky Research Foundation | Silica-based membrane sorbent for heavy metal sequestration |
CN1562450A (en) * | 2004-03-25 | 2005-01-12 | 复旦大学 | New type nano SiO2 separation membrane and preparation method |
CN1736580A (en) * | 2005-07-11 | 2006-02-22 | 天津大学 | Method for preparing built-in nano pore silica absorbent for medicine separation and purification |
-
2006
- 2006-05-30 CN CNB2006100139630A patent/CN100358616C/en not_active Expired - Fee Related
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6306301B1 (en) * | 1996-10-31 | 2001-10-23 | University Of Kentucky Research Foundation | Silica-based membrane sorbent for heavy metal sequestration |
CN1562450A (en) * | 2004-03-25 | 2005-01-12 | 复旦大学 | New type nano SiO2 separation membrane and preparation method |
CN1736580A (en) * | 2005-07-11 | 2006-02-22 | 天津大学 | Method for preparing built-in nano pore silica absorbent for medicine separation and purification |
Also Published As
Publication number | Publication date |
---|---|
CN1883780A (en) | 2006-12-27 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN100358616C (en) | Process for preparing silicon separating films with specialized selectivity to natural products | |
CN105664738B (en) | A kind of graphene oxide group compound film for Spent Radioactive water process | |
CN108201795B (en) | A kind of preparation method of Selective Separation Enoxacin molecularly imprinted composite membrane material | |
CN107469653B (en) | Synthesis method of molecular imprinting composite membrane for enriching and separating norfloxacin | |
CN102188914B (en) | Method for preparing alcohol permselective silicon rubber composite membrane | |
CN100556518C (en) | Hydrophilic organic ceramic composite permeable vaporizing membrane and its production and application | |
CN103204601B (en) | Wastewater treatment method | |
CN101928828A (en) | Method for extracting lithium from salt lake brine by adsorption method | |
CN104888618B (en) | Method for preparing high-performance B-ZSM-5 molecular sieve membrane in dilute synthesis solution | |
CN101920170B (en) | High-flux molecular-sieve alcohol permselective membrane and preparation method thereof | |
Chen et al. | Design of self-cleaning molecularly imprinted membrane with antibacterial ability for high-selectively separation of ribavirin | |
Li et al. | Continuity control of b-oriented MFI zeolite films by microwave synthesis | |
CN109364769A (en) | The preparation method of pollution-resistant Enoxacin molecularly imprinted composite membrane material | |
CN109364768A (en) | The preparation method of organic inorganic hybridization Enoxacin molecularly imprinted composite membrane material | |
CN104163921A (en) | Mesoporous silicon composite lead ion imprinted polymer and its preparation method and use | |
CN105233701B (en) | A kind of method that macropore carrier surface prepares palladium film | |
CN106512729A (en) | High-desalinization-rate reverse osmosis composite membrane and preparing method thereof | |
CN103127954A (en) | Preparation method of multi-layer composite film capable of catalyzing C-C key coupling reaction | |
CN103908955B (en) | The preparation method of the superhigh cross-linking type polymeric adsorbent that a kind of acetamido is modified and application thereof | |
CN102500243A (en) | Preparation method for molecular sieve/organic composite permeable vaporization membrane | |
CN103846015B (en) | A kind of preparation method of organic and inorganic lamination milipore filter | |
Irani et al. | Preparation of poly (vinyl alcohol)/tetraethyl orthosilicate hybrid membranes modified with TMPTMS by sol-gel method for removal of lead from aqueous solutions | |
CN112023892A (en) | Method for adsorbing antibiotics in water body by using nitrogen-doped porous carbon material derived from zeolite imidazole framework | |
CN1919843A (en) | Preparation method of siliceous inorganic flavonoid molecular engram microsphere | |
CN106914144A (en) | A kind of method that reverse diffusion technique prepares hydrotalcite composite membrane |
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 |