CN115582027A - Preparation method of covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths - Google Patents
Preparation method of covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths Download PDFInfo
- Publication number
- CN115582027A CN115582027A CN202211098548.5A CN202211098548A CN115582027A CN 115582027 A CN115582027 A CN 115582027A CN 202211098548 A CN202211098548 A CN 202211098548A CN 115582027 A CN115582027 A CN 115582027A
- Authority
- CN
- China
- Prior art keywords
- alkyl chains
- different lengths
- modified
- organic solvent
- organic
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 53
- 239000013310 covalent-organic framework Substances 0.000 title claims abstract description 50
- 125000000217 alkyl group Chemical group 0.000 title claims abstract description 42
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 42
- 239000003960 organic solvent Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 29
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 238000010276 construction Methods 0.000 claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 9
- 239000002841 Lewis acid Substances 0.000 claims abstract description 8
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 7
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 5
- 230000009471 action Effects 0.000 claims abstract description 4
- 230000021523 carboxylation Effects 0.000 claims abstract description 4
- 238000006473 carboxylation reaction Methods 0.000 claims abstract description 4
- 230000004048 modification Effects 0.000 claims abstract description 4
- 238000012986 modification Methods 0.000 claims abstract description 4
- 210000004379 membrane Anatomy 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- HZXJVDYQRYYYOR-UHFFFAOYSA-K scandium(iii) trifluoromethanesulfonate Chemical group [Sc+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F HZXJVDYQRYYYOR-UHFFFAOYSA-K 0.000 claims description 13
- CTBCGPDGIWWKAV-UHFFFAOYSA-N 2-[3,5-bis(2-aminophenyl)phenyl]aniline Chemical compound NC1=CC=CC=C1C1=CC(C=2C(=CC=CC=2)N)=CC(C=2C(=CC=CC=2)N)=C1 CTBCGPDGIWWKAV-UHFFFAOYSA-N 0.000 claims description 11
- 150000001299 aldehydes Chemical class 0.000 claims description 11
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 9
- PIWMYUGNZBJTID-UHFFFAOYSA-N 2,5-dihydroxyterephthalaldehyde Chemical group OC1=CC(C=O)=C(O)C=C1C=O PIWMYUGNZBJTID-UHFFFAOYSA-N 0.000 claims description 7
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 210000002469 basement membrane Anatomy 0.000 claims description 3
- UCYRAEIHXSVXPV-UHFFFAOYSA-K bis(trifluoromethylsulfonyloxy)indiganyl trifluoromethanesulfonate Chemical compound [In+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F UCYRAEIHXSVXPV-UHFFFAOYSA-K 0.000 claims description 3
- TWNOVENTEPVGEJ-UHFFFAOYSA-K europium(3+);trifluoromethanesulfonate Chemical compound [Eu+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F TWNOVENTEPVGEJ-UHFFFAOYSA-K 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- AHZJKOKFZJYCLG-UHFFFAOYSA-K trifluoromethanesulfonate;ytterbium(3+) Chemical compound [Yb+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F AHZJKOKFZJYCLG-UHFFFAOYSA-K 0.000 claims description 3
- JPJIEXKLJOWQQK-UHFFFAOYSA-K trifluoromethanesulfonate;yttrium(3+) Chemical compound [Y+3].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F JPJIEXKLJOWQQK-UHFFFAOYSA-K 0.000 claims description 3
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Substances [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 claims description 3
- ZMLPZCGHASSGEA-UHFFFAOYSA-M zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F ZMLPZCGHASSGEA-UHFFFAOYSA-M 0.000 claims description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 2
- MNDIARAMWBIKFW-UHFFFAOYSA-N 1-bromohexane Chemical compound CCCCCCBr MNDIARAMWBIKFW-UHFFFAOYSA-N 0.000 claims description 2
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 238000005904 alkaline hydrolysis reaction Methods 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 230000020477 pH reduction Effects 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- MYMSJFSOOQERIO-UHFFFAOYSA-N 1-bromodecane Chemical compound CCCCCCCCCCBr MYMSJFSOOQERIO-UHFFFAOYSA-N 0.000 claims 1
- PBLNBZIONSLZBU-UHFFFAOYSA-N 1-bromododecane Chemical compound CCCCCCCCCCCCBr PBLNBZIONSLZBU-UHFFFAOYSA-N 0.000 claims 1
- LSXKDWGTSHCFPP-UHFFFAOYSA-N 1-bromoheptane Chemical compound CCCCCCCBr LSXKDWGTSHCFPP-UHFFFAOYSA-N 0.000 claims 1
- AYMUQTNXKPEMLM-UHFFFAOYSA-N 1-bromononane Chemical compound CCCCCCCCCBr AYMUQTNXKPEMLM-UHFFFAOYSA-N 0.000 claims 1
- YZWKKMVJZFACSU-UHFFFAOYSA-N 1-bromopentane Chemical compound CCCCCBr YZWKKMVJZFACSU-UHFFFAOYSA-N 0.000 claims 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 claims 1
- IKPSIIAXIDAQLG-UHFFFAOYSA-N 1-bromoundecane Chemical compound CCCCCCCCCCCBr IKPSIIAXIDAQLG-UHFFFAOYSA-N 0.000 claims 1
- 238000002715 modification method Methods 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000012216 screening Methods 0.000 abstract description 4
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000014759 maintenance of location Effects 0.000 description 17
- 239000010408 film Substances 0.000 description 14
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 5
- 239000012074 organic phase Substances 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- -1 Butoxy Terephthalaldehyde Chemical compound 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CQPFMGBJSMSXLP-UHFFFAOYSA-M acid orange 7 Chemical compound [Na+].OC1=CC=C2C=CC=CC2=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 CQPFMGBJSMSXLP-UHFFFAOYSA-M 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 3
- DDCDZJHDWYGVRO-UHFFFAOYSA-N 2,5-diethoxyterephthalaldehyde Chemical compound CCOC1=CC(C=O)=C(OCC)C=C1C=O DDCDZJHDWYGVRO-UHFFFAOYSA-N 0.000 description 2
- HBPJKNOOUOGSOG-UHFFFAOYSA-N 2,5-dioctoxyterephthalaldehyde Chemical group CCCCCCCCOC1=CC(C=O)=C(OCCCCCCCC)C=C1C=O HBPJKNOOUOGSOG-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- YVTRGUBFSLFACU-UHFFFAOYSA-N 2,5-dibutoxyterephthalaldehyde Chemical compound CCCCOC1=CC(C=O)=C(OCCCC)C=C1C=O YVTRGUBFSLFACU-UHFFFAOYSA-N 0.000 description 1
- MCUCVEHSWHSNRW-UHFFFAOYSA-N 2,5-dihexylterephthalaldehyde Chemical group CCCCCCC1=CC(C=O)=C(CCCCCC)C=C1C=O MCUCVEHSWHSNRW-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000006740 morphological transformation Effects 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940042635 potassium 10 mmol Drugs 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 230000031068 symbiosis, encompassing mutualism through parasitism Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/028—Microfluidic pore structures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides an application of a covalent organic framework membrane modified by alkyl chains with different lengths in nanofiltration of an organic solvent. The method comprises the following steps: (1) Preparing aldehyde group organic construction units modified by alkyl chains with different lengths; performing carboxylation modification on the surface of a base film; (3) Preparing a seed crystal solution and introducing the seed crystal into the carboxylated base film; (4) Under the action of a Lewis acid type catalyst, the amino organic construction unit and the aldehyde organic construction unit modified by alkyl chains with different lengths are subjected to interfacial polymerization on the surface of the base membrane introduced with the seed crystal to obtain the covalent organic framework organic solvent nanofiltration membrane modified by the alkyl chains with different lengths. The microenvironment of the covalent organic frame organic solvent nanofiltration membrane pore channel modified by the alkyl chains with different lengths can be accurately regulated and controlled, and fine screening of an organic solvent is facilitated. The Lewis acid type catalyst ensures the crystallinity of the covalent organic framework and improves the forming and exchange rate of the covalent organic framework; the introduction of the seed crystal strategy improves the commonality between the covalent organic framework and the base membrane, and is beneficial to the long-term stability of the membrane.
Description
Technical Field
The invention belongs to the technical field of novel separation membrane materials, and particularly relates to an application of a covalent organic framework membrane modified by alkyl chains with different lengths in nanofiltration of an organic solvent.
Background
The organic solvent is widely applied to high-added-value concentration processes such as natural medicine synthesis, fine chemical manufacturing and the like. In the traditional processes for recovering the organic solvent, such as rectification, recovery, extraction and the like, the energy consumption of the separation process accounts for 19 percent of the energy consumption of the global total manufacturing industry. Compared with the traditional separation process, the Organic Solvent Nanofiltration process can reduce the equipment investment cost by 40-70%, save the energy by more than 90%, and realize the molecular weight of 200-1000g mol while recovering the Solvent -1 And (4) efficient separation of solutes.
The research bottleneck of the organic solvent nanofiltration membrane is the swelling phenomenon generated when the membrane material is contacted with a solvent, so that the selective permeability is unstable, and the wettability damage and even the disappearance of the separation characteristic occur in the using process. Covalent Organic frameworks (Covalent Organic frameworks) are a class of crystalline Organic porous polymers formed by Organic building units connected by Covalent bonds, and have regular channels, high specific surface area and highly ordered periodic structures. The specific organic molecular sieve property of the covalent organic framework obviously enhances the compressive strength and the solvent affinity of the transfer channel, the one-dimensional through characteristic pore channel can minimize the transmission path, and the transmission efficiency and the screening precision are higher.
At present, the research on the covalent organic framework material organic solvent nanofiltration membrane is still in the initial stage, and the combination of the covalent organic framework property and the actual separation process is not realized. The reported aperture of the covalent organic framework is 0.5-4.7nm, which is between the application range of reverse osmosis and ultrafiltration, and the separation requirements of different organic solvent systems are difficult to meet. Although interfacial polymerization realizes the morphological transformation of covalent organic framework materials from powder to thin film, the growth time is long (more than 72 h), and the control of the reaction process and the organic solvent nanofiltration membrane structure is difficult. Due to the lack of obvious physical or chemical combination between the covalent organic framework and the basement membrane, the long-term service stability is lack of guarantee. In conclusion, the existing preparation method of the organic solvent nanofiltration membrane with the covalent organic framework cannot provide a large-scale continuous membrane with good symbiosis with the base membrane and high practicability.
Disclosure of Invention
The invention relates to a preparation method of a covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths. The aperture of the prepared organic solvent nanofiltration membrane can be finely adjusted, which is beneficial to realizing the precise screening under different separation systems, and the prepared organic solvent nanofiltration membrane has better interception performance and higher solvent flux in different organic solvents.
The invention relates to a preparation method of a covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths, which is characterized by comprising the following steps:
(1) Preparing aldehyde group organic construction units modified by alkyl chains with different lengths;
(2) Performing carboxylation modification on the surface of a base film;
(3) Preparing a seed crystal solution and introducing the seed crystal into the carboxylated base film;
(4) And (3) under the action of a Lewis acid type catalyst, carrying out interfacial polymerization on the amino organic construction unit and the aldehyde organic construction unit modified by alkyl chains with different lengths on the surface of the base membrane obtained in the step (3) to obtain the covalent organic framework organic solvent nanofiltration membrane modified by the alkyl chains with different lengths.
Further, the aldehyde organic building blocks modified by alkyl chains with different lengths in the step (1) can be prepared by the following synthetic route:
the method specifically comprises the following steps: brominated alkane, an ionic reinforcing agent potassium carbonate and an aldehyde organic construction unit 2, 5-dihydroxy terephthalaldehyde with the molar ratio of 3: 1 are dissolved in a certain amount of N, N-Dimethylformamide (DMF) at room temperature. The mixture reacts for 9 to 18 hours at a temperature of between 50 and 100 ℃. The reaction mixture was cooled to room temperature, dispersed in a certain amount of water, and extracted with ethyl acetate. The organic phase was over anhydrous MgSO 4 After drying, the solvent was evaporated in vacuo. Recrystallizing the obtained solid in petroleum ether to remove impurities, and obtainingAldehyde organic building blocks modified by alkyl chains of the same length, namely terephthalaldehyde TPOC modified by alkyl chains of different lengths x (x＝1-12)。
The aldehyde group organic construction unit modified by the alkyl chains with different lengths is terephthalaldehyde TPOC modified by the alkyl chains with different lengths x (x = 1-12) the structure is as follows:
the amino organic building unit 1,3, 5-tri (aminophenyl) benzene (TAPB) has the following structure:
further, in the step (2), the base film is one of polyacrylonitrile, polyetheretherketone, polyamide, polypyrrole, cellulose acetate, polyvinylidene fluoride, anodic alumina, and silica film. The base film adopts 1-3mol L -1 Sodium hydroxide is subjected to alkaline hydrolysis and acidification treatment or ultraviolet grafting treatment in an acrylic acid solution, and a carboxyl group is introduced to the surface of the sodium hydroxide.
Further, in the step (3), the terephthalaldehyde TPOC modified by alkyl chains with different lengths is adopted x (x = 1-12), 1,3, 5-tri (aminophenyl) benzene or covalent organic framework oligomer small particles are used as seed crystals, dispersed in one or more of ethyl acetate, 1, 4-dioxane, mesitylene, acetic acid and dichloromethane to prepare seed crystal solution, and the carboxylated base membrane is soaked in the seed crystal solution for 12-72h for seed crystal introduction.
Further, in the step (4), the covalent organic framework TAPB-TPOC modified by alkyl chains with different lengths is adopted x (x = 1-12) the organic solvent nanofiltration membrane is prepared by modifying 1,3, 5-tri (aminophenyl) benzene and alkyl chains with different lengths by using terephthalaldehyde TPOC x (x = 1-12) prepared by interfacial polymerization of the surface of the seed-introduced base film obtained in the step (3).
The covalent organic framework modified by alkyl chains with different lengths has the following structure:
further, in the step (4), the Lewis acid type catalyst is scandium trifluoromethanesulfonate (Sc (OTf) 3 ) Indium trifluoromethanesulfonate (In (OTf) 3 ) Ytterbium trifluoromethanesulfonate (Yb (OTf) 3 ) Yttrium trifluoromethanesulfonate (Y (OTf) 3 ) Europium trifluoromethanesulfonate (Eu (OTf) 3 ) Zinc trifluoromethanesulfonate (Zn (OTf) 3 ) Can accelerate the formation and exchange rate of covalent organic frameworks.
Preferably, the concentration of 1,3, 5-tris (aminophenyl) benzene in the organic phase solution is from 0.01 to 0.3mol L -1 The molar ratio of 1,3, 5-tri (aminophenyl) benzene to terephthalaldehyde modified by alkyl chains of different lengths is 2: 3.
Preferably, the concentration of the Lewis acid type catalyst in the aqueous phase solution is from 0.01 to 0.03mol L -1 . More preferably, the selective catalyst is scandium triflate.
Preferably, the reaction time is from 10min to 120min, more preferably 30min.
Compared with the prior art, the invention has the following advantages:
(1) The invention finely adjusts the micro-environment of the channel of the nanofiltration membrane by regulating the length of the alkyl chain in the channel of the covalent organic framework, and is more favorable for realizing precise screening in an organic solvent system. Meanwhile, the alkyl chain in the pore channel can enhance the interlayer pi-pi interaction of the covalent organic framework, and the self stability is improved.
(2) The Lewis acid catalyst adopted by the invention improves the formation and exchange rate of a covalent organic framework and accelerates the preparation and formation process of the membrane while ensuring the crystallinity.
(3) According to the invention, the commonness between the base membrane and the covalent organic framework modified by alkyl chains with different lengths is improved by introducing a variety of pretreatment modes on the surface of the base membrane, so that the long-term service capacity of the nanofiltration membrane is improved.
Drawings
FIG. 1 is a schematic of the interfacial polymerization process of examples 1, 2, 3 and 4.
FIG. 2 is a graph comparing dye retention and ethanol flux for examples 1, 2, 3, and 4.
Detailed Description
The invention will be further elucidated with reference to the following examples, in conjunction with the accompanying drawings. It should be understood that the specific examples described herein are intended to be illustrative only and are not intended to be limiting. Unless otherwise stated in the context of this application, the terms and abbreviations referred to in this application are well known to those skilled in the art; unless otherwise indicated below by the manufacturer, all of the drugs referred to are conventional commercial products available through commercial purchase.
Example 1 preparation of ethyl modified covalent organic framework organic solvent nanofiltration membrane:
1) Preparing an ethyl-modified aldehyde organic building unit:
30mmol of 1-bromoethane, 30mmol of potassium carbonate and 10mmol of 2, 5-dihydroxyterephthalaldehyde were dissolved in 50mL of DMF at room temperature, and the mixture was reacted at 90 ℃ for 12 hours. The reaction mixture was cooled to room temperature, poured into 100mL of water, and extracted with 100mL of ethyl acetate each time. Extracting the obtained organic phase with anhydrous MgSO 4 Drying, vacuum evaporating to obtain solid powder, recrystallizing with petroleum ether to obtain yellow powder of 2, 5-diethoxy Terephthalaldehyde (TPOC) 2 )。
2) Performing carboxylation modification on the surface of a base film:
polyacrylonitrile with a molecular weight cut-off of 10w was used as a base film. Ethanol is adopted to pre-swell the polyacrylonitrile basal membrane, and then 1.5mol L at 45 DEG C -1 Hydrolyzing in NaOH for 2.0h, and adopting 1mol L of hydrolyzed polyacrylonitrile base membrane -1 Acidifying with hydrochloric acid to obtain the carboxylated polyacrylonitrile base film.
3) Preparation of seed solution and introduction of carboxylated base film into seed:
a seed crystal solution was prepared by dissolving 15mg of 1,3, 5-tris (aminophenyl) benzene in 40mL of mesitylene/1, 4-dioxane (volume ratio 1: 3). And (3) soaking the carboxylated polyacrylonitrile base membrane obtained in the step (2) in a seed crystal solution for 12h to introduce seed crystals.
4) Carrying out interfacial polymerization on the surface of the polyacrylonitrile-based membrane obtained in the step 3) by using an amino organic construction unit and an aldehyde organic construction unit modified by alkyl chains with different lengths under the action of a Lewis acid type catalyst:
0.01mol of 1,3, 5-tris (aminophenyl) benzene and 0.015mol of 2, 5-diethoxy terephthalaldehyde prepared in step 1 were dissolved in 100mL of ethyl acetate, and 0.002mol of scandium trifluoromethanesulfonate, indium trifluoromethanesulfonate, ytterbium trifluoromethanesulfonate, yttrium trifluoromethanesulfonate, europium trifluoromethanesulfonate and zinc trifluoromethanesulfonate were dissolved in 100mL of water, respectively. And (4) in a self-made diffusion pool, placing an organic phase in the front cavity of the polyacrylonitrile base film introduced with the seed crystal obtained in the step (3), placing a water phase in the back cavity of the base film for interfacial polymerization, and obtaining the ethyl-modified covalent organic framework organic solvent nanofiltration membrane after a period of time.
The membrane prepared in example 1 was subjected to organic solvent nanofiltration performance test. The concentration of each dye in ethanol was 100mg g -1 The nanofiltration experimental result is as follows: the retention rate of orange II is 90.23%, the retention rate of methyl orange is 90.12%, the retention rate of Congo red is 95.26%, and the retention rate of Alsinoblue is 94.52%; the average ethanol flux is 47.51L m -2 h -1 bar -1 As shown in fig. 2.
In particular, to demonstrate the catalytic effect of the catalyst on the covalent organic framework, the covalent organic framework powder produced by homogeneous polymerization in the organic phase under different catalyst systems in example 1 was collected, and the powder had the same composition as the covalent organic framework film. The crystallinity of the powder formed during the preparation of the covalent organic framework film using different catalysts in example 1 of the present invention is summarized in table 1.
Example 2 preparation of n-butyl modified covalent organic framework organic solvent nanofiltration membrane:
the preparation steps of the n-butyl modified covalent organic framework organic solvent nanofiltration membrane are the same as the example 1, the difference is that the step 1 is the preparation of the n-butyl modified aldehyde organic construction unit, reactants are 1-bromobutane, potassium carbonate and 2, 5-dihydroxy terephthalaldehyde, and a product is 2, 5-bis (benzaldehyde)Butoxy Terephthalaldehyde (TPOC) 4 ) (ii) a In the step 4, reactants are 1,3, 5-tri (aminophenyl) benzene and 2, 5-dibutyloxy terephthalaldehyde. The catalyst is scandium trifluoromethanesulfonate with the best catalytic effect in example 1, and the reaction time is 10min. The concentration of each dye in ethanol was 100mg g -1 The nanofiltration experimental result is as follows: the retention rate of orange II is 95.32%, the retention rate of methyl orange is 95.65%, the retention rate of Congo red is 96.95%, and the retention rate of Alsinoblue is 95.05%; the ethanol flux is 45.99L m on average -2 h -1 bar -1 As shown in fig. 2.
Example 3 preparation of n-hexyl modified covalent organic framework organic solvent nanofiltration membrane:
the preparation steps of the n-hexyl modified covalent organic framework organic solvent nanofiltration membrane are the same as the example 1, the difference is that the step 1 is the preparation of the n-hexyl modified aldehyde organic construction unit, reactants are 1-bromohexane, potassium carbonate and 2, 5-dihydroxy terephthalaldehyde, and a product is 2, 5-dihexyl Terephthalaldehyde (TPOC) 6 ) (ii) a In the step 4, reactants are 1,3, 5-tri (aminophenyl) benzene and 2, 5-dihexylyloxyterephthalaldehyde. The catalyst was scandium trifluoromethanesulfonate having the best catalytic effect in example 1, and the reaction time was 10min. The concentration of each dye in ethanol was 100mg g -1 The nanofiltration experimental result is as follows: the retention rate of orange II is 96.52%, the retention rate of methyl orange is 98.54%, the retention rate of Congo red is 97.65%, and the retention rate of Alsinoblue is 96.24%; the ethanol flux is 41.25L m on average -2 h -1 bar -1 As shown in fig. 2.
Example 4 preparation of n-octyl modified covalent organic framework organic solvent nanofiltration membranes:
the preparation steps of the n-octyl modified covalent organic framework organic solvent nanofiltration membrane are the same as the example 1, the difference is that the step 1 is the preparation of the n-octyl modified aldehyde organic construction unit, reactants are 1-bromooctane, potassium carbonate and 2, 5-dihydroxy terephthalaldehyde, and a product is 2, 5-dioctyloxyterephthalaldehyde (TPOC) 8 ) (ii) a In the step 4, reactants are 1,3, 5-tri (aminophenyl) benzene and 2, 5-dioctyloxy terephthalaldehyde. Catalyst selection example 1The reaction time of the scandium trifluoromethanesulfonate with the best catalytic effect is 10min. The concentration of each dye in ethanol was 100mg g -1 The nanofiltration experimental result is as follows: the retention rate of orange II is 99.52%, the retention rate of methyl orange is 99.92%, the retention rate of Congo red is 97.95%, and the retention rate of Alnew blue is 97.05%; the ethanol flux is 36.15L m on average -2 h -1 bar -1 As shown in fig. 2.
The crystallinity of the powder produced by the different catalysts, reaction conditions and interfacial polymerization processes selected in example 1 is summarized in table 1:
TABLE 1
Claims (7)
1. A preparation method of a covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths is characterized by comprising the following steps:
(1) Preparing aldehyde group organic construction units modified by alkyl chains with different lengths;
(2) Performing carboxylation modification on the surface of a base film;
(3) Preparing a seed crystal solution and introducing the seed crystal into the carboxylated base film;
(4) And (3) under the action of a Lewis acid type catalyst, carrying out interfacial polymerization on the amino organic construction unit and the aldehyde organic construction unit modified by alkyl chains with different lengths on the surface of the base membrane obtained in the step (3) to obtain the covalent organic framework organic solvent nanofiltration membrane modified by the alkyl chains with different lengths.
2. The preparation method of the covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths as claimed in claim 1, wherein the preparation method comprises the following steps:
in the step (1), the selected aldehyde organic building unit is 2, 5-dihydroxy terephthalaldehyde;
in the step (1), under certain conditions, brominated alkane reacts with 2, 5-dihydroxy terephthalaldehyde to obtain aldehyde groups modified by alkyl chains with different lengthsBuilding blocks, i.e. terephthalaldehyde TPOC modified with alkyl chains of different lengths x (x＝1-12)；
In the step (1), the brominated alkane is one of bromoethane, 1-bromopropane, 1-bromobutane, 1-bromopentane, 1-bromohexane, 1-bromoheptane, 1-bromooctane, 1-bromononane, 1-bromodecane, 1-bromoundecane and 1-bromododecane.
3. The preparation method of the covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths as claimed in claim 2, wherein the preparation method comprises the following steps:
in the step (2), the base film is one of polyacrylonitrile, polyether-ether-ketone, polyamide, polypyrrole, cellulose acetate, polyvinylidene fluoride, anodic alumina and silicon dioxide film;
in the step (2), the surface modification method of the basement membrane comprises alkaline hydrolysis, acidification or ultraviolet irradiation grafting in acrylic acid solution.
4. The preparation method of the covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths as claimed in claim 3, wherein the preparation method comprises the following steps:
in the step (3), amino organic building units, aldehyde organic building units modified by alkyl chains with different lengths or covalent organic framework oligomer small particles are used as seed crystals to be dispersed in one or more of ethyl acetate, 1, 4-dioxane, mesitylene, acetic acid and dichloromethane to prepare a seed crystal solution, and the carboxylated base film is soaked in the seed crystal solution to introduce the seed crystals.
5. The preparation method of the covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths as claimed in claim 4, wherein the preparation method comprises the following steps:
in the step (4), the Lewis acid type catalyst is scandium trifluoromethanesulfonate (Sc (OTf) 3 ) Indium trifluoromethanesulfonate (In (OTf) 3 ) Ytterbium trifluoromethanesulfonate (Yb (OTf) 3 ) Yttrium trifluoromethanesulfonate (Y (OTf) 3 ) Europium trifluoromethanesulfonate (Eu (OTf) 3 ) Zinc trifluoromethanesulfonate (Zn (OT)f) 3 ) To (3) is provided.
6. The preparation method of the covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths as claimed in claim 5, wherein the preparation method comprises the following steps:
in the step (4), an amino organic construction unit 1,3, 5-tri (aminophenyl) benzene (TAPB) and the terephthalaldehyde TPOC modified by the alkyl chains with different lengths prepared in the step (1) x (x = 1-12) surface interface polymerization is carried out on the modified basement membrane obtained in the step (3), and the covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths is prepared.
7. The application of the covalent organic framework organic solvent nanofiltration membrane modified by the alkyl chains with different lengths as claimed in any one of claims 1 to 6 in the field of organic solvent nanofiltration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211098548.5A CN115582027B (en) | 2022-09-09 | 2022-09-09 | Preparation method of covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211098548.5A CN115582027B (en) | 2022-09-09 | 2022-09-09 | Preparation method of covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115582027A true CN115582027A (en) | 2023-01-10 |
| CN115582027B CN115582027B (en) | 2024-07-19 |
Family
ID=84771258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211098548.5A Active CN115582027B (en) | 2022-09-09 | 2022-09-09 | Preparation method of covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115582027B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116212661A (en) * | 2023-03-16 | 2023-06-06 | 天津工业大学 | Covalent organic framework organic solvent nanofiltration membrane with odd-even effect functionalization and preparation method thereof |
| CN116785952A (en) * | 2023-08-22 | 2023-09-22 | 天津大学浙江研究院 | Covalent organic framework nanofiltration membrane and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2829998A1 (en) * | 2011-03-16 | 2012-09-20 | Creative Therapeutics Gmbh | Substituted diphenyl derivatives |
| WO2013176523A1 (en) * | 2012-05-24 | 2013-11-28 | 주식회사 엘지화학 | Method for manufacturing a reverse osmosis membrane and a reverse osmosis membrane manufactured thereby |
| EP2992947A1 (en) * | 2014-08-25 | 2016-03-09 | Karlsruher Institut für Technologie | Method for the preparation of microporous organic membranes, microporous organic membranes and use of same |
| CN113603912A (en) * | 2021-07-17 | 2021-11-05 | 河南师范大学 | Method for preparing high-crystallinity covalent organic framework film by using ionic liquid-water interface |
-
2022
- 2022-09-09 CN CN202211098548.5A patent/CN115582027B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2829998A1 (en) * | 2011-03-16 | 2012-09-20 | Creative Therapeutics Gmbh | Substituted diphenyl derivatives |
| WO2013176523A1 (en) * | 2012-05-24 | 2013-11-28 | 주식회사 엘지화학 | Method for manufacturing a reverse osmosis membrane and a reverse osmosis membrane manufactured thereby |
| EP2992947A1 (en) * | 2014-08-25 | 2016-03-09 | Karlsruher Institut für Technologie | Method for the preparation of microporous organic membranes, microporous organic membranes and use of same |
| CN113603912A (en) * | 2021-07-17 | 2021-11-05 | 河南师范大学 | Method for preparing high-crystallinity covalent organic framework film by using ionic liquid-water interface |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116212661A (en) * | 2023-03-16 | 2023-06-06 | 天津工业大学 | Covalent organic framework organic solvent nanofiltration membrane with odd-even effect functionalization and preparation method thereof |
| CN116212661B (en) * | 2023-03-16 | 2024-07-19 | 天津工业大学 | Covalent organic framework organic solvent nanofiltration membrane with odd-even effect functionalization and preparation method thereof |
| CN116785952A (en) * | 2023-08-22 | 2023-09-22 | 天津大学浙江研究院 | Covalent organic framework nanofiltration membrane and preparation method thereof |
| CN116785952B (en) * | 2023-08-22 | 2023-12-08 | 天津大学浙江研究院 | Covalent organic framework nanofiltration membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115582027B (en) | 2024-07-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115582027A (en) | Preparation method of covalent organic framework organic solvent nanofiltration membrane modified by alkyl chains with different lengths | |
| CN108275666A (en) | It is a kind of double（Fluorine sulphonyl）The preparation method of imine alkali metal salt | |
| US4810450A (en) | Process for the preparation of polyvinyl alcohol articles of high strength and modulus | |
| CN114456339A (en) | Covalent organic framework film with high content of ionic groups, preparation method and application thereof | |
| CN113522063B (en) | Nanofiltration membrane for treating printing and dyeing wastewater and preparation method thereof | |
| CN110681271B (en) | NH2-MIL-125/POD-COOH ultrathin homogeneous hybrid forward osmosis membrane and preparation method thereof | |
| CN114394895B (en) | Preparation method of 2,4, 6-trimethylphenylacetic acid | |
| CN115445673B (en) | Blend type anion exchange membrane for improving performance by means of hydrogen bond acting force and preparation method | |
| CN110743393A (en) | Preparation of lignin-based polyarylester composite nanofiltration membrane | |
| WO2012155368A1 (en) | Method for preparing 2, 5-dihydroxyterephthalic acid | |
| CN116102758A (en) | Flexible ultrathin ZIF-8 film with charged covalent organic framework participation, and preparation and application thereof | |
| CN114100380A (en) | Mixed matrix membrane with through channel structure and preparation and application thereof | |
| CN112495360B (en) | Solid composite catalyst for continuously preparing 3-hydroxybutyraldehyde, and preparation method and application thereof | |
| CN112409593B (en) | Side chain type polyphenylene oxide containing benzimidazole structure, preparation method thereof and homogeneous anion exchange membrane | |
| CN104370764A (en) | Diethylenetriamine derivatives, and preparation method and application thereof | |
| CN103249838B (en) | Method for producing lactate | |
| CN1432556A (en) | Prepn process of 2,2,2-trifluoroethyl acetate | |
| CN112457495A (en) | Preparation method of homogeneous anion exchange membrane | |
| CN116272433B (en) | Modified polyvinylidene fluoride water treatment film and preparation method thereof | |
| CN116212661B (en) | Covalent organic framework organic solvent nanofiltration membrane with odd-even effect functionalization and preparation method thereof | |
| IL31713A (en) | Preparation of semi-permeable membranes | |
| JPS6410242B2 (en) | ||
| CN1085660C (en) | Process for preparing monomer of sodium allylsulfonate | |
| CN113461491B (en) | Preparation method of trifluoro isopropyl alcohol | |
| CN113620814B (en) | Green preparation method of 2, 2-bis (4-aminophenyl) hexafluoropropane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| DD01 | Delivery of document by public notice |
Addressee: Zhang Han Document name: Notification of Qualified Preliminary Examination of Invention Patent Application Addressee: Zhang Han Document name: Notification of Entry of Invention Patent Application into the Substantial Examination Stage Addressee: Zhang Han Document name: Notification of Publication of Invention Patent Application |
|
| DD01 | Delivery of document by public notice | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |