CN110467193A - A kind of Titanium Sieve Molecular Sieve, preparation method and application - Google Patents
A kind of Titanium Sieve Molecular Sieve, preparation method and application Download PDFInfo
- Publication number
- CN110467193A CN110467193A CN201811301616.7A CN201811301616A CN110467193A CN 110467193 A CN110467193 A CN 110467193A CN 201811301616 A CN201811301616 A CN 201811301616A CN 110467193 A CN110467193 A CN 110467193A
- Authority
- CN
- China
- Prior art keywords
- titanium
- molecular sieve
- pore creating
- creating material
- preparation
- 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
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000010936 titanium Substances 0.000 title claims abstract description 89
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 89
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 66
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 239000011148 porous material Substances 0.000 claims abstract description 57
- 239000000463 material Substances 0.000 claims abstract description 52
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 24
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 23
- 239000010703 silicon Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000011541 reaction mixture Substances 0.000 claims abstract description 19
- DWLVWMUCHSLGSU-UHFFFAOYSA-M n,n-dimethylcarbamate Chemical compound CN(C)C([O-])=O DWLVWMUCHSLGSU-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 230000006315 carbonylation Effects 0.000 claims abstract description 12
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 25
- 239000005457 ice water Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 235000019441 ethanol Nutrition 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- 150000001413 amino acids Chemical class 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 10
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 10
- 229910001868 water Inorganic materials 0.000 claims description 10
- 239000004472 Lysine Substances 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- KXDHJXZQYSOELW-UHFFFAOYSA-M Carbamate Chemical compound NC([O-])=O KXDHJXZQYSOELW-UHFFFAOYSA-M 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PHIQHXFUZVPYII-ZCFIWIBFSA-N (R)-carnitine Chemical compound C[N+](C)(C)C[C@H](O)CC([O-])=O PHIQHXFUZVPYII-ZCFIWIBFSA-N 0.000 claims description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- HNSUOMBUJRUZHJ-REVJHSINSA-N [(2r)-3-carboxy-2-hydroxypropyl]-trimethylazanium;(z)-4-hydroxy-4-oxobut-2-enoate Chemical compound OC(=O)\C=C/C(O)=O.C[N+](C)(C)C[C@H](O)CC([O-])=O HNSUOMBUJRUZHJ-REVJHSINSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- GTCAXTIRRLKXRU-UHFFFAOYSA-N methyl carbamate Chemical group COC(N)=O GTCAXTIRRLKXRU-UHFFFAOYSA-N 0.000 claims description 4
- YNTOKMNHRPSGFU-UHFFFAOYSA-N n-Propyl carbamate Chemical compound CCCOC(N)=O YNTOKMNHRPSGFU-UHFFFAOYSA-N 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 150000005622 tetraalkylammonium hydroxides Chemical class 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 4
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- 150000003673 urethanes Chemical class 0.000 claims description 3
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical class OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 abstract description 11
- 239000000376 reactant Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000013459 approach Methods 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 44
- 239000000243 solution Substances 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 14
- -1 diallyl dimethyl ammoniumchloride quaternary ammonium salt Chemical class 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 229960003646 lysine Drugs 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 235000001014 amino acid Nutrition 0.000 description 7
- 230000001105 regulatory effect Effects 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 235000019766 L-Lysine Nutrition 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000010792 warming Methods 0.000 description 5
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 4
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 description 4
- 238000004817 gas chromatography Methods 0.000 description 4
- 238000009423 ventilation Methods 0.000 description 4
- BVHLGVCQOALMSV-JEDNCBNOSA-N L-lysine hydrochloride Chemical compound Cl.NCCCC[C@H](N)C(O)=O BVHLGVCQOALMSV-JEDNCBNOSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229960005337 lysine hydrochloride Drugs 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- SKKTUOZKZKCGTB-UHFFFAOYSA-N butyl carbamate Chemical compound CCCCOC(N)=O SKKTUOZKZKCGTB-UHFFFAOYSA-N 0.000 description 2
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 235000018977 lysine Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- UCPYLLCMEDAXFR-UHFFFAOYSA-N triphosgene Chemical compound ClC(Cl)(Cl)OC(=O)OC(Cl)(Cl)Cl UCPYLLCMEDAXFR-UHFFFAOYSA-N 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- LFLWJSKDEYXFJD-UHFFFAOYSA-N 1-chloro-3-(1-isocyanatoethyl)benzene Chemical compound O=C=NC(C)C1=CC=CC(Cl)=C1 LFLWJSKDEYXFJD-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- BVCZEBOGSOYJJT-UHFFFAOYSA-N ammonium carbamate Chemical compound [NH4+].NC([O-])=O BVCZEBOGSOYJJT-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N carbonic acid monoamide Natural products NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- UFEJKYYYVXYMMS-UHFFFAOYSA-N methylcarbamic acid Chemical class CNC(O)=O UFEJKYYYVXYMMS-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000003866 trichloromethyl group Chemical group ClC(Cl)(Cl)* 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
- C01B39/085—Group IVB- metallosilicates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
- C07C271/28—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a non-condensed six-membered aromatic ring
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of Titanium Sieve Molecular Sieve, preparation method and applications, and described method includes following steps: (1) mixing titanium source, silicon source, the aqueous solution of micropore pore creating material and mesoporous pore creating material；Obtain reaction mixture；(2) reaction mixture is subjected to hydrothermal crystallizing, obtains reaction product；(3) reaction product is roasted, obtains Titanium Sieve Molecular Sieve.The method reduces template cost, and it is more friendly to environment, efficiently solve the diffusion problem of reactant, obtained Titanium Sieve Molecular Sieve shows excellent catalytic performance in the reaction of m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate, in addition, the present invention also provides a kind of new approaches using Titanium Sieve Molecular Sieve preparation isophthalic dimethyl carbamate.
Description
Technical field
The invention belongs to catalyst technical field, it is related to a kind of Titanium Sieve Molecular Sieve, preparation method and application, more particularly to
A kind of porous structure Titanium Sieve Molecular Sieve, preparation method and the application in preparation isophthalic dimethyl carbamate.
Background technique
Titanium Sieve Molecular Sieve since the advent of the world has played important function petrochemical industry, Industrial Catalysis etc. are multi-field.It is attributed to
Its unique MFI topological structure and titanium atom introduce bring catalytic performance, and making it in a mild condition can be realized to selection
The efficient catalytic of property oxidation reaction.But traditional titanium sieve molecular sieve activity center is located on micropore hole wall, larger-size organic
Object molecule can not diffuse into inside micropore canals.
To solve the above problems, researcher develops the method for largely synthesizing porous Titanium Sieve Molecular Sieve, water is focused primarily upon
Thermal synthesis method, gas phase crystallization method and dry gel conversion method etc..As CN105197956B discloses a kind of system of TS-1 Titanium Sieve Molecular Sieve
Preparation Method, method includes the following steps: 1) hydrolyzing: with molar ratio computing, according to the SiO in silicon source2: the TiO in titanium source2: template
Agent: H2O is 1:(0.01-0.08): (0.05-0.4): the ratio of (10-25) prepares reaction mixture solution, and reaction is mixed
Object is hydrolyzed 3-5 hours under the conditions of 20-70 DEG C；Wherein, the template is tetrapropylammonium hydroxide；2) it catches up with alcohol: will walk
It is rapid 1) obtained in reaction mixture be warming up to 70-95 DEG C, catch up with alcohol 2-6 hours, deionized water added during catching up with alcohol so that
Template agent concentration changing value in reaction mixture is within ± 10%；3) crystallization: hydrothermal crystallizing temperature is 175-200 DEG C,
The hydrothermal crystallizing time is 2-4 hours, can be crystallized in a stationary situation or under stirring condition；4) it is filtered, washed, dries and roasts
Product after crystallization that upper step obtains is filtered, washed, is dried and after roasting 3-6 hours, TS-1 titanium is made at 500 to 600 DEG C
Si molecular sieves, wherein in step 2), the concentration of the tetrapropylammonium hydroxide is 5-10wt%.In all multi-methods, template
The cost control of agent is a common problem.It is using diallyl dimethyl ammoniumchloride quaternary ammonium salt from document report
Since template successfully prepares porous Beta molecular sieve, organic surface active agent starts to be widely used in porous point as soft template
The preparation of son sieve.Relative to common hard template is synthesized in early days, soft template is usually organic surface active agent, has structure and acid
Property the strong advantage of controllability, currently used soft template mainly include containing multi-quaternary ammonium group group alkyl quaternary ammonium salts and parents' organosilicon
Surfactant.But the problem of soft template is simultaneously there is also expensive, high expensive.Therefore, exploitation template low cost
Or recyclable process for preparing titanium-silicon molecular sieve is of great significance.
At present the traditional processing technology of isophthalic dimethylamino diisocyanate be using m-xylene diamine phosgenation low temperature at
Salt method has a small amount of m-chloro methylbenzyl isocyanate in reaction process and generates, and the method is using the phosgene of severe toxicity, use,
There is very big risk in transport and storing process.Existing research person improves phosgenation, designs triphosgene synthesis
The production line of isophthalic dimethylamino diisocyanate, but triphosgene, i.e., two (trichloromethyl) carbonic esters still have certain poison
Property, environment friendly is poor.Therefore, the inexorable trend that new green syt route is technology development is found.
Organic diamine carbonylation prepares isocyanate intermediate diurethane, prepares diisocyanate using pyrolysismethod
Route early have been reported that but severe reaction conditions, catalyst has the problems such as difficult recycling, difficult preparation.With catalyst in recent years
The development of technology of preparing and the appearance of new catalyst, the route have been achieved with the efficient preparation of a variety of diisocyanate.The road
Application of the line in the production of isophthalic dimethylamino diisocyanate is broadly divided into two steps, i.e. intermediate isophthalic dimethyl carbamate
Synthesis and intermediate pyrolysis preparation isophthalic dimethylamino diisocyanate.Preparing key intermediate isophthalic dimethyl carbamate
During, developing effective catalyst is the key that practical application.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of Titanium Sieve Molecular Sieve, preparation method
And application, the method replace expensive pore creating material using the amino acid and its derivative part that can pass through straightforward procedure recycling
Tetrapropylammonium hydroxide efficiently solves the diffusion problem of reactant；Prepared titanium silicon porous molecular screen is applied to isophthalic two
The preparation of methylamino formic acid esters has excellent catalytic effect.
To achieve this purpose, the present invention adopts the following technical scheme:
A kind of preparation method of Titanium Sieve Molecular Sieve, described method includes following steps:
(1) titanium source, silicon source, the aqueous solution of micropore pore creating material and mesoporous pore creating material are mixed；Obtain reaction mixture；
(2) reaction mixture is subjected to hydrothermal crystallizing, obtains reaction product；
(3) reaction product is roasted, obtains Titanium Sieve Molecular Sieve.
The method replaces expensive pore-creating using the amino acid and its derivative part that can pass through straightforward procedure recycling
Agent tetrapropylammonium hydroxide efficiently solves the diffusion problem of reactant.Cost is relatively low for the preparation method, environmentally friendly
Preferably, the new approaches of Titanium Sieve Molecular Sieve preparation are provided.
Step (1) mixing specifically includes: first mixing titanium source and silicon source, obtains the first mixture；Later by first
Mixture is mixed with the aqueous solution of micropore pore creating material, obtains the second mixture；The second mixture is mixed with mesoporous pore creating material again.
The hydrolysis of titanium can be reduced using this kind of order by merging, effectively inhibit the formation of anatase.
The mixing of the titanium source and silicon source includes the following steps: in ice water bath environment, and silicon source is added into titanium source.Pass through
Low temperature controls the hydrolysis of titanium, to reduce the formation of anatase.
Preferably, the form of the addition is to be added dropwise.
Preferably, the rate of addition be 0.5~1.5mL/min, as 0.5mL/min, 0.6mL/min, 0.7mL/min,
0.8mL/min, 0.9mL/min, 1.0mL/min, 1.1mL/min, 1.2mL/min, 1.3mL/min, 1.4mL/min or 1.5mL/
Min etc., preferably 0.6~1.2mL/min, further preferred 1mL/min.
Preferably, the mixing of the titanium source and silicon source carries out under agitation.
Preferably, the time of the stirring be 0.2~1.2h, as 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h,
0.9h, 1.0h, 1.1h or 1.2h etc., preferably 0.5~1h, further preferred 0.8~1h.
Preferably, the mixing speed be 50~350rpm, as 60rpm, 80rpm, 100rpm, 120rpm, 140rpm,
160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, 320rpm or 340rpm etc., preferably
100~300rpm, further preferred 150~200rpm.
Preferably, the titanium source is any in titanium tetrachloride, tetraethyl titanate, metatitanic acid orthocarbonate or butyl titanate
It is a kind of or at least two combination.Typical but non-limiting combination such as titanium tetrachloride and tetraethyl titanate, metatitanic acid orthocarbonate with
Butyl titanate.
Preferably, the silicon source is selected from methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate or silica gel
In any one or at least two combination.Typical but non-limiting combination such as methyl orthosilicate and ethyl orthosilicate, just
Silicic acid propyl ester, butyl silicate and silica gel.
Preferably, the mixing of the aqueous solution of first mixture and micropore pore creating material includes the following steps: in ice-water bath
In environment, the aqueous solution of micropore pore creating material is added into the first mixture.
Preferably, the form of the addition is to be added dropwise.
Preferably, the rate of addition be 0.5~1.5mL/min, as 0.5mL/min, 0.6mL/min, 0.7mL/min,
0.8mL/min, 0.9mL/min, 1.0mL/min, 1.1mL/min, 1.2mL/min, 1.3mL/min, 1.4mL/min or 1.5mL/
Min etc., preferably 0.6~1.2mL/min, further preferred 1mL/min.
Preferably, the mixing of first mixture and the aqueous solution of micropore pore creating material carries out under agitation.
Preferably, the time of the stirring be 0.2~1.2h, as 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h,
0.9h, 1.0h, 1.1h or 1.2h etc., preferably 0.5~1h, further preferred 0.8~1h.
Preferably, the speed of the stirring be 50~350rpm, as 60rpm, 80rpm, 100rpm, 120rpm, 140rpm,
160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, 320rpm or 340rpm etc., preferably
100~300rpm, further preferred 150~200rpm.
Preferably, the micropore pore creating material is selected from tetra-alkyl ammonium hydroxide, preferably tetramethylammonium hydroxide, tetraethyl hydrogen
In amine-oxides, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide any one or at least two combination.Typical but non-limit
The combination such as tetramethylammonium hydroxide and tetraethyl ammonium hydroxide of property processed, tetrapropylammonium hydroxide and tetrabutylammonium hydroxide.
Preferably, the mixing of second mixture and mesoporous pore creating material includes the following steps: under agitation, to the
Mesoporous pore creating material is added in two mixtures.
Preferably, the time of the stirring be 0.2~1.2h, as 0.3h, 0.4h, 0.5h, 0.6h, 0.7h, 0.8h,
0.9h, 1.0h, 1.1h or 1.2h etc., preferably 0.5~1h, further preferred 0.8~1h.
Preferably, the mixing speed be 50~350rpm, as 60rpm, 80rpm, 100rpm, 120rpm, 140rpm,
160rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, 320rpm or 340rpm etc., preferably
100~300rpm, further preferred 150~200rpm.
Preferably, the mesoporous pore creating material is selected from the derivative of amino acid and/or amino acid, preferably lysine, bad ammonia
Any one in acid hydrochloride, L-carnitine, L-carnitine fumarate or L-carnitine-L-tartrate or at least two
Combination.Typical but non-limiting combination such as lysine and lysine hydrochloride, L-carnitine and L-carnitine fumarate, rely
Propylhomoserin, lysine hydrochloride and L-carnitine-L-tartrate.
SiO in step (1) described silicon source2, TiO in titanium source2, micropore pore creating material, mesoporous pore creating material and water molar ratio
For 1:(0.001-0.1): (0.001-5): (0.001-1): (5-400), such as 1:0.002:0.005:0.003:10,1:0.005:
0.05:0.04:50、1:0.02:0.1:0.05:100、1:0.05:1:0.01:200、1:0.08:2:0.07:300、1:0.09:
4:0.1:350 or 1:0.05:3:0.7:380 etc..
The temperature of step (2) described hydrothermal crystallizing is 160-210 DEG C, such as 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C, excellent
Select 180~200 DEG C.
Preferably, the time of the hydrothermal crystallizing is 12-48h, such as 15h, 18h, 20h, 25h, 30h, 35h, 40h or 45h
Deng preferably 16~40h.
The temperature of step (3) described roasting is 400-800 DEG C, such as 420 DEG C, 450 DEG C, 480 DEG C, 500 DEG C, 550 DEG C, 600
DEG C, 650 DEG C or 750 DEG C etc., preferably 500~700 DEG C, further preferred 550~650 DEG C.
Preferably, the time of step (3) described roasting is 4-24h, such as 5h, 8h, 10h, 18h, 20h or 22h, preferably 10
~20h.
Preferably, also reaction product is pre-processed before step (3) described roasting, the pretreatment includes solid-liquid point
From washing and drying.
The preparation method of the Titanium Sieve Molecular Sieve includes the following steps: as a preferred technical solution,
(1) under ice-water bath and stirring condition, titanium source and silicon source is mixed, the first mixture is obtained；Keep ice-water bath and
The aqueous solution of micropore pore creating material is added into the first mixture, obtains the second mixture for stirring condition；Ice-water bath is removed, to
Mesoporous pore creating material is added in two mixtures, obtains reaction mixture；Wherein, the SiO in silicon source2, TiO in titanium source2, micropore makes
The molar ratio of hole agent, mesoporous pore creating material and water is 1:(0.001-0.1): (0.001-5): (0.001-1): (5-400)；Micropore is made
Hole agent is selected from tetra-alkyl ammonium hydroxide；Mesoporous pore creating material is selected from the derivative of amino acid and/or amino acid；
(2) reaction mixture is obtained into reaction product in 160-210 DEG C of hydrothermal crystallizing 12-48h；
(3) reaction product is separated by solid-liquid separation, washs and dry, and for 400-800 DEG C of roasting 4-24h, obtain it is described
Titanium Sieve Molecular Sieve.
The present invention also provides using Titanium Sieve Molecular Sieve made from above-mentioned preparation method, the aperture of the Titanium Sieve Molecular Sieve is
1~2 μm；Specific surface area is 40~600m2/g。
The present invention also provides a kind of method of m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate, this method makes
Use above-mentioned Titanium Sieve Molecular Sieve as catalyst.I.e. the present invention also provides a kind of purposes of Titanium Sieve Molecular Sieve.
There is excellent catalysis to imitate for the preparation that prepared titanium silicon porous molecular screen is applied to isophthalic dimethyl carbamate
Fruit.
The method of the m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate includes: in an inert atmosphere, with ammonia
Carbamate and m-xylene diamine are raw material or using urea and m-phenylene diamine (MPD) as raw material, and alcohol is solvent, and Titanium Sieve Molecular Sieve is catalysis
Agent, heating are reacted, and isophthalic dimethyl carbamate is obtained.
Preferably, the inert atmosphere is selected from nitrogen atmosphere or inert gas atmosphere etc..
Preferably, the reaction carries out in a high pressure reaction kettle.
Preferably, the carbamate is selected from methyl carbamate, urethanes, carbamic acid propyl ester or ammonia
In base butyl formate any one or at least two combination.
Preferably, the molar ratio of the m-xylene diamine and carbamate is 1:(5-20), such as 1:6,1:8,1:10,1:
12,1:15 or 1:18 etc..
Preferably, the molar ratio of the m-phenylene diamine (MPD) and urea is 1:(5-20), such as 1:6,1:8,1:10,1:12,1:15
Or 1:18 etc..
Preferably, the alcohol in methanol, ethyl alcohol, propyl alcohol or butanol any one or at least two combination.Allusion quotation
Type but unrestricted combination such as methanol and ethyl alcohol, methanol and butanol, ethyl alcohol, propyl alcohol and butanol.
Preferably, the molar ratio of the alcohol and m-xylene diamine is (8-40): 1, such as 10:1,12:1,18:1,20:1,25:
1,30:1 or 36:1 etc.
Preferably, the mass ratio of the catalyst and m-xylene diamine be (0.001-1): 1, as 0.003:1,0.005:1,
0.008:1,0.01:1,0.03:1,0.04:1,0.07:1 or 0.09:1 etc..
Preferably, the temperature of the reaction is 180-260 DEG C, such as 190 DEG C, 200 DEG C, 220 DEG C, 230 DEG C or 250 DEG C.
Preferably, the time of the reaction is 0.5-12h, such as 1h, 2h, 3h, 5h, 8h or 10h.
The method packet of the m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate as a preferred technical solution,
It includes:
It in an inert atmosphere, is raw material or using urea and m-phenylene diamine (MPD) as raw material using carbamate and m-xylene diamine,
Alcohol is solvent, and Titanium Sieve Molecular Sieve is catalyst, reacts 0.5-12h under the conditions of 180-260 DEG C, obtains isophthalic dimethylamino formic acid
Ester；Wherein, the molar ratio of m-xylene diamine and carbamate or urea is 1:(5-20)；The molar ratio of alcohol and m-xylene diamine
For (8-40): 1；The mass ratio of catalyst and m-xylene diamine is (0.001-1): 1.
Numberical range of the present invention not only includes enumerated point value, further includes the above-mentioned numerical value not included
Arbitrary point value between range, as space is limited and for concise consideration, range described in the present invention no longer exclusive list includes
Specific point value.
Compared with prior art, the invention has the benefit that
The preparation method of Titanium Sieve Molecular Sieve provided by the invention has by using recyclable amino acid and its derivative etc.
Machine object does pore creating material, partially instead of expensive conventional template agent, reduces the cost of template, efficiently solves reactant
Diffusion problem.
Titanium Sieve Molecular Sieve provided by the invention is in the reaction of m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate
Show excellent catalytic performance, wherein m-xylene diamine conversion ratio is greater than 99%, the isophthalic dimethylamino first under optimum condition
The yield of acid esters is greater than 90%.
Cost is relatively low for the preparation method of Titanium Sieve Molecular Sieve provided by the invention, more friendly to environment, while providing one
Kind prepares the application new approaches of isophthalic dimethyl carbamate using titanium-silicon molecular sieve catalyst.
Detailed description of the invention
Fig. 1 is the X-ray diffractogram of the sample 1 prepared in the embodiment of the present invention 1.
Fig. 2 is the scanning electron microscope (SEM) photograph of the sample 1 prepared in the embodiment of the present invention 1.
Fig. 3 is the low power transmission electron microscope picture of the sample 1 prepared in the embodiment of the present invention 1.
Fig. 4 is that the high power of the sample 1 prepared in the embodiment of the present invention 1 projects electron microscope.
Fig. 5 is the infrared test figure of sample 1 and L-lysine after the washing that the embodiment of the present invention 1 provides.
Specific embodiment
To further illustrate the technical scheme of the present invention below with reference to the accompanying drawings and specific embodiments.
Embodiment 1
A kind of preparation method of Titanium Sieve Molecular Sieve, includes the following steps:
(1) under ice-water bath and stirring condition, the positive silicic acid tetrem of 13.2mL is slowly added into 0.72g butyl titanate
Ester is stirred 30 minutes, is then added dropwise under stirring 25mL tetrapropylammonium hydroxide solution (25wt%), stirring 12
Hour；Ice-water bath is removed, 3.46g L-lysine is added into reaction mixture, stirs 3 hours, obtains clear solution；
(2) clear solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of 170 DEG C
Crystallization 48 hours, obtain reaction product；
(3) reaction product is centrifuged, is washed, separated, it is dry, and the sample dried is roasted 6 hours at 550 DEG C,
Cooled to room temperature obtains porous Titanium Sieve Molecular Sieve sample 1.
It is tested through BET, the area ratio of the sample intermediary hole and micropore is 21%.
Fig. 1 is the X-ray diffractogram of sample 1 prepared by embodiment 1, be shown in figure 7.8 °, 8.8 °, 23.2 °,
23.8 ° occur the characteristic peak of MFI topological structure with 24.3 °, and 24.3 ° become single diffraction maximum with 29.4 ° of double diffraction peak, this quilt
It is considered that Ti enters the strong evidence of skeleton.Fig. 2 is the scanning electron microscope (SEM) photograph of sample 1, it can be seen that the Titanium Sieve Molecular Sieve of synthesis is big
Small uniform, crystallinity is higher, and shows unique pattern.Fig. 3 and Fig. 4 is respectively the low power transmission electron microscope of sample 1 in example 1
Figure and high power transmission electron microscope picture, it can be observed that the lattice fringe of rule, and certain intergranular pore channel is formd, be conducive to react
The diffusion and absorption of object.Fig. 5 is the infrared test figure of sample 1 and L-lysine after washing, it can be seen that L- relies ammonia after washing
Characteristic peak (the 1421cm of acid-1With 1204cm-1) disappear substantially, illustrate to recycle L-lysine by simply washing.
Embodiment 2
A kind of preparation method of Titanium Sieve Molecular Sieve, includes the following steps:
(1) under ice-water bath and stirring condition, the positive silicic acid tetrem of 13.2mL is slowly added into 0.72g butyl titanate
Ester is stirred 30 minutes, is then added dropwise under stirring 12.5mL tetrapropylammonium hydroxide solution (25wt%), is stirred
12 hours；Ice-water bath is removed, 3.81g L-carnitine is added into reaction mixture, stirs 3 hours, obtains clear solution；
(2) clear solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of 180 DEG C
Crystallization 48 hours, obtain reaction product；
(3) reaction product is centrifuged, is washed, separated, it is dry, and the sample dried is roasted 6 hours at 550 DEG C,
Cooled to room temperature obtains porous Titanium Sieve Molecular Sieve sample 2.
X-ray diffraction test is carried out to sample 2, test result is shown in 7.8 °, 8.8 °, 23.2 °, 23.8 ° and goes out with 24.3 °
The characteristic peak of existing MFI topological structure, and 24.3 ° become single diffraction maximum with 29.4 ° of double diffraction peak.
To sample 2 be scanned Electronic Speculum test, test structure are as follows: the Titanium Sieve Molecular Sieve size of synthesis is uniform, crystallinity compared with
Height, and show unique pattern.
Transmissioning electric mirror test, test result are as follows: sample 2 has well-regulated lattice fringe, and forms one are carried out to sample 2
Fixed intergranular pore channel is conducive to the diffusion and absorption of reactant.
Embodiment 3
A kind of preparation method of Titanium Sieve Molecular Sieve, includes the following steps:
(1) under ice-water bath and stirring condition, the positive silicic acid tetrem of 13.2mL is slowly added into 0.72g butyl titanate
Ester is stirred 30 minutes, is then added dropwise under stirring 12.5mL tetrapropylammonium hydroxide solution (25wt%), is stirred
12 hours；Ice-water bath is removed, 3.46g L-carnitine-L-tartrate is added into reaction mixture, stirs 3 hours, is clarified
Solution；
(2) clear solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of 180 DEG C
Crystallization 48 hours, obtain reaction product；
(3) reaction product is centrifuged, is washed, separated, it is dry, and the sample dried is roasted 6 hours at 550 DEG C,
Cooled to room temperature obtains porous Titanium Sieve Molecular Sieve sample 3.
X-ray diffractogram test is carried out to sample 3, test result is shown in 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °
There is the characteristic peak of MFI topological structure, and 24.3 ° become single diffraction maximum with 29.4 ° of double diffraction peak.
To sample 3 be scanned Electronic Speculum test, test structure are as follows: the Titanium Sieve Molecular Sieve size of synthesis is uniform, crystallinity compared with
Height, and show unique pattern.
Transmissioning electric mirror test, test result are as follows: sample 3 has well-regulated lattice fringe, and forms one are carried out to sample 3
Fixed intergranular pore channel is conducive to the diffusion and absorption of reactant.
Embodiment 4
A kind of preparation method of Titanium Sieve Molecular Sieve, includes the following steps:
(1) it under ice-water bath and stirring condition, is slowly added to positive silicic acid propyl ester into titanium tetrachloride, stirs 30 minutes, so
Tetraethyl ammonium hydroxide aqueous solution is added dropwise under stirring afterwards, stirs 12 hours；Ice-water bath is removed, to reaction mixture
Middle addition L-carnitine fumarate stirs 3 hours, obtains clear solution；SiO in silicon source2, TiO in titanium source2, micropore makes
The molar ratio of hole agent, mesoporous pore creating material and water is SiO2:TiO2: micropore pore creating material: mesoporous pore creating material: solvent=1:0.001:5:
0.001:400；
(2) clear solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of 210 DEG C
Crystallization 12 hours, obtain reaction product；
(3) reaction product is centrifuged, is washed, separated, it is dry, and the sample dried is roasted 24 hours at 400 DEG C,
Cooled to room temperature obtains porous Titanium Sieve Molecular Sieve sample 4.
X-ray diffractogram test is carried out to sample 4, test result is shown in 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °
There is the characteristic peak of MFI topological structure, and 24.3 ° become single diffraction maximum with 29.4 ° of double diffraction peak.
To sample 4 be scanned Electronic Speculum test, test structure are as follows: the Titanium Sieve Molecular Sieve size of synthesis is uniform, crystallinity compared with
Height, and show unique pattern.
Transmissioning electric mirror test, test result are as follows: sample 4 has well-regulated lattice fringe, and forms one are carried out to sample 4
Fixed intergranular pore channel is conducive to the diffusion and absorption of reactant.
Embodiment 5
A kind of preparation method of Titanium Sieve Molecular Sieve, includes the following steps:
(1) under ice-water bath and stirring condition, it is slowly added to silica gel into metatitanic acid orthocarbonate, stirs 30 minutes, then exists
Tetramethylammonium hydroxide aqueous solution is added dropwise under stirring, stirs 12 hours；Ice-water bath is removed, is added into reaction mixture
Enter lysine hydrochloride, stirs 3 hours, obtain clear solution；SiO in silicon source2, TiO in titanium source2, micropore pore creating material, be situated between
The molar ratio of hole pore creating material and water is SiO2:TiO2: micropore pore creating material: mesoporous pore creating material: solvent=1:0.1:0.001:1:5；
(2) clear solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of 160 DEG C
Crystallization 48 hours, obtain reaction product；
(3) reaction product is centrifuged, is washed, separated, it is dry, and the sample dried is roasted 4 hours at 800 DEG C,
Cooled to room temperature obtains porous Titanium Sieve Molecular Sieve sample 5.
X-ray diffractogram test is carried out to sample 5, test result is shown in 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °
There is the characteristic peak of MFI topological structure, and 24.3 ° become single diffraction maximum with 29.4 ° of double diffraction peak.
To sample 5 be scanned Electronic Speculum test, test structure are as follows: the Titanium Sieve Molecular Sieve size of synthesis is uniform, crystallinity compared with
Height, and show unique pattern.
Transmissioning electric mirror test, test result are as follows: sample 5 has well-regulated lattice fringe, and forms one are carried out to sample 5
Fixed intergranular pore channel is conducive to the diffusion and absorption of reactant.
Embodiment 6
A kind of preparation method of Titanium Sieve Molecular Sieve, includes the following steps:
(1) under ice-water bath and stirring condition, slowly add into metatitanic acid orthocarbonate and tetramethoxy titanate ester (molar ratio 1:1)
Enter methyl orthosilicate and ethyl orthosilicate (molar ratio 2:1), stirs 30 minutes, four fourths are then added dropwise under stirring
Base ammonium hydroxide and tetramethylammonium hydroxide aqueous solution (tetrabutylammonium hydroxide and tetramethylammonium hydroxide molar ratio are 1:
2) it, stirs 12 hours；Ice-water bath is removed, L-carnitine-L-tartrate and L-carnitine (molar ratio are added into reaction mixture
For 3:2), stirs 3 hours, obtain clear solution；SiO in silicon source2, TiO in titanium source2, micropore pore creating material, mesoporous pore creating material
Molar ratio with water is SiO2:TiO2: micropore pore creating material: mesoporous pore creating material: solvent=1:0.05:3:0.5:200；
(2) clear solution is transferred in the stainless steel cauldron with polytetrafluoroethyllining lining, under conditions of 200 DEG C
Crystallization 30 hours, obtain reaction product；
(3) reaction product is centrifuged, is washed, separated, it is dry, and the sample dried is roasted 20 hours at 600 DEG C,
Cooled to room temperature obtains porous Titanium Sieve Molecular Sieve sample 6.
X-ray diffractogram test is carried out to sample 6, test result is shown in 7.8 °, 8.8 °, 23.2 °, 23.8 ° and 24.3 °
There is the characteristic peak of MFI topological structure, and 24.3 ° become single diffraction maximum with 29.4 ° of double diffraction peak.
To sample 6 be scanned Electronic Speculum test, test structure are as follows: the Titanium Sieve Molecular Sieve size of synthesis is uniform, crystallinity compared with
Height, and show unique pattern.
Transmissioning electric mirror test, test result are as follows: sample 6 has well-regulated lattice fringe, and forms one are carried out to sample 6
Fixed intergranular pore channel is conducive to the diffusion and absorption of reactant.
Application Example 1
A kind of method of m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate, comprising:
1.36g m-xylene diamine, 4.45g urethanes are taken, 7.8g ethyl alcohol and 0.2g sample 1 are added to 50mL high pressure
In reaction kettle, it is passed through nitrogen, is hunted leak, after being warming up to 200 DEG C, reaction 8 hours after ventilation under nitrogen protection under normal pressure, sampling enters
Gas-chromatography is analyzed.
The result shows that m-xylene diamine conversion ratio is greater than 99%, isophthalic dimethylamino Ethyl formate yield is 97.7%
Product.
Application Example 2
A kind of method of m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate, comprising:
Using urea and m-xylene diamine as raw material, methanol is solvent, and sample 3 is catalyst, and above-mentioned material is added to
In autoclave, be passed through nitrogen, hunt leak, be warming up to 180 DEG C after ventilation under nitrogen protection under normal pressure, after reacting 12h, sample into
Enter gas-chromatography to be analyzed；Wherein, the molar ratio of m-xylene diamine and urea is 1:5；Mole of methanol and m-xylene diamine
Than for 40:1；The mass ratio of catalyst and m-xylene diamine is 1:1.
The result shows that m-xylene diamine conversion ratio is greater than 99%, isophthalic dimethylamino Ethyl formate yield is 91.3%
Product.
Application Example 3
A kind of method of m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate, comprising:
Using butyl carbamate and m-xylene diamine as raw material, butanol is solvent, and sample 5 is catalyst, by above-mentioned object
Material is added in autoclave, is passed through nitrogen, is hunted leak, and is warming up to 260 DEG C after ventilation under nitrogen protection under normal pressure, reacts 0.5h
Afterwards, sampling enters gas-chromatography and is analyzed；Wherein, the molar ratio of m-xylene diamine and butyl carbamate is 1:20；Butanol
Molar ratio with m-xylene diamine is 8:1；The mass ratio 0.001:1 of catalyst and m-xylene diamine.
The result shows that m-xylene diamine conversion ratio is greater than 99%, isophthalic dimethylamino Ethyl formate yield is 90.1%
Product.
Application Example 4
A kind of method of m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate, comprising:
Using carbamic acid propyl ester and m-xylene diamine as raw material, propyl alcohol is solvent, and sample 2 is catalyst, by above-mentioned object
Material is added in autoclave, is passed through nitrogen, is hunted leak, and is warming up to 230 DEG C after ventilation under nitrogen protection under normal pressure, reacts 10h
Afterwards, sampling enters gas-chromatography and is analyzed；Wherein, the molar ratio of m-xylene diamine and carbamic acid propyl ester is 1:10；Propyl alcohol
Molar ratio with m-xylene diamine is 20:1；The mass ratio of catalyst and m-xylene diamine is 0.5:1.
The result shows that m-xylene diamine conversion ratio is greater than 99%, isophthalic dimethylamino Ethyl formate yield is 95.4%
Product.
Comparative example 1
A kind of preparation method of Titanium Sieve Molecular Sieve is removed the L-lysine in step (1) replacing with tetrapropylammonium hydroxide
Outside, remaining is same as Example 1.Porous Titanium Sieve Molecular Sieve sample 7 is made.
It is tested through BET, the area ratio of the sample intermediary hole and micropore is 13%.
X-ray diffraction test is carried out to sample 7, test result is shown in 7.8 °, 8.8 °, 23.2 °, 23.8 ° and goes out with 24.3 °
The characteristic peak of existing MFI topological structure, and 24.3 ° become single diffraction maximum with 29.4 ° of double diffraction peak.
Electronic Speculum test is scanned to sample 7, tests structure are as follows: sample size is uniform, and crystallinity is higher, and particle size is
200-400nm。
Transmissioning electric mirror test, test result are as follows: sample 7 has well-regulated lattice fringe, but without apparent are carried out to sample 7
Intergranular pore channel.
Comparative example 2
A kind of preparation method of Titanium Sieve Molecular Sieve, in addition to the L-lysine in step (1) is replaced with starch, remaining and reality
It is identical to apply example 1.Porous Titanium Sieve Molecular Sieve sample 8 is made.
It is tested through BET, the area ratio of the sample intermediary hole and micropore is 35%.
X-ray diffraction test is carried out to sample 8, test result is shown in 7.8 °, 8.8 °, 23.2 °, 23.8 ° and goes out with 24.3 °
The characteristic peak of existing MFI topological structure, and 24.3 ° become single diffraction maximum with 29.4 ° of double diffraction peak, but crystallinity is slightly decreased.
Electronic Speculum test is scanned to sample 8, tests structure are as follows: sample size is uniform, particle size 350-550nm.
Transmissioning electric mirror test, test result are as follows: sample 8 has well-regulated lattice fringe, and forms one are carried out to sample 8
Fixed intergranular pore channel is conducive to the diffusion and absorption of reactant.
The Applicant declares that the foregoing is merely a specific embodiment of the invention, but protection scope of the present invention not office
It is limited to this, it should be clear to those skilled in the art, any to belong to those skilled in the art and take off in the present invention
In the technical scope of dew, any changes or substitutions that can be easily thought of, and all of which fall within the scope of protection and disclosure of the present invention.
Claims (10)
1. a kind of preparation method of Titanium Sieve Molecular Sieve, which is characterized in that described method includes following steps:
(1) titanium source, silicon source, the aqueous solution of micropore pore creating material and mesoporous pore creating material are mixed；Obtain reaction mixture；
(2) reaction mixture is subjected to hydrothermal crystallizing, obtains reaction product；
(3) reaction product is roasted, obtains Titanium Sieve Molecular Sieve.
2. the preparation method of Titanium Sieve Molecular Sieve according to claim 1, which is characterized in that step (1) mixing is specific
Include: first to mix titanium source and silicon source, obtains the first mixture；The aqueous solution of the first mixture and micropore pore creating material is mixed later
It closes, obtains the second mixture；The second mixture is mixed with mesoporous pore creating material again.
3. the preparation method of Titanium Sieve Molecular Sieve according to claim 2, which is characterized in that the mixing of the titanium source and silicon source
Include the following steps: in ice water bath environment, silicon source is added into titanium source；
Preferably, the form of the addition is to be added dropwise；
Preferably, the rate of addition is 0.5~1.5mL/min, preferably 0.6~1.2mL/min, further preferred 1mL/min；
Preferably, the mixing of the titanium source and silicon source carries out under agitation；
Preferably, the time of the stirring is 0.2~1.2h, preferably 0.5~1h, further preferred 0.8~1h；
Preferably, the speed of the stirring is 50~350rpm, preferably 100~300rpm, further preferred 150~200rpm；
Preferably, any one of the titanium source in titanium tetrachloride, tetraethyl titanate, metatitanic acid orthocarbonate or butyl titanate
Or at least two combination；
Preferably, the silicon source is in methyl orthosilicate, ethyl orthosilicate, positive silicic acid propyl ester, butyl silicate or silica gel
Any one or at least two combination；
Preferably, the mixing of the aqueous solution of first mixture and micropore pore creating material includes the following steps: in ice water bath environment
In, the aqueous solution of micropore pore creating material is added into the first mixture；
Preferably, the form of the addition is to be added dropwise；
Preferably, the rate of addition is 0.5~1.5mL/min, preferably 0.6~1.2mL/min, further preferred 1mL/min；
Preferably, the mixing of first mixture and the aqueous solution of micropore pore creating material carries out under agitation；
Preferably, the time of the stirring is 0.2~1.2h, preferably 0.5~1h, further preferred 0.8~1h；Preferably, institute
The speed for stating stirring is 50~350rpm, preferably 100~300rpm, further preferred 150~200rpm；
Preferably, the micropore pore creating material is selected from tetra-alkyl ammonium hydroxide, preferably tetramethylammonium hydroxide, tetraethyl hydroxide
In ammonium, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide any one or at least two combination；
Preferably, the mixing of second mixture and mesoporous pore creating material includes the following steps: under agitation, mixed to second
It closes in object and mesoporous pore creating material is added；
Preferably, the time of the stirring is 0.2~1.2h, preferably 0.5~1h, further preferred 0.8~1h；
Preferably, the speed of the stirring is 50~350rpm, preferably 100~300rpm, further preferred 150~200rpm；
Preferably, the mesoporous pore creating material is selected from the derivative of amino acid and/or amino acid, preferably lysine, lysine salt
In hydrochlorate, L-carnitine, L-carnitine fumarate or L-carnitine-L-tartrate any one or at least two combination.
4. the preparation method of Titanium Sieve Molecular Sieve described in one of -3 according to claim 1, which is characterized in that step (1) described silicon
SiO in source2, TiO in titanium source2, micropore pore creating material, mesoporous pore creating material and water molar ratio be 1:(0.001-0.1):
(0.001-5):(0.001-1):(5-400)。
5. the preparation method of Titanium Sieve Molecular Sieve described in one of -4 according to claim 1, which is characterized in that step (2) described water
The temperature of thermal crystallisation is 160~210 DEG C, preferably 180~200 DEG C；
Preferably, the time of the hydrothermal crystallizing is 12~48h, preferably 16~40h.
6. the preparation method of Titanium Sieve Molecular Sieve described in one of -5 according to claim 1, which is characterized in that step (3) described roasting
The temperature of burning is 400~800 DEG C, preferably 500~700 DEG C, further preferred 550~650 DEG C；
Preferably, the time of step (3) described roasting is 4-24h, preferably 10~20h；
Preferably, also reaction product is pre-processed before step (3) described roasting, the pretreatment includes being separated by solid-liquid separation, washing
It washs and dries.
7. the preparation method of Titanium Sieve Molecular Sieve described in one of -6 according to claim 1, which is characterized in that the preparation method packet
Include following steps:
(1) under ice water bath environment and stirring condition, titanium source and silicon source is mixed, the first mixture is obtained；Keep ice-water bath and
The aqueous solution of micropore pore creating material is added into the first mixture, obtains the second mixture for stirring condition；Ice-water bath is removed, to
Mesoporous pore creating material is added in two mixtures, obtains reaction mixture；Wherein, the SiO in silicon source2, TiO in titanium source2, micropore makes
The molar ratio of hole agent, mesoporous pore creating material and water is 1:(0.001-0.1): (0.001-5): (0.001-1): (5-400)；Micropore is made
Hole agent is selected from tetra-alkyl ammonium hydroxide；Mesoporous pore creating material is selected from the derivative of amino acid and/or amino acid；
(2) reaction mixture is obtained into reaction product in 160-210 DEG C of hydrothermal crystallizing 12-48h；
(3) reaction product is separated by solid-liquid separation, washs and dries, and roast 4-24h at 400-800 DEG C, obtained described
Titanium Sieve Molecular Sieve.
8. Titanium Sieve Molecular Sieve made from a kind of preparation method described in one of -7 according to claim 1, which is characterized in that the titanium
The aperture of si molecular sieves is 1~2 μm, and specific surface area is 400~600m2/g。
9. a kind of method of m-xylene diamine carbonylation preparation isophthalic dimethyl carbamate, which is characterized in that use claim 8
The Titanium Sieve Molecular Sieve is as catalyst.
10. according to the method described in claim 9, it is characterized in that, the m-xylene diamine carbonylation prepares isophthalic dimethylamino
The method of formic acid esters includes: in an inert atmosphere, using carbamate and m-xylene diamine as raw material or with urea and isophthalic two
Amine is raw material, and alcohol is solvent, and Titanium Sieve Molecular Sieve is catalyst, and heating is reacted, and obtains isophthalic dimethyl carbamate；
Preferably, the inert atmosphere is selected from nitrogen atmosphere or inert gas atmosphere；
Preferably, the reaction carries out in a high pressure reaction kettle；
Preferably, the carbamate is selected from methyl carbamate, urethanes, carbamic acid propyl ester or amino first
In acid butyl ester any one or at least two combination；
Preferably, the molar ratio of the m-xylene diamine and carbamate is 1:(5-20)；
Preferably, the molar ratio of the m-phenylene diamine (MPD) and urea is 1:(5-20)；
Preferably, the alcohol in methanol, ethyl alcohol, propyl alcohol or butanol any one or at least two combination；
Preferably, the molar ratio of the alcohol and m-xylene diamine is (8-40): 1；
Preferably, the mass ratio of the catalyst and m-xylene diamine is (0.001-1): 1；
Preferably, the temperature of the reaction is 180-260 DEG C；
Preferably, the time of the reaction is 0.5-12h.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2018104449037 | 2018-05-10 | ||
| CN201810444903 | 2018-05-10 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110467193A true CN110467193A (en) | 2019-11-19 |
| CN110467193B CN110467193B (en) | 2023-06-27 |
Family
ID=68504754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811301616.7A Active CN110467193B (en) | 2018-05-10 | 2018-11-02 | Titanium-silicon molecular sieve, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110467193B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110813373A (en) * | 2019-11-27 | 2020-02-21 | 吉林大学 | Titanium-silicon molecular sieve catalyst, preparation method and application thereof in olefin epoxidation reaction |
| CN113694961A (en) * | 2021-09-26 | 2021-11-26 | 吉林化工学院 | Nano hierarchical pore BEA structure molecular sieve catalyst and preparation method and application thereof |
| CN114441521A (en) * | 2022-01-27 | 2022-05-06 | 宜宾五粮液股份有限公司 | Preparation method of white spirit ethyl carbamate quick-detection test paper |
| CN115073327A (en) * | 2022-07-05 | 2022-09-20 | 中国科学院过程工程研究所 | Method for preparing pentanedicarbamate by using urea as carbonylation agent |
| CN115974094A (en) * | 2022-12-21 | 2023-04-18 | 中触媒新材料股份有限公司 | Titanium-silicon molecular sieve, and synthesis method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190794A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Method for synthesizing mesoporous titanium-silicon molecular screen material |
| CN101519214A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicon materials with mesoporous and microporous structures |
| US20150118149A1 (en) * | 2013-10-29 | 2015-04-30 | China Petroleum & Chemical Corporation | Titanium silicalite molecular sieve and its synthesis |
| CN105819464A (en) * | 2016-03-16 | 2016-08-03 | 大连理工大学 | High yield rapid synthesis method of titanium-silicon molecular sieve TS-1 |
| CN106379912A (en) * | 2016-08-29 | 2017-02-08 | 上海交通大学 | Preparation method of hierarchical porous titanium silicalite molecular sieves |
-
2018
- 2018-11-02 CN CN201811301616.7A patent/CN110467193B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101190794A (en) * | 2006-11-30 | 2008-06-04 | 中国石油化工股份有限公司 | Method for synthesizing mesoporous titanium-silicon molecular screen material |
| CN101519214A (en) * | 2008-02-28 | 2009-09-02 | 中国石油化工股份有限公司 | Method for synthesizing titanium-silicon materials with mesoporous and microporous structures |
| US20150118149A1 (en) * | 2013-10-29 | 2015-04-30 | China Petroleum & Chemical Corporation | Titanium silicalite molecular sieve and its synthesis |
| CN105819464A (en) * | 2016-03-16 | 2016-08-03 | 大连理工大学 | High yield rapid synthesis method of titanium-silicon molecular sieve TS-1 |
| CN106379912A (en) * | 2016-08-29 | 2017-02-08 | 上海交通大学 | Preparation method of hierarchical porous titanium silicalite molecular sieves |
Non-Patent Citations (2)
| Title |
|---|
| QIANG ZHANG ET AL.: "High-Quality Single-Crystalline MFI-Type Nanozeolites: A Facile Synthetic Strategy and MTP Catalytic Studies", 《CHEMISTRY OF MATERIALS》 * |
| R.SRIVASTAVA ET AL.: "Phosgene-free synthesis of carbamates over zeolite-based catalysts", 《CATALYSIS LETTERS》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110813373A (en) * | 2019-11-27 | 2020-02-21 | 吉林大学 | Titanium-silicon molecular sieve catalyst, preparation method and application thereof in olefin epoxidation reaction |
| CN113694961A (en) * | 2021-09-26 | 2021-11-26 | 吉林化工学院 | Nano hierarchical pore BEA structure molecular sieve catalyst and preparation method and application thereof |
| CN113694961B (en) * | 2021-09-26 | 2023-11-10 | 吉林化工学院 | Nano hierarchical pore BETA structure molecular sieve catalyst, and preparation method and application thereof |
| CN114441521A (en) * | 2022-01-27 | 2022-05-06 | 宜宾五粮液股份有限公司 | Preparation method of white spirit ethyl carbamate quick-detection test paper |
| CN115073327A (en) * | 2022-07-05 | 2022-09-20 | 中国科学院过程工程研究所 | Method for preparing pentanedicarbamate by using urea as carbonylation agent |
| CN115974094A (en) * | 2022-12-21 | 2023-04-18 | 中触媒新材料股份有限公司 | Titanium-silicon molecular sieve, and synthesis method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110467193B (en) | 2023-06-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110467193A (en) | A kind of Titanium Sieve Molecular Sieve, preparation method and application | |
| CN104944441A (en) | Method for synthesizing titanium-silicon molecular sieve | |
| CN113233472B (en) | Synthesis method of nano small-grain ZSM-22 molecular sieve | |
| CN101423225A (en) | Method for preparing silica zeolite Silicalite-2 | |
| CN107188194B (en) | A method of preparing high catalytic activity Ti-MWW molecular sieve | |
| CN106587102B (en) | The synthetic method of ZSM-12 type zeolite molecular sieves | |
| CN106316810B (en) | A kind of preparation method improving 1,1,3- trichloroacetone synthesis yields | |
| CN103818924B (en) | Preparation method of titanium-silicon molecular sieve and application | |
| CN1234458C (en) | Method for preparing titanium-silicon molecular sieve | |
| WO2022165911A1 (en) | Single-crystal hierarchically porous hzsm-5 molecular sieve and green preparation method therefor | |
| CN106006665A (en) | Method for preparing titanium silicalite molecular sieve TS-1 | |
| CN112744831B (en) | Method for preparing titanium-containing molecular sieve, titanium-containing molecular sieve produced by method and cyclohexanone oximation reaction method | |
| CN111217379B (en) | Method for synthesizing MTW type molecular sieve with low silicon-aluminum ratio | |
| CN114507152B (en) | Synthesis process and optimization method of cocamidopropyl betaine | |
| CN116425171A (en) | Preparation method of high-performance hydroisomerization catalyst mesoporous and microporous step structure ZSM 48 molecular sieve | |
| CN112744834A (en) | Titanium-containing molecular sieve, preparation method thereof and phenol hydroxylation reaction method | |
| CN1500728A (en) | Process for preparing titanium silicon molecular sieves | |
| CN111498862B (en) | Preparation method and application of spherical SBA-15 mesoporous molecular sieve | |
| CN106829996B (en) | A kind of Titanium Sieve Molecular Sieve and preparation method thereof | |
| CN112028775A (en) | Synthetic method of p-phenylenediamine hydrochloride | |
| CN104609440B (en) | TS-1 molecular sieve prepared from amino-terminated polymer as well as preparation method and application thereof | |
| CN114920259B (en) | Mesoporous template agent for manufacturing hierarchical pore molecular sieve and synthesis method thereof | |
| CN107778178B (en) | Method for preparing monophenyl maleate | |
| CN112678844A (en) | Method for regulating morphology of molecular sieve | |
| CN1060411C (en) | Process of synthesizing titanium-silicon molecular sieve TS-1 using silica gel as raw material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240729 Address after: 277500 residence of Mushi Town, Tengzhou City, Zaozhuang City, Shandong Province (Mushi Industrial Park) Patentee after: Lianhong New Materials Technology Co.,Ltd. Country or region after: China Address before: 100190 north two street, Zhongguancun, Haidian District, Beijing, 1 Patentee before: Institute of Process Engineering, Chinese Academy of Sciences Country or region before: China |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20241017 Address after: No. 1688 Kesheng Road, Mushi Town, Tengzhou City, Shandong Province, China (with multiple photos at one location) Patentee after: Lianhong Ruisheng (Shandong) Special Materials Co.,Ltd. Country or region after: China Address before: 277500 residence of Mushi Town, Tengzhou City, Zaozhuang City, Shandong Province (Mushi Industrial Park) Patentee before: Lianhong New Materials Technology Co.,Ltd. Country or region before: China |