CN104001541B - For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst - Google Patents
For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst Download PDFInfo
- Publication number
- CN104001541B CN104001541B CN201410064149.6A CN201410064149A CN104001541B CN 104001541 B CN104001541 B CN 104001541B CN 201410064149 A CN201410064149 A CN 201410064149A CN 104001541 B CN104001541 B CN 104001541B
- Authority
- CN
- China
- Prior art keywords
- pore
- nano
- catalyst
- resin
- fluoride resin
- 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.)
- Active
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 108
- 239000011347 resin Substances 0.000 title claims abstract description 93
- 229920005989 resin Polymers 0.000 title claims abstract description 93
- 238000006703 hydration reaction Methods 0.000 title claims abstract description 54
- 239000011148 porous material Substances 0.000 title claims abstract description 46
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 45
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 37
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 34
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000002253 acid Substances 0.000 claims abstract description 27
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011737 fluorine Substances 0.000 claims abstract description 12
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- 238000007306 functionalization reaction Methods 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 238000010790 dilution Methods 0.000 claims abstract description 6
- 239000012895 dilution Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims description 38
- 239000000178 monomer Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 239000004088 foaming agent Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 238000007334 copolymerization reaction Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 239000002086 nanomaterial Substances 0.000 claims description 13
- 238000010792 warming Methods 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 238000004132 cross linking Methods 0.000 claims description 12
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 12
- 229920002554 vinyl polymer Polymers 0.000 claims description 12
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 11
- 229910003480 inorganic solid Inorganic materials 0.000 claims description 11
- 239000012071 phase Substances 0.000 claims description 11
- 239000011343 solid material Substances 0.000 claims description 11
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 10
- 241001566735 Archon Species 0.000 claims description 10
- 108010010803 Gelatin Proteins 0.000 claims description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 10
- 241000209094 Oryza Species 0.000 claims description 10
- 235000007164 Oryza sativa Nutrition 0.000 claims description 10
- 239000008346 aqueous phase Substances 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 239000008273 gelatin Substances 0.000 claims description 10
- 229920000159 gelatin Polymers 0.000 claims description 10
- 235000019322 gelatine Nutrition 0.000 claims description 10
- 235000011852 gelatine desserts Nutrition 0.000 claims description 10
- 235000009566 rice Nutrition 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 238000006277 sulfonation reaction Methods 0.000 claims description 8
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 7
- -1 diallyl benzene Chemical compound 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 5
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical class CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000001256 steam distillation Methods 0.000 claims description 5
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 claims description 5
- 230000008961 swelling Effects 0.000 claims description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
- 230000036571 hydration Effects 0.000 abstract description 22
- 239000011973 solid acid Substances 0.000 abstract description 16
- 238000006555 catalytic reaction Methods 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 150000002191 fatty alcohols Chemical class 0.000 abstract description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 27
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 15
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 14
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 14
- 239000003729 cation exchange resin Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 230000007423 decrease Effects 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000004451 qualitative analysis Methods 0.000 description 5
- 238000004445 quantitative analysis Methods 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 230000002209 hydrophobic effect Effects 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000009257 reactivity Effects 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 238000005804 alkylation reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 235000013847 iso-butane Nutrition 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N trimethylmethane Natural products CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- PYGSKMBEVAICCR-UHFFFAOYSA-N hexa-1,5-diene Chemical group C=CCCC=C PYGSKMBEVAICCR-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000004044 response Effects 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
- 239000007858 starting material Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method for olefin hydration reaction nano-pore fluoride resin acidic catalyst, comprise the steps: that porous nano is inorganic material-modified; The suspension polymerisation synthesis of catalyst body resin; The acid functionalization of resin sulfonating reaction; Acidic resins microballoon loads tubular reactor; pass into the fluorine gas through nitrogen dilution; obtain for olefin hydration reaction nano-pore fluoride resin acidic catalyst; the rate of fluoridizing of this catalyst with fluorine in fluoride resin weight for 9.0 ~ 9.8wt%, fluoride resin acid exchange capacity & gt; 4.2mmol/g, specific area is 180-250m
2/ g.Advantage of the present invention is: the pore volume of the solid acid catalyst of preparation and specific area are large, acid strong, be applied to as solid acid catalyst in the catalytic reaction of olefin hydration Reactive Synthesis fatty alcohol, significantly improve the hydration reaction catalytic activity of resin solid acid and selective.
Description
Technical field
The present invention relates to catalyst preparation technical field, especially relate to a kind of preparation method for olefin hydration reaction nano-pore fluoride resin acidic catalyst.
Background technology
The course of reaction producing fatty alcohol by olefin hydration is an important chemical production technology, mainly comprise butylene hydration legal system sec-butyl alcohol (SBA) in actual industrial production, and propylene direct hydration becomes isopropyl alcohol (IPA) catalytic reaction technology.
In recent years, the expansion of MEK demand facilitates the production of sec-butyl alcohol.Produce sec-butyl alcohol by the n-butene in hybrid C 4, there is the features such as cheaper starting materials is easy to get.Economical comparision analysis display is carried out from the aspect such as production technology, three-protection design to indirect hydration method, direct hydration method, storng-acid cation exchange resin is that the butylene direct hydration legal system sec-butyl alcohol of catalyst has that catalyst activity is high, technological process is simple and direct, product is easily separated with catalyst, catalyst long service life, equipment corrosion are little, the productive rate advantages of higher of sec-butyl alcohol, is the preferred option of producing sec-butyl alcohol engineering design from now on.Germany just develops from early 1980s the new technology that storng-acid cation exchange resin is the direct hydration legal system sec-butyl alcohol of catalyst, within 1984, drives successfully on 60,000 t/a sec-butyl alcohol commercial plants, instead of butylene sulfuric acid indirect hydration method.Existing domesticly builtly have butylene hydration legal system sec-butyl alcohol (SBA) large production equipment more than ten to overlap.The key factor having a high catalytic activity for ion-exchange resin catalyst is that requirement resin catalyst possesses larger specific area and pore volume and resin acidic intensity.
Industrial direct hydration method take acidic resins as catalysts, carry out hydration reaction at high temperature under high pressure, butylene conversion per pass lower (5%-6%), the butene feedstock that non-hydration transforms in a large number need after high pressure conditions step-down, reaction cycle is carried out in recompression pressurization, and energy consumption is very high.
Sulfonated phenylethylene hydrogen form cation acidic resins have homogeneous acid strength, stronger acidity and good stability, at present replace sulfuric acid to be widely used in the various acid catalyzed reactions such as various esterification, etherificate, alkylation of phenol, olefin hydration as solid acid resin catalyst, have product postprocessing simple, little to equipment corrosion degree, be convenient to the advantages such as continuous prodution.Preparation and application about storng-acid cation exchange resin acidic catalyst have many disclosed patents.Such as, notification number is the preparation method that the Chinese invention patent of CN1389297A discloses a kind of macroporous cation exchange resin catalyst with high exchange capacity; Notification number is that the Chinese invention patent of CN1555924A discloses a kind of high-capacity resin Catalysts and its preparation method.But the pore volume of common styrene-divinylbenzene cationic ion-exchange resin itself and specific area is little, the sour amount of hole surface is less, cause its Reaction-diffusion terms as solid acid catalyst restricted, thus make its reactivity and selective lower in heterogeneous catalysis application.
Common cationic ion-exchange resin ethene and the crosslinked of divinylbenzene make pellet shapes polymer, through the sulfonic resin of sulfonation gained; As the catalyst of hydration reaction, its stability increases with the increase of divinylbenzene content, but on sulfonic resin, the hydrolysis of sulfonation group also increases thereupon.Not only hydrolysis makes sulfonic acid group run off, and affects catalyst activity, and the sour gas corrosion equipment discharged, and therefore its serviceability temperature limit is between 130-150 DEG C.In order to improve the resistant to hydrolysis performance of sulfonation group on sulfonic resin, US Patent No. 4269943 proposes a kind of carries out chlorination modified processing scheme to storng-acid cation exchange resin, effectively can improve resin heatproof stability and reactive applications temperature between 150-160 DEG C.People are to carrying out chlorination modified process to strong acid cation exchange resin catalyst, and be applied to (Lv Zhihui in butylene direct hydration legal system sec-butyl alcohol technique, " petrochemical industry ", 32nd volume the 2nd phase 153-355 page in 2004), although butylene conversion per pass can rise to 6%-8%, but the specific area of resin catalyst and pore volume are not enhanced, therefore not yet significantly can change the still lower problem of butylene conversion per pass.
In recent years, for resin catalyst specific area and pore volume and the lower deficiency of resin acidic intensity, people attempt the olefin hydration reaction super acidic catalyst of development of new.Chinese invention patent CN1128250A discloses a kind of catalyst for hydration of olefines and preparation method thereof, become in isopropyl alcohol (IPA) catalytic reaction for propylene direct hydration, although have good isopropyl alcohol (IPA) selectivity of product, but this catalyst propylene conversion per pass is lower, and there is the loss of active constituent facile hydrolysis, cause the problem of Long-Time Service less stable, constrain its industrial applications.German patent DE 19829747A1 discloses a kind of acidic catalyst of solid montmorillonite load phosphoric acid, for in ethene, propylene direct hydration catalytic reaction, although can use at high temperature under high pressure to improve this catalyst propylene conversion per pass, but still there is the problem that active constituent facile hydrolysis runs off, stability in use is poor.The Nafion perfluorinated sulfonic resin of Dupont company exploitation is the solid super-strong acid be prepared from by perfluorinated sulfonic acid ether and tetrafluoroethene copolymerization, is applicable to the direct alkylation catalytic reaction of iso-butane butylene.But the very low (0.02m of the surface area due to Nafion resin
2/ g), need be carried on porous material just has higher catalytic activity.(ShenW on the SBA-15 that Nafion is synthesized at trimethylethoxysilane by dip loading by researcher, GuaY, XuHL.AppliedCatalysisA:General, 2010,377:1 – 8.), obtain surface hydrophobic, acid stronger Organic-inorganic composite solid-acid material.Result shows, and under equal sour load capacity, its catalyzing iso-butane alkane and butene alkylated effect are better than carried heteropoly acid and molecular sieve catalyst.But Nafion resin and the preparation cost both mesoporous material all higher, and be easy in load preparation process block SBA-15 duct, also exist operation wayward, preparation poor repeatability shortcoming, limit the possibility of its industrial applications.Foreign patent JP11216363A2 proposes at pore volume 0.20-0.90ml/g; aperture 10-5; the acidic catalyst of 000nm inorganic carrier load perfluorinated sulfonic acid; for in alkene direct hydration catalytic reaction; although can use at high temperature under high pressure; to improve alkene conversion per pass, but still this catalyst also exists, and preparation cost is high, repeatability is poor, the problem of stability in use, constrains its large-scale industrial application.Chinese invention patent CN1167011A discloses the preparation method of high thermal stability sulfonic acid type cation exchange resin catalyst, and Chinese invention patent CN1569334A also discloses comparatively similar Thermostable strong acid cation resin Catalysts and its preparation method.The resistance to elevated temperatures of polystyrene highly acidic resin catalyst is improved by introducing the electron withdraw groups such as F, Cl, Br on phenyl ring, but resin catalyst specific area still lower (30-50m
2/ g), cause its reactivity lower, and easily fouling and inactivation is very fast.
In sum, the above-mentioned analysis to existing alkene direct hydration reaction technology and cation acid resin catalyst method is visible, and the subject matter of restriction resin solid acid catalyzed reaction performance is resin catalyst specific area still lower (30-50m at present
2/ g) and resin acidic intensity, cause that its reactivity is lower, reaction selectivity is poor.
Summary of the invention
The object of this invention is to provide the preparation method of a kind of olefin hydration reaction nano-pore fluoride resin acidic catalyst, it has, and can to prepare pore volume and specific area large, acid strong, the suitable feature be applied to as solid acid catalyst in olefin hydration catalytic reaction.
The technical solution adopted in the present invention is: for the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst, comprise the steps:
(1) porous nano is inorganic material-modified: be that the nano inorganic solid material of 50 ~ 250nm and 5 ~ 20 parts of ethyl orthosilicates are in acetone solvent by parts by weight 80 ~ 95 parts, aperture 5 ~ 15nm, particle diameter, 1 ~ 3h is flooded under temperature is 30 ~ 50 DEG C of conditions, then at 90 ~ 110 DEG C, evaporative removal acetone solvent is carried out, roasting 1 ~ 3h at 450 ~ 550 DEG C again, forms modified Nano material;
(2) the suspension polymerisation synthesis of catalyst body resin: modified Nano material, vinyl monomer, crosslinking copolymerization monomer, initator, pore-foaming agent and solvent are made into oil-phase solution; Wherein, by weight percentage:
All the other are solvent;
With pure water, gelatin dispersant and imvite decentralized photo for aqueous phase, pure water, gelatin dispersant and imvite decentralized photo weight ratio are 100:1 ~ 3:1 ~ 3, oil-phase solution is mixed with weight ratio 1:2 ~ 3 with aqueous phase solution, stir under the speed conditions of 250 ~ 280 revs/min and be warming up to 81 ~ 84 DEG C, reaction 2h ~ 4h, lowers the temperature afterwards, filters the polymer microballoon that washing obtains containing porous nanometer material; And then adopt steam distillation method to remove pore-foaming agent and residual monomer at 100 ~ 105 DEG C this polymer microballoon, obtain bulk resin catalyst Archon;
(3) resin sulfonating reaction acid functionalization: the nano-pore resin Archon that step (2) is obtained: oleum: dichloroethane solvent: the weight ratio of sulfonation catalyst is that the ratio of 100:400 ~ 500:200 ~ 300:3 ~ 5 prepares reaction raw materials, is warming up to 60 ~ 80 DEG C of swelling 1 ~ 3h; Be warming up to 84 ~ 130 DEG C of stirring reaction 3 ~ 5h, washing filtering removes remaining sulfuric acid, then at 70 ~ 110 DEG C, removes dichloroethane solvent with distillating method, obtains the nano-pore acidic resins microballoon containing sulfonate functional group;
(4) acidic resins microballoon step (3) obtained loads tubular reactor, passing into through nitrogen dilution is the fluorine gas of 5 ~ 25wt% content, at 50 ~ 70 DEG C of reaction 3 ~ 5h, obtain for olefin hydration reaction nano-pore fluoride resin acidic catalyst;
In fluoride resin, weight is for 9.0 ~ 9.8wt% with fluorine for the rate of fluoridizing of this catalyst described, and fluoride resin acid exchange capacity >4.2mmol/g, specific area is 180-250m
2/ g.
Nano inorganic solid material in described step (1) is sodium rice SiO
2or sodium rice TiO
2.
Vinyl monomer in described step (2) is at least one in methyl styrene, styrene, p-methylstyrene.
Crosslinking copolymerization monomer in described step (2) is at least one in diallyl benzene, divinylbenzene.
Initator in described step (2) is at least one in azodiisobutyronitrile, cumyl peroxide.
Solvent in described step (2) is at least one in toluene, butanone, ethyl acetate.
Pore-foaming agent in described step (2) is at least one in butanols, normal heptane, n-hexane.
The present invention is compared to the prior art advantageously: the preparation method that the present invention is used for olefin hydration reaction nano-pore fluoride resin acidic catalyst should have comparatively highly acid based on desirable olefin hydration reaction solid acid catalyst, bigger serface, high porosity, the diffusible requirement of sound response, adopt porous inorganic solid material as pore-foaming agent, suspension copolymerization synthetic macromolecule resin is carried out by the inorganic material of surface-hydrophobicized modification and styrene/divinylbenzene, nano inorganic pore-foaming agent Direct Uniform is mixed, thus form nano pore in macromolecule styrene resin, then carry out sulfonating reaction and realize acid functionalization, acid through flaorination process strengthening again, and the Performances of Novel Nano-Porous metre hole resin solid acid catalyst simultaneously with sulfonic acid group and fluoro substituents on obtained resin matrix, can be used as in the acid catalyzed reaction of catalyst for olefin hydration alcohol, the pore volume and the specific area that solve resin solid acid are in the past little, hole surface acid amount is less, and it is lower as the acid intensity of solid acid, cause reactivity and selective lower problem.Namely, pore volume for olefin hydration reaction nano-pore fluoride resin acidic catalyst prepared by the inventive method is large, by force acid with specific area, be applied in olefin hydration catalytic reaction as solid acid catalyst, show this catalyst there is more than 15wt% high olefin conversion to reach the fatty alcohol selectivity of product with more than 99wt%, and hydration reaction technological process is simple, non-environmental-pollution.Namely, the pore volume of solid acid catalyst prepared by the inventive method and specific area are large, acid strong, be applied in the catalytic reaction of olefin hydration Reactive Synthesis fatty alcohol as solid acid catalyst, significantly improve the hydration reaction catalytic activity of resin solid acid and selective, there is very important using value, achieve good technique effect.
Detailed description of the invention
Embodiment 1
For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst, in turn include the following steps:
(1) porous nano is inorganic material-modified: be that the nano inorganic solid material of 50nm and 6 parts of ethyl orthosilicates are in acetone solvent by parts by weight 95 parts, aperture 5nm, particle diameter, 3h is flooded under temperature is 30 DEG C of conditions, then at 91 DEG C, evaporative removal acetone solvent is carried out, at 460 DEG C, carry out roasting 3h again, namely complete the hydrophobic modification of inorganic nano material carrier.Wherein, this nano inorganic solid material adopts sodium rice SiO
2material.
(2) the suspension polymerisation synthesis of catalyst body resin: vinyl monomer, crosslinking copolymerization monomer, initator, modified Nano material, pore-foaming agent and solvent are made into oil-phase solution; By weight percentage:
Modified Nano material 5%,
Vinyl monomer adopts styrene 60%,
Crosslinking copolymerization monomer adopts divinylbenzene copolymerization 20%,
Initator adopts cumyl peroxide 0.1%,
Pore-foaming agent adopts butanols 6%,
All the other are solvent, and solvent adopts toluene solvant.
With pure water, gelatin dispersant and imvite decentralized photo for aqueous phase, pure water, gelatin dispersant and imvite decentralized photo weight ratio are 100:2:2, oil-phase solution is mixed with weight ratio 1:2.6 with aqueous phase solution, stir under the speed conditions of 250 revs/min and be warming up to 81 DEG C, reaction 4h, lower the temperature afterwards, filters washing obtain contain porous sodium rice SiO
2polymer microballoon; And then adopt steam distillation method to remove pore-foaming agent and residual monomer at 100 DEG C this polymer microballoon, obtain bulk resin catalyst Archon;
(3) resin sulfonating reaction acid functionalization: the nano-pore resin Archon that step (2) is obtained: oleum: dichloroethane solvent: the weight ratio of sulfonation catalyst is that the ratio of 100:400:200:3 prepares reaction raw materials, and temperature is to 60 DEG C of swelling 3h; Be warming up to 84 DEG C of stirring reaction 5h, washing filtering removes remaining sulfuric acid, then at 70 DEG C, removes dichloroethane solvent with distillating method, obtains the nano-pore acidic resins microballoon containing sulfonate functional group;
(4) acidic resins microballoon step (3) obtained loads tubular reactor, passing into through nitrogen dilution is the fluorine gas of 5wt% content, at 50 DEG C of reaction 5h, obtain for olefin hydration reaction nano-pore fluoride resin acidic catalyst, the rate of fluoridizing of this catalyst with fluorine in fluoride resin weight for 9.0wt%, fluoride resin acid exchange capacity 4.25mmol/g, specific area is 182m
2/ g.
The present embodiment gained catalyst is labeled as: catalyst A.
Embodiment 2
For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst, in turn include the following steps:
(1) porous nano is inorganic material-modified: be that the nano inorganic solid material of 250nm and 20 parts of ethyl orthosilicates are in acetone solvent by parts by weight 80 parts, aperture 15nm, particle diameter, 1h is flooded under temperature is 50 DEG C of conditions, then at 110 DEG C, evaporative removal acetone solvent is carried out, at 550 DEG C, carry out roasting 1h again, namely complete the hydrophobic modification of inorganic nano material carrier.Wherein, this nano inorganic solid material adopts sodium rice SiO
2material.
(2) the suspension polymerisation synthesis of catalyst body resin: vinyl monomer, crosslinking copolymerization monomer, initator, modified Nano material, pore-foaming agent and solvent are made into oil-phase solution; By weight percentage:
Modified Nano material 30%,
Vinyl monomer adopts methyl styrene 40%,
Crosslinking copolymerization monomer adopts diallyl crosslinking copolymerization monomer 3%,
Initator adopts azodiisobutyronitrile 2%,
Pore-foaming agent adopts normal heptane 18%,
All the other are solvent, and solvent adopts butanone solvent.
With pure water, gelatin dispersant and imvite decentralized photo for aqueous phase, pure water, gelatin dispersant and imvite decentralized photo weight ratio are 100:1:3, oil-phase solution is mixed with weight ratio 1:2 with aqueous phase solution, stir under the speed conditions of 280 revs/min and be warming up to 84 DEG C, reaction 2h, lower the temperature afterwards, filters washing obtain contain porous sodium rice SiO
2polymer microballoon; And then adopt steam distillation method to remove pore-foaming agent and residual monomer at 105 DEG C this polymer microballoon, obtain bulk resin catalyst Archon;
(3) resin sulfonating reaction acid functionalization: the nano-pore resin Archon that step (2) is obtained: oleum: dichloroethane solvent: the weight ratio of sulfonation catalyst is that the ratio of 100:500:300:5 prepares reaction raw materials, is warming up to 80 DEG C of swelling 1h; Be warming up to 130 DEG C of stirring reaction 3h, washing filtering removes remaining sulfuric acid, then at 110 DEG C, removes dichloroethane solvent with distillating method, obtains the nano-pore acidic resins microballoon containing sulfonate functional group;
(4) acidic resins microballoon step (3) obtained loads tubular reactor, passing into through nitrogen dilution is the fluorine gas of 25wt% content, at 50 DEG C of reaction 3h, obtain for olefin hydration reaction nano-pore fluoride resin acidic catalyst, the rate of fluoridizing of this catalyst with fluorine in fluoride resin weight for 9.8wt%, fluoride resin acid exchange capacity 4.5mmol/g, specific area is 250m
2/ g.
The present embodiment gained catalyst is labeled as: catalyst B.
Embodiment 3
For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst, in turn include the following steps:
(1) porous nano is inorganic material-modified: be that the nano inorganic solid material of 150nm and 10 parts of ethyl orthosilicates are in acetone solvent by parts by weight 90 parts, aperture 10nm, particle diameter, 2h is flooded under temperature is 50 DEG C of conditions, then at 90 DEG C, evaporative removal acetone solvent is carried out, at 450 DEG C, carry out roasting 2h again, namely complete the hydrophobic modification of inorganic nano material carrier.Wherein, this nano inorganic solid material adopts sodium rice TiO
2material.
(2) the suspension polymerisation synthesis of catalyst body resin: vinyl monomer, crosslinking copolymerization monomer, initator, modified Nano material, pore-foaming agent and solvent are made into oil-phase solution; Comprise following component by weight percentage:
Modified Nano material 20%,
Vinyl monomer adopts styrene 50%,
Crosslinking copolymerization monomer adopts divinylbenzene 10%,
Initator adopts cumyl peroxide 1%,
Pore-foaming agent adopts n-hexane 10%,
All the other are solvent, and solvent adopts ethyl acetate solvent.
With pure water, gelatin dispersant and imvite decentralized photo for aqueous phase, pure water, gelatin dispersant and imvite decentralized photo weight ratio are 100:3:1, oil-phase solution is mixed with weight ratio 1:3 with aqueous phase solution, stir under the speed conditions of 270 revs/min and be warming up to 83 DEG C, reaction 3h, lower the temperature afterwards, filters washing obtain contain porous sodium rice SiO
2polymer microballoon; And then adopt steam distillation method to remove pore-foaming agent and residual monomer at 102 DEG C this polymer microballoon, obtain bulk resin catalyst Archon;
(3) resin sulfonating reaction acid functionalization: the nano-pore resin Archon that step (2) is obtained: oleum: dichloroethane solvent: the weight ratio of sulfonation catalyst is that the ratio of 100:450:260:4 prepares reaction raw materials, and temperature is to 70 DEG C of swelling 2h; Be warming up to 100 DEG C of stirring reaction 4h, washing filtering removes remaining sulfuric acid, then at 90 DEG C, removes dichloroethane solvent with distillating method, obtains the nano-pore acidic resins microballoon containing sulfonate functional group;
(4) acidic resins microballoon step (3) obtained loads tubular reactor, passing into through nitrogen dilution is the fluorine gas of 15wt% content, at 60 DEG C of reaction 4h, obtain for olefin hydration reaction nano-pore fluoride resin acidic catalyst, the rate of fluoridizing of this catalyst with fluorine in fluoride resin weight for 9.5wt%, fluoride resin acid exchange capacity 4.3mmol/g, specific area is 210m
2/ g.
The present embodiment gained catalyst is labeled as: catalyst C.
Embodiment 4
Only be with the difference of embodiment 1: vinyl monomer replaces with p-methylstyrene, crosslinking copolymerization monomer is to wait diallyl benzene, the divinyl benzene mixtures replacement of weight portion, initator replaces with the mixture of the weight portion such as azodiisobutyronitrile, cumyl peroxide, solvent is to wait toluene, the replacement of butanone mixture of weight portion, and butanols, the normal heptane mixture of the weight portions such as pore-foaming agent replace.
The present embodiment gained catalyst is labeled as: catalyst D.
Embodiment 5
Only be with the difference of embodiment 2: vinyl monomer replaces to wait the p-methylstyrene of weight portion, methyl styrene, styrene mixture, solvent replaces to wait the toluene of weight portion, butanone, ethyl acetate mixture, and the butanols of the weight portions such as pore-foaming agent, normal heptane, hexane mixture replace.
The present embodiment gained catalyst is labeled as: catalyst E.
Embodiment 6
Acid catalyst A10.0 gram is placed in successive reaction still, butylene air speed 0.8/h, reaction temperature 175 DEG C, reacting system pressure is normal pressure, and water/butylene (mol/mol)=1.2:1, product carries out qualitative and quantitative analysis with HP5890 gas-chromatography.Result display butylene conversion per pass is up to 16.1%.Product sec-butyl alcohol is to selective 99.2%, successive reaction 100h of butylene, and catalyst activity does not obviously decline.
Embodiment 7
Above-mentioned catalyst B 10.0 grams is placed in continuous fixed bed reactors, butylene air speed 1.8/h, reaction temperature 190 DEG C, reacting system pressure is normal pressure, water/butylene (mol/mol)=1.5:1, product carries out qualitative and quantitative analysis with HP5890 gas-chromatography.Result display product butylene conversion per pass is up to 18.5%.Product sec-butyl alcohol is to selective 99.1%, successive reaction 100h of butylene, and catalyst activity does not obviously decline.
Embodiment 8
Above-mentioned catalyst C10.0 gram is placed in continuous fixed bed reactors, propylene air speed 1.0/h, reaction temperature 185 DEG C, reacting system pressure is normal pressure, water/propylene (mol/mol)=1.8:1, product carries out qualitative and quantitative analysis with HP5890 gas-chromatography.Result shows product isopropyl alcohol to the once through yield of propylene up to 85.8%.Successive reaction 100h, catalyst activity does not obviously decline.
Embodiment 9
Above-mentioned catalyst D10.0 gram is placed in continuous fixed bed reactors, propylene air speed 1.0/h, reaction temperature 185 DEG C, reacting system pressure is normal pressure, water/propylene (mol/mol)=1.8:1, product carries out qualitative and quantitative analysis with HP5890 gas-chromatography.Result shows product isopropyl alcohol to the once through yield of propylene up to 88.8%.Successive reaction 100h, catalyst activity does not obviously decline.
Embodiment 10
Above-mentioned catalyst E10.0 gram is placed in continuous fixed bed reactors, propylene air speed 1.0/h, reaction temperature 185 DEG C, reacting system pressure is normal pressure, water/propylene (mol/mol)=1.8:1, product carries out qualitative and quantitative analysis with HP5890 gas-chromatography.Result shows product isopropyl alcohol to the once through yield of propylene up to 92.1%.Successive reaction 100h, catalyst activity does not obviously decline.
The foregoing is only the preferred embodiments of the present invention; not thereby the scope of the claims of the present invention is limited; every utilize description of the present invention to do equivalent structure or equivalent flow process conversion; or be directly or indirectly used in other relevant technical fields, be all in like manner included in scope of patent protection of the present invention.
Claims (7)
1., for the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst, comprise the steps:
(1) porous nano is inorganic material-modified: be that the nano inorganic solid material of 50 ~ 250nm and 5 ~ 20 parts of ethyl orthosilicates are in acetone solvent by parts by weight 80 ~ 95 parts, aperture 5 ~ 15nm, particle diameter, 1 ~ 3h is flooded under temperature is 30 ~ 50 DEG C of conditions, then at 90 ~ 110 DEG C, evaporative removal acetone solvent is carried out, roasting 1 ~ 3h at 450 ~ 550 DEG C again, forms modified Nano material;
(2) the suspension polymerisation synthesis of catalyst body resin: modified Nano material, vinyl monomer, crosslinking copolymerization monomer, initator, pore-foaming agent and solvent are made into oil-phase solution; Wherein, by weight percentage:
With pure water, gelatin dispersant and imvite decentralized photo for aqueous phase, pure water, gelatin dispersant and imvite decentralized photo weight ratio are 100:1 ~ 3:1 ~ 3, oil-phase solution is mixed with weight ratio 1:2 ~ 3 with aqueous phase solution, stir under the speed conditions of 250 ~ 280 revs/min and be warming up to 81 ~ 84 DEG C, reaction 2h ~ 4h, lowers the temperature afterwards, filters the polymer microballoon that washing obtains containing porous nanometer material; And then adopt steam distillation method to remove pore-foaming agent and residual monomer at 100 ~ 105 DEG C this polymer microballoon, obtain bulk resin catalyst Archon;
(3) resin sulfonating reaction acid functionalization: the nano-pore resin Archon that step (2) is obtained: oleum: dichloroethane solvent: the weight ratio of sulfonation catalyst is that the ratio of 100:400 ~ 500:200 ~ 300:3 ~ 5 prepares reaction raw materials, is warming up to 60 ~ 80 DEG C of swelling 1 ~ 3h; Be warming up to 84 ~ 130 DEG C of stirring reaction 3 ~ 5h, washing filtering removes remaining sulfuric acid, then at 70 ~ 110 DEG C, removes dichloroethane solvent with distillating method, obtains the nano-pore acidic resins microballoon containing sulfonate functional group;
(4) acidic resins microballoon step (3) obtained loads tubular reactor, passing into through nitrogen dilution is the fluorine gas of 5 ~ 25wt% content, at 50 ~ 70 DEG C of reaction 3 ~ 5h, obtain for olefin hydration reaction nano-pore fluoride resin acidic catalyst; And
In fluoride resin, weight is for 9.0 ~ 9.8wt% with fluorine for the rate of fluoridizing of described catalyst, and fluoride resin acid exchange capacity >4.2mmol/g, specific area is 180-250m
2/ g.
2. the preparation method for olefin hydration reaction nano-pore fluoride resin acidic catalyst according to claim 1, is characterized in that: the nano inorganic solid material in described step (1) is sodium rice SiO
2or sodium rice TiO
2.
3. the preparation method for olefin hydration reaction nano-pore fluoride resin acidic catalyst according to claim 1, is characterized in that: the vinyl monomer in described step (2) is at least one in methyl styrene, styrene, p-methylstyrene.
4. the preparation method for olefin hydration reaction nano-pore fluoride resin acidic catalyst according to claim 1, is characterized in that: the crosslinking copolymerization monomer in described step (2) is at least one in diallyl benzene, divinylbenzene.
5. the preparation method for olefin hydration reaction nano-pore fluoride resin acidic catalyst according to claim 1, is characterized in that: the initator in described step (2) is at least one in azodiisobutyronitrile, cumyl peroxide.
6. the preparation method for olefin hydration reaction nano-pore fluoride resin acidic catalyst according to claim 1, is characterized in that: the solvent in described step (2) is at least one in toluene, butanone, ethyl acetate.
7. the preparation method for olefin hydration reaction nano-pore fluoride resin acidic catalyst according to claim 1, is characterized in that: the pore-foaming agent in described step (2) is at least one in butanols, normal heptane, n-hexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410064149.6A CN104001541B (en) | 2014-02-25 | 2014-02-25 | For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410064149.6A CN104001541B (en) | 2014-02-25 | 2014-02-25 | For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104001541A CN104001541A (en) | 2014-08-27 |
| CN104001541B true CN104001541B (en) | 2016-03-30 |
Family
ID=51362615
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410064149.6A Active CN104001541B (en) | 2014-02-25 | 2014-02-25 | For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104001541B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11216363A (en) * | 1998-01-30 | 1999-08-10 | Asahi Chem Ind Co Ltd | Catalyst for hydration reaction of olefin |
| CN101255218A (en) * | 2007-12-18 | 2008-09-03 | 兰州理工大学 | Method for preparing adsorption resin |
| CN101284767A (en) * | 2008-05-27 | 2008-10-15 | 浙江大学 | Process for preparing cyclohexanol by cyclohexene hydration reaction |
| CN102614916A (en) * | 2012-02-28 | 2012-08-01 | 同济大学 | Preparation method of high-acidity fluorination resin catalyst used for alkylating of isobutane and butene |
-
2014
- 2014-02-25 CN CN201410064149.6A patent/CN104001541B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11216363A (en) * | 1998-01-30 | 1999-08-10 | Asahi Chem Ind Co Ltd | Catalyst for hydration reaction of olefin |
| CN101255218A (en) * | 2007-12-18 | 2008-09-03 | 兰州理工大学 | Method for preparing adsorption resin |
| CN101284767A (en) * | 2008-05-27 | 2008-10-15 | 浙江大学 | Process for preparing cyclohexanol by cyclohexene hydration reaction |
| CN102614916A (en) * | 2012-02-28 | 2012-08-01 | 同济大学 | Preparation method of high-acidity fluorination resin catalyst used for alkylating of isobutane and butene |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104001541A (en) | 2014-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1213003C (en) | Method for preparing high-purity diisobutene | |
| Zhou et al. | One-pot conversion of carbohydrates into gamma-valerolactone catalyzed by highly cross-linked ionic liquid polymer and Co/TiO 2 | |
| KR100940327B1 (en) | Metal-Doped Sulfonated Ion Exchange Resin Catalysts | |
| CN111957346B (en) | Etherification catalyst for preparing methyl tertiary butyl ether from methanol-tertiary butyl alcohol and preparation method thereof | |
| CN101961660B (en) | Porous hybrid-resin solid acid catalyst and preparation method thereof | |
| JPH10511648A (en) | Porous microcomposite for olefin isomerization derived from sol-gel from perfluorinated polymer and metal oxide for ion exchange | |
| CN102614916B (en) | Preparation method of high-acidity fluorination resin catalyst used for alkylating of isobutane and butene | |
| JPWO2008123530A1 (en) | Method for producing solid acid catalyst comprising sulfonic acid group-containing carbonaceous material and use thereof | |
| WO2012003708A1 (en) | Composite catalyst of ti-si molecular sieve and resin, preparation method and application thereof | |
| CN103611571A (en) | Preparation method of nano-pore resin solid acid for alkylation of butane and butylene | |
| CN110787830B (en) | Ruthenium oxide-loaded carbon nitride hollow tube photocatalyst and preparation and application thereof | |
| CN108794662B (en) | Preparation method and application of macroporous strong-acid resin | |
| CN103028440A (en) | Macroporous resin catalyst for preparing alkyl carbonate | |
| CN104725225A (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| CN104001541B (en) | For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst | |
| Weaver et al. | Supported fluorocarbonsulfonic acid catalysts | |
| CN106916237B (en) | A kind of acidity polymeric ionic liquid and its preparation method and application | |
| CN106552657A (en) | A kind of platinum based catalyst of SiC carriers confinement and preparation method thereof | |
| CN102264685A (en) | Method for producing acetic acid ester | |
| CN115475659B (en) | Metal organic framework material/molecular sieve series catalyst and preparation method and application thereof | |
| CN103709010B (en) | A kind of by tetrahydrobenzene, carboxylic acid and water Reactive Synthesis hexalin method | |
| Karam et al. | Significant enhancement on selectivity in silica supported sulfonic acids catalyzed reactions | |
| CN109225349B (en) | Preparation method of catalyst for preparing isobutene by cracking methyl tert-butyl ether | |
| CN102755910A (en) | Titanium silicon molecular sieve and resin composite modified catalyst and preparation method thereof | |
| CN105503529B (en) | Method for preparing ethyl glycol by hydrolysis of ethylene carbonate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB03 | Change of inventor or designer information |
Inventor after: Zhu Zhirong Inventor after: Li Xiaohong Inventor after: Cai Jianguo Inventor after: Shi Hongyan Inventor before: Zhu Zhirong Inventor before: Li Xiaohong Inventor before: Shi Hongyan Inventor before: Qian Hongming |
|
| COR | Change of bibliographic data | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparing method of nanopore fluororesin acid catalysts used for olefin hydration reaction Effective date of registration: 20160719 Granted publication date: 20160330 Pledgee: Suzhou Rongfeng Technology Microfinance Co.,Ltd. Pledgor: JIANGSU HELPER FUNCTIONAL MATERIALS CO.,LTD. Registration number: 2016990000606 |
|
| PLDC | Enforcement, change and cancellation of contracts on pledge of patent right or utility model | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20170602 Granted publication date: 20160330 Pledgee: Suzhou Rongfeng Technology Microfinance Co.,Ltd. Pledgor: JIANGSU HELPER FUNCTIONAL MATERIALS CO.,LTD. Registration number: 2016990000606 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparing method of nanopore fluororesin acid catalysts used for olefin hydration reaction Effective date of registration: 20180207 Granted publication date: 20160330 Pledgee: Bank of Communications Ltd. Suzhou science and Technology Branch Pledgor: JIANGSU HELPER FUNCTIONAL MATERIALS CO.,LTD. Registration number: 2018320010007 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20200110 Granted publication date: 20160330 Pledgee: Bank of Communications Ltd. Suzhou science and Technology Branch Pledgor: JIANGSU HELPER FUNCTIONAL MATERIALS CO.,LTD. Registration number: 2018320010007 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20140827 Assignee: Suzhou ronghua Leasing Co.,Ltd. Assignor: JIANGSU HELPER FUNCTIONAL MATERIALS CO.,LTD. Contract record no.: X2021320010036 Denomination of invention: Preparation method of nano porous fluorinated resin acid catalyst for olefin hydration reaction Granted publication date: 20160330 License type: Exclusive License Record date: 20211116 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: Preparation method of nano porous fluorinated resin acid catalyst for olefin hydration reaction Effective date of registration: 20211116 Granted publication date: 20160330 Pledgee: Suzhou ronghua Leasing Co.,Ltd. Pledgor: JIANGSU HELPER FUNCTIONAL MATERIALS CO.,LTD. Registration number: Y2021320010475 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20231108 Granted publication date: 20160330 Pledgee: Suzhou ronghua Leasing Co.,Ltd. Pledgor: JIANGSU HELPER FUNCTIONAL MATERIALS CO.,LTD. Registration number: Y2021320010475 |
|
| EC01 | Cancellation of recordation of patent licensing contract |
Assignee: Suzhou ronghua Leasing Co.,Ltd. Assignor: JIANGSU HELPER FUNCTIONAL MATERIALS CO.,LTD. Contract record no.: X2021320010036 Date of cancellation: 20231108 |
|
| EC01 | Cancellation of recordation of patent licensing contract |