CN1330416C - Modification method of titanium silicone molecular sieve and its application - Google Patents
Modification method of titanium silicone molecular sieve and its application Download PDFInfo
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- CN1330416C CN1330416C CNB2004100210379A CN200410021037A CN1330416C CN 1330416 C CN1330416 C CN 1330416C CN B2004100210379 A CNB2004100210379 A CN B2004100210379A CN 200410021037 A CN200410021037 A CN 200410021037A CN 1330416 C CN1330416 C CN 1330416C
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 31
- 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 31
- 239000010936 titanium Substances 0.000 title abstract description 9
- 229910052719 titanium Inorganic materials 0.000 title abstract description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title abstract description 6
- 238000002715 modification method Methods 0.000 title abstract 2
- 229920001296 polysiloxane Polymers 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000012986 modification Methods 0.000 claims abstract description 23
- 230000004048 modification Effects 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 16
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 4
- -1 plumbous Chemical compound 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 159000000021 acetate salts Chemical class 0.000 claims description 2
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 39
- 238000006243 chemical reaction Methods 0.000 abstract description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 8
- 150000003839 salts Chemical class 0.000 abstract description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 238000006735 epoxidation reaction Methods 0.000 abstract description 3
- 229910052710 silicon Inorganic materials 0.000 abstract description 3
- 239000010703 silicon Substances 0.000 abstract description 3
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 abstract 1
- 230000003993 interaction Effects 0.000 abstract 1
- 101710154778 Thymidylate synthase 1 Proteins 0.000 description 70
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 40
- 239000003054 catalyst Substances 0.000 description 32
- 239000001294 propane Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical class COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 150000002894 organic compounds Chemical class 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 101710134784 Agnoprotein Proteins 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- HOPRXXXSABQWAV-UHFFFAOYSA-N anhydrous collidine Natural products CC1=CC=NC(C)=C1C HOPRXXXSABQWAV-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical class CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Natural products C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 1
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 description 1
- SUAKHGWARZSWIH-UHFFFAOYSA-N N,N‐diethylformamide Chemical compound CCN(CC)C=O SUAKHGWARZSWIH-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention provides a modification method for a TS-1 titanium and silicon molecular sieve having an MF1 structure, which is characterized in that the method comprises a metal salt water solution and a synthetized TS-1 molecular sieve, wherein the TS-1 is added in the metal salt water solution to be statically placed for 6 to 100 hours according to the ratio: metal salt: water: molecular sieve = 0.01 to 10g: 10 to 100 ml: 1g, the water is dried in the water bath of 30 to 100 DEG C, the TS-1 and the metal salt water solution are dried in an oven for 1 to 20 hours at the temperature of 110 to 200 DEG C, the room temperature is risen to 200 to 800 DEG C for 1 to 12 hours by using a temperature programming way, the TS-1 titanium molecular sieve with the metal oxide modification of the present invention is obtained by roasting 2 to 20 hours under the temperature, and the loading capacity of metal oxides is 0.1 to 30% (mass percentage). The present invention has the effects and the advantages that the activity of the present invention is increased because of the interaction of the metal oxides and the TS-1, and the TS-1 with the metal oxide modification not only can increase the percent conversion of hydrogen dioxide but also can increase the selectivity of propylene oxide for being used for propene epoxidation reaction.
Description
Technical field
The invention belongs to the preparation method of metal oxide modified titanium-silicon molecular sieve catalyst and the application in propylene ring oxidation reaction.
Background technology
HTS is the novel hetero-atom molecular-sieve of early eighties exploitation, and He Cheng molecular sieve comprises the TS-1 with MFI structure, the TS-2 of MEL structure and have than the TS-48 of macroporous structure etc.Taramasso etc. adopt TPAOH (TPAOH) to be the template agent first, and tetraethyl titanate is the titanium source, has synthesized titanium-silicon molecular sieve TS-1 first.At entering weak points such as the skeleton Ti content is few in this method, the more weak butyl titanate (TBOT) of employing hydrolysing activities such as Thangaraj replaces too sour tetra-ethyl ester (TEOT) to carry out the prehydrolysis processing, the hydrolysis rate in titanium source and silicon source is mated more, thereby can improve the Ti content of molecular sieve.In said method, expensive TPAOH is the template agent owing to employing, and very high to the purity requirement of raw material, is unfavorable for the commercial Application of HTS.For fear of adopting expensive TPAOH is the template agent, and Muller etc. are the template agent with 4-propyl bromide (TPABr), and ammoniacal liquor is that alkali source replaces TPAOH to synthesize titanium-silicon molecular sieve TS-1, greatly reduces the synthetic expense of TS-1.
Because the catalytic oxidation performance of TS-1 uniqueness, be used to the hydroxylating, cyclohexanone oximate, the partial oxidation of alkane, the oxidation of alcohol of epoxidation, benzene and the phenol of alkene etc. very soon.Particularly TS-1 is used for the oxidation of propylene, has obtained good selective oxidation effect.With the hydrogen peroxide for oxidant methyl alcohol is that HTS has advantages of high catalytic activity to propylene under the condition of solvent, but the selectivity of expoxy propane is lower.European patent EP 0940393 has disclosed and added the organic compound that contains the N-C=O group in propylene ring oxidation reaction, and in coming and the acid site on the titanium-silicon molecular sieve TS-1 is to improve the expoxy propane selectivity.The organic compound that contains the N-C=O group in the above-mentioned patent comprises N, N-dimethyl-formamide, N, N-diethyl-formamide, N, compounds such as N-dipropyl-formamide.Mixed liquor at 460g methyl alcohol and 23g water is a solvent, and propylene pressure is 2.2atm, and the TS-1 of 1.67g makes catalyst, 29.55g hydrogen peroxide (mass concentration is 57.55%) is made oxidant, reaction temperature is under 40 ℃ of conditions, and the hydrogen peroxide conversion ratio is 90%, and the expoxy propane selectivity is 71%.As in course of reaction, adding the 1-Methyl-2-Pyrrolidone of 1000ppm, under the situation that keeps the hydrogen peroxide conversion ratio not reduce, can make the expoxy propane selectivity reach 91%.And adding other organic compound that contains the N-C=O group or different content 1-Methyl-2-Pyrrolidone, the expoxy propane selectivity has only 83.7～90.4%.Can improve the expoxy propane selectivity though in reaction, add compound such as 1-Methyl-2-Pyrrolidone, still have 9～16% propylene glycol monomethyl ethers to generate.European patent EP 1144398 has disclosed and added tertiary amine and oxide thereof in propylene ring oxidation reaction, improves the expoxy propane selectivity.Tertiary amine and oxide thereof in the above-mentioned patent comprise pyridine, trimethylpyridine, 2,6-lutidines, halogeno-group pyridine, cyano group halogeno-group pyridine, triazole, triazine, aniline, N, accelerine, 1-alkyl imidazole, 1-Alkylpiperidine, compounds such as 1-alkyl morpholine.At 34g methyl alcohol is solvent, and the 14g propylene is a substrate, and the TS-1 of 250mg (containing 2.1%Ti) makes catalyst, 8g hydrogen peroxide (mass concentration is 30%) is done under the oxidant condition, 40 ℃ of reactions 30 minutes, the hydrogen peroxide conversion ratio was 94%, and the expoxy propane selectivity is 91.6%.If in reaction system, add 2 of 200mg, the 6-lutidines, the expoxy propane selectivity can reach 98.5%, but the hydrogen peroxide conversion ratio reduces to 74%.Though add 2 in reaction, compounds such as 6-lutidines can improve the expoxy propane selectivity, and the hydrogen peroxide conversion ratio is reduced.Therefore, under hydrogen peroxide conversion ratio conditions of higher, can't obtain the high selectivity expoxy propane.
The subject matter that above-mentioned prior art exists is: (1) can't obtain the high selectivity expoxy propane under hydrogen peroxide conversion ratio conditions of higher, and (2) have a spot of the third two to enjoy monomethyl ether and generate under hydrogen peroxide conversion ratio conditions of higher.The water that contains a spot of propylene glycol monomethyl ether directly discharging can cause environmental pollution, and propylene glycol monomethyl ether is very difficult with separating of water.Because water and propylene glycol monomethyl ether form azeotropic mixture, needing adding benzene to remove a large amount of water as entrainer could separate water with propylene glycol monomethyl ether, and solvent methanol also needs separating cycle to use, and these all cause energy consumption too big, have therefore restricted the commercial Application of HTS.
Summary of the invention
The purpose of this invention is to provide and a kind ofly titanium-silicon molecular sieve TS-1 with MFI structure is carried out method of modifying with metal oxide.
The present invention is that the aqueous solution with slaine or mixed metal salt carries out modification to the TS-1 molecular sieve.The slaine that can be used as modification comprises ammonium salt of metal nitrate, metal acetate salt, metal etc., as: copper nitrate, plumbi nitras, silver nitrate, magnesium nitrate, zirconium oxychloride, ammonium molybdate, chromic nitrate, manganese nitrate, ferric nitrate, cobalt nitrate, nickel nitrate, zinc nitrate, strontium nitrate, ammonium tungstate etc., wherein preferred copper nitrate, plumbi nitras, cobalt nitrate, nickel nitrate, silver nitrate.Slaine: water: TS-1=0.01～10g: 10～100ml: 1g, optimum range are slaine: water: TS-1=0.05～5g: 10～50ml: 1g.The step of the TS-1 molecular sieve being carried out modification is as follows: slaine or mixed metal salt are dissolved in 10～100ml distilled water, add the TS-1 molecular sieve, left standstill 6～100 hours, in 30～90 ℃ of water-baths with the water evaporate to dryness, preferably adopt 10～60ml distilled water to leave standstill 10～60 hours and in 50～80 ℃ of water-baths with the water evaporate to dryness, drying is 1～12 hour in 110～200 ℃ of baking ovens, adopt temperature-programmed mode, rose to 200～800 ℃ with 2～10 hours, and this roasting temperature 2～20 hours, preferably drying also rose to 300～700 ℃ of roastings 3～10 hours with 3～6 hours in 3～8 hours in 110～150 ℃ of baking ovens, obtained metal oxide modified TS-1.The load capacity of metal oxide is 0.1～30% (quality percentage composition), and optimum load amount is 0.2～20%.
Adopt the titanium-silicon molecular sieve TS-1 of modification of the present invention, interact, its activity is improved because metal oxide and TS-1 exist.By load different metal oxides and mixed-metal oxides the activity of TS-1 is improved in various degree; By regulating the load capacity of metal oxide or mixed-metal oxides, not only can improve the active of TS-1 but also can improve the expoxy propane selectivity; After operating condition optimization, TS-1 after the modification is used for propylene ring oxidation reaction, keeping obtaining high expoxy propane selectivity under the high hydrogen peroxide conversion ratio condition.By optimizing modified condition, with 4%Ag
2O is carried on the TS-1, then this catalyst is used for the water as solvent propylene ring oxidation reaction, and be under 96.3% condition at the hydrogen peroxide conversion ratio, the expoxy propane selectivity can reach high to 100%.
Effect of the present invention and benefit are to adopt metal oxide or composite metal oxide modification TS-1, and TS-1 catalyst after the modification is applied in the propylene ring oxidation reaction of water as solvent, because no longer with an organic solvent, have reduced cost, have simplified technological process.And owing to there is not the generation of propylene glycol monomethyl ether, the accessory substance propane diols can not form azeotrope with water, need not re-use benzene as entrainer, makes water and propane diols carry out simple separation and just can discharge, and has reduced energy consumption, has reduced pollution.
The specific embodiment
Be described in detail the specific embodiment of the present invention and most preferred embodiment below.
Said TS-1 molecular sieve can be the TS-1 molecular sieve that synthesizes according to the whole bag of tricks of the prior art in the method for modifying of the HTS of the MFI of having structure provided by the invention.
The invention provides that said slaine can be that single slaine also can be two or more slaine in the method for modifying.
The invention provides and to comprise in the method for modifying that the repetition one or many carries out the process of modification to molecular sieve with above-mentioned slaine.
Reference examples 1
The synthetic employing hydrothermal synthesis method of titanium-silicon molecular sieve TS-1 carries out.Adopting 4-propyl bromide (TPABr) is the template agent, and organic ethamine is alkali source, and Ludox is the silicon source, and the titanium tetrachloride alcoholic solution is titanium source (alcoholic solution comprises isopropyl alcohol, n-butanol etc.), and the mole of reactant consists of: SiO
2: TiO
2: C
2H
5N: TPABr: H
2O=1: 0.01～0.03: 0.5～3.0: 0.1～0.3: 30～60.Material is successively added in the reaction vessel under 100～400rmp stirring condition by said ratio, be transferred in the autoclave after reinforced the finishing, under 130～190 ℃ of conditions, crystallization 10～60 hours, after filtration, washing, drying, roasting obtains titanium-silicon molecular sieve TS-1 catalyst.
Embodiment 1
The preparation of TS-1 is undertaken by reference examples 1.With 0.6075 gram Cu (NO
3)
23H
2O is dissolved in 14 ml deionized water, adds 5 gram TS-1, leaves standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, drying is 2 hours in 120 ℃ of baking ovens, the catalyst that drying is good is in the mode of temperature programming, rose to 540 ℃ from room temperature with 3 hours, and this roasting temperature 5 hours, make CuO modification TS-1 catalyst, wherein CuO accounts for 4% (quality percentage composition) of TS-1 content.
Embodiment 2
The preparation of TS-1 is undertaken by reference examples 1.With 0.9113 gram Cu (NO
3)
23H
2O is dissolved in 14 ml deionized water, adds 5 gram TS-1, leaves standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, drying is 2 hours in 120 ℃ of baking ovens, the catalyst that drying is good is in the mode of temperature programming, rose to 540 ℃ from room temperature with 3 hours, and this roasting temperature 5 hours, make CuO modification TS-1 catalyst, wherein CuO accounts for 6% (quality percentage composition) of TS-1 content.
Embodiment 3
The preparation of TS-1 is undertaken by reference examples 1.With 0.3024 gram Pb (NO
3)
2Be dissolved in 14 ml deionized water, add 5 gram TS-1, left standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, drying is 2 hours in 120 ℃ of baking ovens, the catalyst that drying is good is in the mode of temperature programming, rose to 300 ℃ from room temperature with 3 hours, and this roasting temperature 5 hours, make PbO modification TS-1 catalyst, wherein PbO accounts for 4% (quality percentage composition) of TS-1 content.
Embodiment 4
The preparation of TS-1 is undertaken by reference examples 1.With 0.7769 gram Co (NO
3)
26H
2O is dissolved in 14 ml deionized water, adds 5 gram TS-1, leaves standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, drying is 2 hours in 120 ℃ of baking ovens, the catalyst that drying is good is in the mode of temperature programming, rose to 300 ℃ from room temperature with 3 hours, and this roasting temperature 5 hours, make CoO modification TS-1 catalyst, wherein CoO accounts for 4% (quality percentage composition) of TS-1 content.
Embodiment 5
The preparation of TS-1 is undertaken by reference examples 1.With 0.7786 gram Ni (NO
3)
26H
2O is dissolved in 14 ml deionized water, adds 5 gram TS-1, leaves standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, drying is 2 hours in 120 ℃ of baking ovens, the catalyst that drying is good is in the mode of temperature programming, rose to 300 ℃ from room temperature with 3 hours, and this roasting temperature 5 hours, make NiO modification TS-1 catalyst, wherein NiO accounts for 4% (quality percentage composition) of TS-1 content.
Embodiment 6
The preparation of TS-1 is undertaken by reference examples 1.With 0.2932 gram AgNO
3Be dissolved in 14 ml deionized water, add 5 gram TS-1, left standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, in 120 ℃ of baking ovens dry 2 hours, the catalyst that drying is good rose to 500 ℃ from room temperature with 3 hours in the mode of temperature programming, and this roasting temperature 5 hours, made Ag
2O modification TS-1 catalyst, wherein Ag
2O accounts for 4% (quality percentage composition) of TS-1 content.
Embodiment 7
The preparation of TS-1 is undertaken by reference examples 1.With 0.3038 gram Cu (NO
3)
23H
2O and 0.1466 gram AgNO
3Be dissolved in 14 ml deionized water, add 5 gram TS-1, left standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, in 120 ℃ of baking ovens dry 2 hours, the catalyst that drying is good rose to 500 ℃ from room temperature with 2 hours in the mode of temperature programming, and this roasting temperature 5 hours, made CuO and Ag
2The composite modified TS-1 catalyst of O, wherein CuO and Ag
2O respectively accounts for 2% (quality percentage composition) of TS-1 content.
Embodiment 8
The preparation of TS-1 is undertaken by reference examples 1.With 0.563 gram Mn (CH
3COOH)
29H
2O is dissolved in 14 ml deionized water, adds 5 gram TS-1, leaves standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, in 120 ℃ of baking ovens dry 2 hours, the catalyst that drying is good rose to 550 ℃ from room temperature with 3 hours in the mode of temperature programming, and this roasting temperature 5 hours, made MnO
2Modification TS-1 catalyst, wherein MnO
2Account for 4% (quality percentage composition) of TS-1 content.
Embodiment 9
The preparation of TS-1 is undertaken by reference examples 1.With 1.7172 gram (NH
4)
6MoO
244H
2O is dissolved in 28 ml deionized water, adds 5 gram TS-1, leaves standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, in 120 ℃ of baking ovens dry 2 hours, the catalyst that drying is good rose to 300 ℃ from room temperature with 3 hours in the mode of temperature programming, and this roasting temperature 5 hours, made MoO
3Modification TS-1 catalyst, wherein MoO
3Account for 4% (quality percentage composition) of TS-1 content.
Embodiment 10
The preparation of TS-1 is undertaken by reference examples 1.With 1.053 gram Cr (NO
3)
39H
2O is dissolved in 14 ml deionized water, adds 5 gram TS-1, leaves standstill 24 hours.Then under continuous stirring condition in 80 ℃ of water-baths with the water evaporate to dryness, in 120 ℃ of baking ovens dry 2 hours, the catalyst that drying is good rose to 300 ℃ from room temperature with 3 hours in the mode of temperature programming, and this roasting temperature 5 hours, made Cr
2O
3Modification TS-1 catalyst, wherein Cr
2O
3Account for 4% (quality percentage composition) of TS-1 content.
Embodiment 11-21
In the 250ml stainless steel autoclave, the catalyst that adds 0.4g reference examples 1 and embodiment 1-10 system respectively, the 32ml deionized water, the hydrogen peroxide of 2ml30%, magnetic agitation, propylene pressure 0.4MPa, 60 ℃ of reaction temperatures, reaction time is 60 minutes, the conversion ratio of iodometric determination hydrogen peroxide, and gas chromatograph is analyzed the expoxy propane selectivity.The results are shown in table 1.
The epoxidation of propylene performance of the various catalyst of table 1
| Title | Hydrogen peroxide conversion ratio (%) | Expoxy propane selectivity (%) |
| Reference examples 1 | 56.02 | 83.52 |
| Embodiment 1 | 87.61 | 95.01 |
| Embodiment 2 | 92.04 | 94.46 |
| Embodiment 3 | 95.37 | 100 |
| Embodiment 4 | 91.67 | 82.90 |
| Embodiment 5 | 73.15 | 82.77 |
| Embodiment 6 | 96.30 | 100 |
| Embodiment 7 | 88.60 | 94.31 |
| Embodiment 8 | 96.30 | 70.27 |
| Embodiment 9 | 76.85 | 4.13 |
| Embodiment 10 | 95.37 | 32.40 |
As can be seen, the TS-1 molecular sieve of using modification of the present invention is as catalyst, and the hydrogen peroxide conversion ratio all has raising in various degree, and wherein embodiment 6 and embodiment 8 preparation activity of such catalysts are the highest, and the hydrogen peroxide conversion ratio reaches 96.3%.The TS-1 molecular sieve that adopts embodiment 1, embodiment 2, embodiment 3, embodiment 6, embodiment 7 modifications is as catalyst, the expoxy propane selectivity all has raising in various degree, wherein adopt the TS-1 molecular sieve effect of embodiment 3 and embodiment 6 modifications best, the expoxy propane selectivity can be up to 100%.Therefore, at the TS-1 molecular sieve catalyst of propylene ring oxidation reaction employing metal oxide modified, keeping to obtain high expoxy propane selectivity under the high hydrogen peroxide conversion ratio prerequisite.
Claims (5)
1. the method for modifying of a HTS, it is characterized in that this method comprises: with the aqueous solution of slaine and the TS-1 molecular sieve that has synthesized according to slaine: water: the ratio of molecular sieve=0.01～10g: 10～100ml: 1g is added to TS-1 in the aqueous solution of slaine, left standstill 6～100 hours, in 30～90 ℃ of water-baths with the water evaporate to dryness, drying is 1～12 hour in 110～200 ℃ of baking ovens, mode with temperature programming, rose to 200～800 ℃ from room temperature with 2～10 hours, and this roasting temperature 2～20 hours, the load capacity of gained metal oxide is 0.2～20 quality %, promptly obtain the TS-1 molecular sieve with metal oxide modified of the present invention, said here slaine is meant copper, plumbous, cobalt, nickel or silver salt.
2. the method for modifying of a kind of HTS according to claim 1 is characterized in that slaine: water: TS-1=0.05～5g: 10～50ml: 1g.
3. the method for modifying of a kind of HTS according to claim 1, its feature also is: wherein said slaine is single slaine or two kinds and two or more slaines; Slaine comprises metal nitrate or metal acetate salt.
4. the method for modifying of a kind of HTS according to claim 1 is characterized in that: comprise in this method that the repetition one or many carries out the process of modification to molecular sieve with above-mentioned slaine.
5. according to the application of the HTS of each described method of modifying preparation among the claim 1-4, it is characterized in that modifying titanium-silicon molecular sieve is used for doing with water the propylene ring oxidation reaction of solvent.
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