CN1720097A - 环氧化催化剂的制备方法 - Google Patents
环氧化催化剂的制备方法 Download PDFInfo
- Publication number
- CN1720097A CN1720097A CN200380104860.XA CN200380104860A CN1720097A CN 1720097 A CN1720097 A CN 1720097A CN 200380104860 A CN200380104860 A CN 200380104860A CN 1720097 A CN1720097 A CN 1720097A
- Authority
- CN
- China
- Prior art keywords
- carrier
- catalyst
- aforementioned
- alkylene oxide
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 17
- 239000010703 silicon Substances 0.000 claims abstract description 17
- 125000002947 alkylene group Chemical group 0.000 claims abstract description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000007598 dipping method Methods 0.000 claims description 15
- 230000007062 hydrolysis Effects 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 14
- 239000000741 silica gel Substances 0.000 claims description 13
- 229910002027 silica gel Inorganic materials 0.000 claims description 13
- 150000003608 titanium Chemical class 0.000 claims description 11
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 11
- 239000001294 propane Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 150000002432 hydroperoxides Chemical class 0.000 claims description 9
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 9
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 8
- GQNOPVSQPBUJKQ-UHFFFAOYSA-N 1-hydroperoxyethylbenzene Chemical compound OOC(C)C1=CC=CC=C1 GQNOPVSQPBUJKQ-UHFFFAOYSA-N 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 claims description 4
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 230000018044 dehydration Effects 0.000 claims 1
- 238000006297 dehydration reaction Methods 0.000 claims 1
- 239000010936 titanium Substances 0.000 abstract description 13
- 229910052719 titanium Inorganic materials 0.000 abstract description 11
- -1 titanium halide Chemical class 0.000 abstract description 5
- 229960001866 silicon dioxide Drugs 0.000 description 14
- 238000001354 calcination Methods 0.000 description 13
- 239000007789 gas Substances 0.000 description 12
- 239000000377 silicon dioxide Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 6
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 4
- 150000003609 titanium compounds Chemical class 0.000 description 4
- FRIBMENBGGCKPD-UHFFFAOYSA-N 3-(2,3-dimethoxyphenyl)prop-2-enal Chemical compound COC1=CC=CC(C=CC=O)=C1OC FRIBMENBGGCKPD-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003377 silicon compounds Chemical class 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- RNDNSYIPLPAXAZ-UHFFFAOYSA-N 2-Phenyl-1-propanol Chemical compound OCC(C)C1=CC=CC=C1 RNDNSYIPLPAXAZ-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 238000011021 bench scale process Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical group C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000000640 hydroxylating effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052909 inorganic silicate Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 235000013847 iso-butane Nutrition 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000004756 silanes Chemical class 0.000 description 1
- 125000005372 silanol group Chemical group 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0272—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255
- B01J31/0274—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing elements other than those covered by B01J31/0201 - B01J31/0255 containing silicon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0238—Impregnation, coating or precipitation via the gaseous phase-sublimation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/72—Epoxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0209—Impregnation involving a reaction between the support and a fluid
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
一种制备环氧化催化剂的方法，该方法包括利用由卤化钛组成的气体物流浸渍含硅载体，以及利用这种催化剂制备环氧烷的方法。
Description
技术领域
本发明涉及环氧化催化剂的制备以及利用这种催化剂制备环氧烷的方法。
背景技术
环氧化催化剂被认为是一种促进含环氧基的化合物的制备的催化剂。一种公知的方法包括使氢过氧化物和链烯与非均相环氧化催化剂接触，并采出含环氧烷和醇的产物物流。
用于制备含环氧基的化合物的催化剂是公知的。EP-A-345856描述了这种催化剂的制备，所述催化剂包含与固体二氧化硅和/或无机硅酸盐化合组合的钛。所述制备方法包括：(a)用优选包含惰性气体的气态四氯化钛物流浸渍硅化合物，(b)煅烧步骤(a)得到的反应产物，和(c)使步骤(b)的产物水解。惰性气体物流还具有气态四氯化钛的载体的功能。对于这种用途，所述气体以相对较大量存在。
总体来说人们一直对提高环氧化方法的选择性有兴趣，更具体是对环氧烷的制备方法有兴趣。我们发现了一种简单且吸引人的方法来实现这一目的。
发明内容
本发明涉及一种制备环氧化催化剂的方法，所述方法包括利用由卤化钛组成的气体物流浸渍含硅的载体。
即使载体已与相同量的卤化钛接触过，也可以得到选择性提高的催化剂。
具体实施方式
本发明的催化剂通过浸渍含硅载体得到。原则上，任何含硅载体都适用于本发明的制备方法。含硅载体的例子包括沸石。含硅载体优选为二氧化硅载体。
二氧化硅载体主要由二氧化硅组成。但也可以存在有限量的其它化合物如污染物。
已知污染物可能影响最终催化剂的性能。用于本发明的二氧化硅载体优选含有至多1200ppm的钠，更具体为至多1000ppm的钠。另外，二氧化硅载体优选包含至多500ppm的铝、至多500ppm的钙、至多200ppm的钾、至多100ppm的镁和至多100ppm的铁。所述量均以载体的量为基准。
二氧化硅载体优选为硅胶。用于本发明的硅胶载体原则上可以为任何由含硅凝胶得到的载体。硅胶通常为含水二氧化硅的固体无定形形式，其与其它含水二氧化硅的区别在于它们的微孔度和羟基化表面。硅胶通常含有胶体尺寸的聚集二氧化硅颗粒的三维网络。它们通常通过以下方法制备：通过与强无机酸混合而使硅酸钠水溶液酸化至pH小于11。酸化造成单硅酸(Si(OH)4)的形成，其与内部的硅氧烷键和外部的硅烷醇基聚合成颗粒。在确定的pH下，聚合物颗粒聚集，从而形成链且最终形成凝胶网络。硅酸盐的浓度、温度、pH和凝结剂的加入将影响胶凝时间和最终的凝胶性质，如密度、强度、硬度、表面积和孔体积。所得的水凝胶通常被洗掉电解质，并进行干燥和活化。合适的硅胶载体为二氧化硅载体V432和DAVICAT P-732，它们可由GraceDavison商购得到。
用于本发明的硅胶的重均粒度优选为至多2毫米。已发现特别合适的粒度是重均粒度为0.2-1.8mm，更具体为0.4-1.6mm，最特别为0.6-1.4mm。
当与卤化钛接触时，含硅载体优选具有低的水含量。低的水含量可以通过对本领域技术人员已知的任何方法来实现。一种优选的方法包括在利用由卤化钛组成的气体物流浸渍含硅载体前干燥所述含硅载体。一种合适的干燥方法包括在温度为200-700℃下处理所述含硅载体。已经令人惊奇地发现，在特定条件下干燥将得到更为改善的催化剂。优选的干燥条件包括在高于200℃至300℃的温度下干燥载体。优选地，实施干燥1-8小时，并优选在惰性气体如氮存在下实施。优选的方法已在要求欧洲申请02258294.4优先权的共同待审专利申请中进行了更为详细的描述。
如果含硅载体已经进行包含如下步骤预处理，则可以观察到更进一步的改善：煅烧所述含硅载体，随后水解所得到的载体。水解包括用水或蒸汽处理所述载体。水解优选用蒸汽来实施。可替换地，水解处理可以包括用无机酸的水溶液、铵盐的水溶液或它们的组合进行洗涤处理。在进一步处理载体前，优选脱除水解后仍可能存在的任意水。水优选通过干燥来脱除。优选在相对高的温度下实施煅烧。一种优选的煅烧处理包括：(a)在温度为至少400℃下煅烧硅胶载体，(b)水解煅烧后的硅胶载体，(c)用含钛浸渍剂浸渍步骤(b)中得到的水解载体，和(d)煅烧浸渍后的载体。步骤(a)的煅烧优选在温度为450-800℃下实施，更优选为500-700℃。
用于本发明的硅胶的表面积优选为至多1000m2/g，更优选为至多800m2/g，最优选为至多500m2/g。
可以用于本发明方法的卤化钛包括三-和四-取代的钛复合物，其具有1-4个卤素取代基，并且如果存在，剩余的取代基为醇盐或氨基基团。卤化钛可以是单一卤化钛化合物，也可以是卤化钛化合物的混合物。卤化钛优选包含至少50wt％的四氯化钛，更特别为至少70wt％的四氯化钛。最优选地，所述气体物流由四氯化钛组成。
本发明包括利用由卤化钛组成的气体浸渍载体。令人惊奇地发现：如果利用由卤化钛组成的气体浸渍含硅载体，则可能得到对所希望环氧烷具有较高选择性的催化剂。本发明的制备是在没有载气存在下实施的。不希望被任何理论所束缚，据认为载气将干扰浸渍。但在含硅载体与气态卤化钛的接触过程中，允许存在有限量的其它气态化合物。在浸渍过程中与载体接触的气体优选含至少70wt％的卤化钛，更具体为至少80wt％，更特别为至少90wt％，最特别为至少95wt％。
气态卤化钛可以按本领域技术人员已知的任何方法制备。一种简单且容易的方法包括加热含卤化钛的容器至一定温度得到气态卤化钛。
在用作催化剂之前，浸渍后的载体通常进行煅烧并随后水解。确信的是煅烧将脱除卤化氢，更具体为氯化氢，所述卤化氢通过卤化钛与含硅载体表面上存在的硅化合物反应而形成。
浸渍载体的任选煅烧通常包括使浸渍载体经受至少500℃的温度，更具体为至少600℃。煅烧优选在温度为至少650℃下实施。从实际角度考虑，所应用的煅烧温度优选为至多1000℃。
浸渍且煅烧后载体的水解可以消除Ti-卤离子键。在某种程度上，浸渍后载体的水解通常比浸渍前载体的任选水解更苛刻。因此，浸渍后载体的这种水解合适地在温度为150-400℃下用蒸汽实施。
水解后的浸渍载体随后优选进行甲硅烷基化，例如通过使水解后的浸渍载体与甲硅烷基化试剂接触进行甲硅烷基化，优选在温度为100-425℃下实施。合适的甲硅烷基化试剂包括有机硅烷，如带有C1-C3烃基取代基的四取代硅烷。一种非常合适的甲硅烷基化试剂为六甲基二硅氮烷。合适甲硅烷基化方法和甲硅烷基化试剂的具体例子在US-A-3,829,392和US-3,923,843中有述，这些文献在US-A-6,011,162和EP-A-734764中也被引用。
以催化剂总重量为基准，钛量(以金属钛计)通常为0.1-10wt％，适当为1-5wt％。优选地，钛或钛化合物如盐或氧化物是存在的唯一金属和/或金属化合物。
正如上面所述，在本领域中公知的是：应用氢过氧化物如过氧化氢或有机氢过氧化物作氧源，通过相应烯烃的环氧化作用制备环氧烷如环氧丙烷。氢过氧化物可以是过氧化氢或任意的有机氢过氧化物如叔丁基氢过氧化物、枯烯氢过氧化物和乙苯氢过氧化物。得到环氧烷的链烯通常为丙烯，其得到环氧丙烷。已经发现本发明所制备的催化剂在这种方法中得到特别好的结果。因此，本发明进一步涉及制备环氧烷的方法，该方法包括使氢过氧化物和链烯与非均相环氧化催化剂接触，并采出包含环氧烷和醇和/或水的产物物流，其中催化剂按本发明来制备。
具体的有机氢过氧化物为乙苯氢过氧化物，在此情况下得到的醇为1-苯基乙醇。1-苯基乙醇通常通过脱水进一步转化得到苯乙烯。
制备环氧丙烷的另一种方法是由异丁烷和丙烯开始共同制备环氧丙烷和甲基叔丁基醚(MTBE)。这种方法在本领域中是公知的，其包括与前段中描述的苯乙烯/环氧丙烷制备方法类似的反应步骤。在环氧化步骤中，叔丁基氢过氧化物与丙烯反应形成环氧丙烷和叔丁醇。随后叔丁醇被醚化为MTBE。
另一种方法包括利用枯烯制备环氧丙烷。在这种方法中，枯烯与氧或空气反应形成枯烯氢过氧化物。这样得到的枯烯氢过氧化物在环氧化催化剂存在下与丙烯反应，得到环氧丙烷和2-苯基丙醇。后者利用非均相催化剂和氢可以转化为枯烯。合适的方法例如在WO 02/48126中有述。
本发明的环氧化反应的条件为通常应用的条件。对于利用乙苯氢过氧化物的丙烯环氧化反应来说，通常的反应条件包括：温度为50-140℃，合适为75-125℃，压力高达80bar，且反应介质为液相。
通过如下实施例进一步描述本发明。
实施例
在实施例中应用的硅胶载体的表面积为300m2/g，并且重均粒度为约1mm。基本上所有颗粒都具有0.6-1.4mm的粒度。
将75克硅胶载体在250℃下干燥2小时。
干燥后的硅胶载体与含四氯化钛的气体物流接触。借助电加热系统加热四氯化钛至200℃而得到所述气体物流。通过加入不同量的氮气而得到不同的气体物流。在每次试验结束时，每种二氧化硅载体均已与相同量的四氯化钛接触。
这样得到的浸渍催化剂在600℃下煅烧7小时。随后，煅烧后的催化剂在325℃下与蒸汽接触6小时。蒸汽物流由每小时3克水和每小时8N1氮气组成。最后，在每小时1.4N1的氮气流中，在185℃在2小时内通过与每小时18克六甲基二硅氮烷接触，使催化剂甲硅烷基化。
对得到的催化剂分析载体上沉积的钛量。
在一个连续的小试规模的环氧化装置中测试催化剂的选择性，所述装置包括：分别含有乙苯氢过氧化物和丙烯原料物流的多个自动重量平衡的容器，两个高压泵，一个固定床反应器，用于为反应器泵送循环物流的第三泵，持续保持反应器在温度为60-120℃下的设备，脱除轻沸点组分如丙烯的汽提器，一个冷却器和用于接收产物的容器。
通过两个高压泵为反应器提供原料，并在进入反应器前混合。反应器在40bar的压力和90℃下全充液操作。在反应器上保持较大的循环物流，从而使反应器床层等温操作，确保待再活化的催化剂与环氧化反应产物接触。在引入反应器前，原料与循环物流混合。
原料由40wt％的丙烯、20wt％的乙苯氢过氧化物和40wt％的乙苯组成。
所得结果在表1中给出。选择性为所形成的环氧丙烷与所转化的乙苯氢过氧化物的摩尔比。
实施例2
以与实施例1中所描述的相似的方式制备其它催化剂。但浸渍后催化剂煅烧6小时(而不是7小时)，同时在随后的水解中蒸汽物流含每小时5克水(而不是每小时3克水)。实验结果在表2中给出。
表1
| 实施例1 | 对比例1 | 对比例2 | |
| 浸渍气体wt％四氯化钛 | 100 | 75 | 60 |
| 催化剂钛(wt％)钠(wt％) | 4.10.07 | 4.00.07 | 4.10.07 |
| 对环氧丙烷的选择性投入生产100-200小时投入生产200-300小时 | 90.991.3 | 89.790.4 | 90.191.1 |
表2
| 实施例2 | 对比例3 | 对比例4 | |
| 浸渍气体wt％四氯化钛 | 100 | 26 | 1 |
| 催化剂钛(wt％)钠(wt％) | 3.80.07 | 4.10.05 | 4.10.07 |
| 对环氧丙烷的选择性投入生产100-200小时投入生产200-270小时投入生产270-340小时投入生产340-420小时 | 90.590.592.592.5 | 89.689.391.291.4 | 88.488.390.690.8 |
Claims (11)
1.制备环氧化催化剂的方法，该方法包括利用由卤化钛组成的气体物流浸渍含硅载体。
2.权利要求1的方法，其中含硅载体为硅胶。
3.前述权利要求任一项的方法，其中气体物流由四氯化钛组成。
4.前述权利要求任一项的方法，其中以载体的量为基准计，含硅载体包含至多1200ppm的钠。
5.前述权利要求任一项的方法，包括在浸渍前干燥所述含硅载体。
6.前述权利要求任一项的方法，其中煅烧浸渍后的载体并随后水解。
7.权利要求6的方法，其中使水解后的浸渍载体随后与甲硅烷基化试剂接触。
8.制备环氧烷的方法，该方法包括使氢过氧化物和链烯与非均相环氧化催化剂接触，并采出包含环氧烷和醇和/或水的产物物流，其中所述催化剂由前述权利要求任一项的方法制备。
9.权利要求8的方法，其中链烯为丙烯，和环氧烷为环氧丙烷。
10.权利要求9的方法，其中有机氢过氧化物为乙苯氢过氧化物，和所述醇为1-苯基乙醇。
11.权利要求10的方法，进一步包括使1-苯基乙醇脱水得到苯乙烯。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP02258296.9 | 2002-12-02 | ||
| EP02258296 | 2002-12-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1720097A true CN1720097A (zh) | 2006-01-11 |
Family
ID=32405785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200380104860.XA Pending CN1720097A (zh) | 2002-12-02 | 2003-11-24 | 环氧化催化剂的制备方法 |
Country Status (8)
| Country | Link |
|---|---|
| EP (1) | EP1567261A1 (zh) |
| JP (1) | JP2006507932A (zh) |
| CN (1) | CN1720097A (zh) |
| AU (1) | AU2003298312A1 (zh) |
| BR (1) | BR0316825A (zh) |
| CA (1) | CA2508043A1 (zh) |
| MX (1) | MXPA05005699A (zh) |
| WO (1) | WO2004050233A1 (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549205A (zh) * | 2013-10-11 | 2015-04-29 | 雷普索尔有限公司 | 用于再生多相环氧化催化剂的方法及该催化剂用于催化环氧化反应的用途 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2012917A1 (en) | 2006-05-02 | 2009-01-14 | Shell Internationale Research Maatschappij B.V. | Titanium catalyst, its preparation and its use in epoxidation reactions |
| US8664412B2 (en) | 2010-07-19 | 2014-03-04 | Shell Oil Company | Epoxidation process |
| CN108349918A (zh) | 2015-11-09 | 2018-07-31 | 国际壳牌研究有限公司 | 催化剂制备 |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8813484D0 (en) * | 1988-06-08 | 1988-07-13 | Shell Int Research | Process for preparation of oxirane compound |
| FI87892C (fi) * | 1991-07-16 | 1993-03-10 | Neste Oy | Foerfarande foer framstaellning av heterogena katalysatorer med oenskad metallhalt |
| FR2704159B1 (fr) * | 1993-04-22 | 1995-06-09 | Atochem Elf Sa | Catalyseur solide à base de silice particulaire, comportant du titane, Procédé d'obtention, et utilisation dans l'époxydation d'oléfines. |
| FI96611C (fi) * | 1993-09-10 | 1996-07-25 | Neste Oy | Heterogeeninen polymerointikatalyytti ja menetelmä sen valmistamiseksi |
| KR100592442B1 (ko) * | 1997-05-05 | 2006-06-22 | 아르코 케미컬 테크날러쥐. 엘.피. | 개선된 불균일 촉매 조성물을 이용하는 에폭시화물 제조방법 |
| US6114552A (en) * | 1999-09-28 | 2000-09-05 | Arco Chemical Technology, L.P. | Heterogeneous epoxidation catalyst |
-
2003
- 2003-11-24 CA CA002508043A patent/CA2508043A1/en not_active Abandoned
- 2003-11-24 EP EP03796044A patent/EP1567261A1/en not_active Withdrawn
- 2003-11-24 MX MXPA05005699A patent/MXPA05005699A/es not_active Application Discontinuation
- 2003-11-24 CN CN200380104860.XA patent/CN1720097A/zh active Pending
- 2003-11-24 AU AU2003298312A patent/AU2003298312A1/en not_active Abandoned
- 2003-11-24 WO PCT/EP2003/050875 patent/WO2004050233A1/en not_active Application Discontinuation
- 2003-11-24 JP JP2004556324A patent/JP2006507932A/ja active Pending
- 2003-11-24 BR BR0316825-5A patent/BR0316825A/pt not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549205A (zh) * | 2013-10-11 | 2015-04-29 | 雷普索尔有限公司 | 用于再生多相环氧化催化剂的方法及该催化剂用于催化环氧化反应的用途 |
Also Published As
| Publication number | Publication date |
|---|---|
| BR0316825A (pt) | 2005-10-18 |
| MXPA05005699A (es) | 2005-07-26 |
| WO2004050233A8 (en) | 2004-08-05 |
| EP1567261A1 (en) | 2005-08-31 |
| WO2004050233A1 (en) | 2004-06-17 |
| JP2006507932A (ja) | 2006-03-09 |
| AU2003298312A1 (en) | 2004-06-23 |
| CA2508043A1 (en) | 2004-06-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1140335C (zh) | 含钛氧化硅催化剂 | |
| CN101437609A (zh) | 钛催化剂、其制备及其在环氧化反应中的应用 | |
| US7713906B2 (en) | Catalyst composition, process for its preparation and use thereof | |
| CN108349918A (zh) | 催化剂制备 | |
| CN1894030A (zh) | 催化剂制备 | |
| CN100548492C (zh) | 制备环氧化催化剂的方法和制备环氧化物的方法 | |
| CN1720097A (zh) | 环氧化催化剂的制备方法 | |
| CN1016172B (zh) | 表氯醇的制备方法 | |
| US20130116454A1 (en) | Epoxidation process | |
| US7125819B2 (en) | Catalyst preparation | |
| WO2006098421A1 (ja) | チタン含有珪素酸化物触媒の保存方法 | |
| JP2003520124A (ja) | 触媒担体材料及びその使用 | |
| RU2588128C2 (ru) | Способ эпоксидирования с титансодержащим катализатором на пористом силикатном носителе | |
| KR20220091553A (ko) | 티탄화 촉매, 티탄화 촉매의 제조 방법, 및 에폭시화 방법 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |