WO2018157685A1 - 一种包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂及制备方法和应用 - Google Patents
一种包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂及制备方法和应用 Download PDFInfo
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- WO2018157685A1 WO2018157685A1 PCT/CN2018/074144 CN2018074144W WO2018157685A1 WO 2018157685 A1 WO2018157685 A1 WO 2018157685A1 CN 2018074144 W CN2018074144 W CN 2018074144W WO 2018157685 A1 WO2018157685 A1 WO 2018157685A1
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- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- 238000002360 preparation method Methods 0.000 title description 15
- 239000010410 layer Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011247 coating layer Substances 0.000 claims abstract description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 196
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 107
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 89
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 52
- 229910003310 Ni-Al Inorganic materials 0.000 claims description 50
- 239000007864 aqueous solution Substances 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 238000005984 hydrogenation reaction Methods 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 31
- 150000002815 nickel Chemical class 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- 239000012686 silicon precursor Substances 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 24
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 21
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims description 21
- NMPJHMFXHISVBR-UHFFFAOYSA-N 4-(oxolan-2-yloxy)butan-1-ol Chemical compound OCCCCOC1CCCO1 NMPJHMFXHISVBR-UHFFFAOYSA-N 0.000 claims description 19
- 150000001241 acetals Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 18
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 18
- 125000004122 cyclic group Chemical group 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 15
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 13
- 229910052759 nickel Inorganic materials 0.000 claims description 13
- 239000012074 organic phase Substances 0.000 claims description 13
- PIAOXUVIBAKVSP-UHFFFAOYSA-N γ-hydroxybutyraldehyde Chemical compound OCCCC=O PIAOXUVIBAKVSP-UHFFFAOYSA-N 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910017604 nitric acid Inorganic materials 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 10
- 238000010992 reflux Methods 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- OZCRKDNRAAKDAN-UHFFFAOYSA-N but-1-ene-1,4-diol Chemical compound O[CH][CH]CCO OZCRKDNRAAKDAN-UHFFFAOYSA-N 0.000 claims description 6
- 238000007036 catalytic synthesis reaction Methods 0.000 claims description 6
- 238000005253 cladding Methods 0.000 claims description 6
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 5
- -1 aluminum alkoxide Chemical class 0.000 claims description 5
- 239000006227 byproduct Substances 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 238000005470 impregnation Methods 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 3
- 238000009489 vacuum treatment Methods 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims 1
- CQZWRJNSEROBSG-UHFFFAOYSA-N butane-1,4-diol but-1-yne-1,4-diol Chemical compound C(#CCCO)O.C(CCCO)O CQZWRJNSEROBSG-UHFFFAOYSA-N 0.000 claims 1
- 150000004702 methyl esters Chemical class 0.000 claims 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 229910052593 corundum Inorganic materials 0.000 abstract 5
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 4
- 229910052681 coesite Inorganic materials 0.000 abstract 3
- 229910052906 cristobalite Inorganic materials 0.000 abstract 3
- 239000000377 silicon dioxide Substances 0.000 abstract 3
- 229910052682 stishovite Inorganic materials 0.000 abstract 3
- 229910052905 tridymite Inorganic materials 0.000 abstract 3
- 229910003849 O-Si Inorganic materials 0.000 description 6
- 229910003872 O—Si Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 4
- MYWQGROTKMBNKN-UHFFFAOYSA-N tributoxyalumane Chemical compound [Al+3].CCCC[O-].CCCC[O-].CCCC[O-] MYWQGROTKMBNKN-UHFFFAOYSA-N 0.000 description 4
- 229910002800 Si–O–Al Inorganic materials 0.000 description 3
- 150000002373 hemiacetals Chemical class 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229910018173 Al—Al Inorganic materials 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N tetrahydrofuran Substances C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910018516 Al—O Inorganic materials 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical class [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J37/18—Reducing with gases containing free hydrogen
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
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- C07C31/20—Dihydroxylic alcohols
- C07C31/207—1,4-Butanediol; 1,3-Butanediol; 1,2-Butanediol; 2,3-Butanediol
Definitions
- the invention belongs to a coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst, a preparation method and application thereof.
- the cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran is a by-product which is difficult to avoid during the hydrogenation of Reppe 1,4-butynediol to produce 1,4-butanediol, which itself cannot It is removed by direct hydrogenation and forms an azeotrope with 1,4-butanediol, which is difficult to separate by conventional distillation.
- the residue of acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran seriously affects the purity and color of the 1,4-butanediol product, directly affecting the quality of 1,4-butanediol and its downstream field. application.
- US 6,137,016 describes a process for the purification of 1,4-butanediol containing a small amount of cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran by hydrogenation, since the hydrogenation catalyst used is a universal hydrogenation Catalyst, its hydrogenation effect is not ideal.
- CN 102145286 B discloses a Ni-SiO 2 /Al 2 O 3 catalyst and a preparation method thereof, which can effectively realize hydrolysis and hydrogenation conversion of a cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran. However, its preparation process is relatively complicated.
- the object of the present invention is to provide a catalyst and a preparation method and application for coating a Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst which is simple and selective.
- the present invention provides a coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst in which an active component Ni particles are present in an amorphous or highly dispersed state in a carrier Al 2 O 3 .
- the present invention also provides a preparation method of the above coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst, comprising the following steps:
- Impregnation step introducing an active component Ni on the Al 2 O 3 support by a dipping method, and distributing tetrahedral and octahedral holes on the surface of the alumina, and growing the crystal into microcrystalline particles;
- Deposition step the surface of the Ni/Al 2 O 3 catalyst obtained in the impregnation step is introduced into the Al 2 O 3 -SiO 2 layer by deposition, and Al 2 O 3 -SiO 2 is deposited only on the surface of the alumina exposed by the gap of the Ni particles. ;as well as
- Washing step The deposited sample is washed and removed to remove weakly adsorbed components remaining on the surface of the catalyst.
- the present invention also provides another preparation method of the above-mentioned Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst, comprising the following steps:
- the Al 2 O 3 carrier is treated at 100 ° C to 150 ° C and then lowered to room temperature for use;
- the nickel salt aqueous solution prepared in the step (2) is immersed in the carrier of the step (1) at a ratio of 80 mL to 130 mL of the nickel salt aqueous solution per 100 g of the Al 2 O 3 carrier, and allowed to stand, dried, and calcined to obtain NiO/Al 2 O 3 precursor;
- NiO obtained in the step (3) is obtained by taking the amount of 1000-2000 mL of the aluminum precursor and the ethanol-aqueous solution of the silicon precursor per 100 g of Al 2 O 3 in the NiO/Al 2 O 3 precursor in the step (3).
- the Al 2 O 3 precursor is suspended in the solution prepared in the step (4), stirred under reflux at a constant temperature, filtered, and then washed with absolute ethanol, dilute nitric acid, deionized water, and dried;
- the present invention also provides a further preparation method of the above-mentioned Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst, comprising the following steps:
- the Al 2 O 3 carrier is subjected to vacuum treatment at 100 ° C to 150 ° C for 10 min to 30 min, or directly at 100 ° C to 150 ° C for 1 h to 10 h, and then lowered to room temperature for use;
- NiO obtained in the step (3) is obtained by taking the amount of 1000-2000 mL of the aluminum precursor and the ethanol-aqueous solution of the silicon precursor per 100 g of Al 2 O 3 in the NiO/Al 2 O 3 precursor in the step (3).
- the Al 2 O 3 precursor is suspended in the solution prepared in the step (4), and stirred under reflux at 20 ° C to 60 ° C for 1 h to 24 h. After filtration, the mixture is washed with absolute ethanol, 0.01 M diluted nitric acid and deionized water. After 5 to 5 times, the sample is dried at 80 ° C ⁇ 150 ° C for 2 h ⁇ 24 h;
- the sample obtained in the step (5) is calcined in an air or nitrogen atmosphere, and is heated from 2 ° C / min to 10 ° C / min to 400 ° C to 550 ° C, at a constant temperature of 1 h to 24 h; The reduction was carried out at 350 ° C to 650 ° C for 1 h to 24 h under h to 2000/h; a Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst was obtained.
- the method for preparing a coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst according to the present invention wherein the specific surface area of the Al 2 O 3 support described in the step (1) is preferably 110 m 2 /g ⁇
- the pore volume is preferably from 0.5 cm 3 /g to 1.3 cm 3 /g at 260 m 2 /g.
- the method for preparing a coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst according to the present invention wherein the nickel salt in the aqueous solution of the nickel salt in the step (2) is preferably nickel nitrate, nickel sulfate or chlorine.
- the nickel salt in the aqueous solution of the nickel salt in the step (2) is preferably nickel nitrate, nickel sulfate or chlorine.
- the nickels is preferably nickel nitrate, nickel sulfate or chlorine.
- the method for preparing a Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst coated according to the present invention wherein the drying time in the step (3) is preferably from 3 h to 12 h.
- the method for preparing a coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst according to the present invention wherein the silicon precursor in the step (3) is preferably tetraethyl orthosilicate or methyl orthosilicate.
- the silicon precursor in the step (3) is preferably tetraethyl orthosilicate or methyl orthosilicate.
- the method for preparing a Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst coated according to the present invention wherein the silicon precursor is further preferably ethyl orthosilicate.
- the method for preparing a coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst according to the present invention wherein the aluminum precursor described in the step (3) is preferably aluminum isopropoxide or aluminum n-butoxide.
- the aluminum precursor described in the step (3) is preferably aluminum isopropoxide or aluminum n-butoxide.
- the method for preparing a coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst according to the present invention wherein the aluminum precursor is further preferably aluminum nitrate.
- the method for preparing a coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst according to the present invention wherein the molar ratio of ethanol:water in the ethanol-water solution described in the step (3) is preferably 4 to 100. : 1.
- the method for preparing a Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst coated according to the present invention wherein the drying time in the step (5) is preferably from 3 h to 12 h.
- the present invention further provides the use of the above-mentioned Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst for hydrogenation catalytic synthesis of 1,4-butynediol, 4-butanediol.
- step A The use of the coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst of the present invention, wherein preferably, comprises the following step A:
- the catalyst is used for the catalytic synthesis of 1,4-butanediol by high-pressure hydrogenation of 1,4-butynediol, the water content of the raw material is 64wt%-72wt%; the content of 1,4-butanediol in the organic phase is 90wt%-91.5wt% ; butanol content 1wt% ⁇ 2wt%; 4-hydroxybutyraldehyde content 1.3wt% ⁇ 1.8wt%; 1,4-butynediol content 1.5wt% ⁇ 2wt%; 1,4-butenediol content 2.7 From wt% to 3.2 wt%; cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran content: 0.8 wt% to 1.2 wt%; carbonyl number: 8 mg (KOH) / g to 12 mg (KOH) / g, The hydrogenation is carried out at a reaction temperature of 100
- the invention relates to the coating of the Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst, wherein the content of the 1,4-butanediol in the organic phase product after the step A hydrogenation is 96.44 wt% to 97.76 wt.
- step B The application of the coated Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst according to the present invention, wherein preferably, the following step B is included:
- the catalyst is used for direct hydroconversion of an aqueous solution containing 5% but not more than 5% by weight of 1,4-butynediol, using an external circulation hydrogenation reaction process, feeding mode: up and down; reaction conditions: reaction temperature 105 °C ⁇ 150 ° C, hydrogen pressure 10MPa ⁇ 22MPa, liquid space velocity 1.0 / h ⁇ 1.7 / h, cycle ratio 18 ⁇ 22: 1.
- the active component Ni is introduced on the alumina support by the impregnation method, and the tetrahedral and octahedral voids of Ni are distributed on the surface of the alumina, and the core is grown into microcrystalline particles, and the particles have high dispersion.
- Al 2 O 3 -SiO 2 layer is introduced by deposition and precipitation. Since there is no reaction between SiO 2 and NiO, and the interaction is extremely weak, Al 2 O 3 -SiO 2 Deposited only on the surface of the alumina exposed by the NiO particles. As the content of Al 2 O 3 -SiO 2 increases, when the exposed alumina surface is completely covered by a single layer of Al 2 O 3 -SiO 2 , it will be exposed in a single layer. The Al 2 O 3 -SiO 2 surface further grows two, three, four... layers of Al 2 O 3 -SiO 2 .
- the sample is washed with absolute ethanol, 0.01M dilute nitric acid and deionized water, effectively removing the weakly adsorbed components remaining on the catalyst surface during the grafting process, especially the weakly adsorbed Al on the surface of NiO.
- the 2 O 3 -SiO 2 species ensure efficient exposure of the active component Ni species.
- the Al-O-Si structure formed by the Al 2 O 3 -SiO 2 layer has a specific surface acid property and can promote the hydrolysis of the cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran to 4-Hydroxybutyraldehyde is then hydroconverted to 1,4-butanediol under the catalysis of an adjacent high activity exposed hydrogenation site, Ni.
- the synergistic action of the acidic center and the hydrogenation active center in the catalyst achieves efficient conversion of the cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran, and finally reduces the cyclic acetal 2-(4'- The content of hydroxybutoxy)-tetrahydrofuran improves the product quality of 1,4-butanediol and achieves the purpose of reducing the color of the product.
- the Al 2 O 3 -SiO 2 layer is coated on the surface of alumina, which prevents the attack of water on the alumina carrier, inhibits the hydration and desorption structure of the carrier alumina, and effectively improves the hydrothermal stability of the catalyst in the aqueous system. , prolongs the life of the catalyst.
- Figure 1 is a schematic view showing the structure of a Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst of the present invention
- Figure 2 is an XRD pattern of the catalyst of the present invention.
- Figure 3 is an FT-IR diagram of the catalyst of the present invention.
- the preparation method of the Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst provided by the invention comprises the following steps:
- the Al 2 O 3 carrier is subjected to vacuum treatment at 100 ° C to 150 ° C for 10 min to 30 min, or directly at 100 ° C to 150 ° C for 1 h to 10 h, and then lowered to room temperature for use;
- step by step (3) 2 O 3 precursor NiO / Al In 2 O 3 taken 1000mL ⁇ 2000mL aluminum, silicon precursor per 100g Al ethanol - the amount of the aqueous solution of step (3) obtained NiO / Al 2
- the O 3 precursor is suspended in the solution prepared in the step (4), and stirred under reflux at 20 ° C to 60 ° C for 1 h to 24 h. After filtration, the mixture is washed three times with absolute ethanol, 0.01 M diluted nitric acid and deionized water. 5 times, the sample is dried at 80 ° C ⁇ 150 ° C for 2h ⁇ 24h, preferably 3h ⁇ 12h;
- the sample obtained in the step (5) is calcined in an air or nitrogen atmosphere, and is heated from 2 ° C / min to 10 ° C / min to 400 ° C to 550 ° C, at a constant temperature of 1 h to 24 h; The reduction was carried out at 350 ° C to 650 ° C for 1 h to 24 h under h to 2000/h; a Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst was obtained.
- Step (1) a specific surface area of the Al 2 O 3 was 110m 2 / g ⁇ 260m 2 / g, a pore volume of 0.5cm 3 /g ⁇ 1.3cm 3 / g.
- the nickel salt described in the step (2) is one selected from the group consisting of nickel nitrate, nickel sulfate or nickel chloride.
- the silicon precursor according to the step (4) is one of tetraethyl orthosilicate and methyl orthosilicate, preferably tetraethyl orthosilicate;
- the aluminum precursor is aluminum isopropoxide and aluminum n-butoxide.
- One of the aluminum nitrates is preferably aluminum nitrate;
- the ethanol-water solution has an ethanol:water molar ratio of 4 to 100:1.
- the application of the catalyst of the invention comprises the following steps:
- the catalyst is used for the catalytic synthesis of 1,4-butanediol by high-pressure hydrogenation of 1,4-butynediol, the water content of the raw material is 64wt%-72wt%, and the content of 1,4-butanediol in the organic phase is 90wt%-91.5wt%.
- the content of 1,4-butanediol in the organic phase after hydrogenation is 96.44 wt% to 97.76 wt. %; butanol content 1.3 wt% to 2.5 wt%; 4-hydroxybutyraldehyde content 0.03 wt% to 0.08 wt%; 1,4-butynediol content 0.01 to 0.05 wt%; 1,4-butenediol
- the content is 0.03 wt% to 0.07 wt%; the content of the cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran is 0.01 wt% to 0.03 wt%; the number of carbonyl groups is 0.03 mg (KOH) / g - 0.05 mg (KOH) ) / g.
- the catalyst can also be applied to direct hydroconversion of an aqueous solution containing 5% but not more than 5% by weight of 1,4-butynediol, using an external circulation hydrogenation reaction process, feeding mode: up and down; reaction conditions: The reaction temperature is 105 ° C to 150 ° C, the hydrogen pressure is 10 MPa to 22 MPa, the liquid space velocity is 1.0/h to 1.7 / h, and the cycle ratio is 18 to 22:1.
- the content of 1,4-butanediol in the organic phase of the hydrogenated product is ⁇ 96wt%, the butanol content of the by-product is ⁇ 1.2wt%, the unsaturated chromogenic material 1,4-butynediol, 1,4-butene
- the total content of diol, 4-hydroxybutanal, hemiacetal and acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran is ⁇ 0.06wt%, and the rest is macromolecular polymer.
- the carbonyl number of the material is 0.03mg. (KOH) / g ⁇ 0.05 mg (KOH) / g.
- the Al 2 O 3 carrier with a specific surface area of 110 m 2 /g and a pore volume of 0.5 cm 3 /g was vacuum treated at 100 ° C for 10 min, and then cooled to room temperature for use; nickel nitrate with a nickel content of 0.05 g/mL was prepared.
- aluminum isopropoxide and ethyl orthosilicate were weighed to prepare ethanol of aluminum and silicon precursor with a concentration of 0.0001 g/mL as Al 2 O 3 -SiO 2 .
- the aqueous solution, the ethanol-water solution has a molar ratio of ethanol:water of 4:1, and the pH of the aqueous solution is adjusted to 8.0 with ammonia water; before the preparation of the above-mentioned Al 2 O 3 : Ni mass ratio of 100:4 by NiO/Al 2 O 3
- the suspension was suspended in 1000 mL of aluminum and silicon precursor in ethanol-water solution, and stirred under reflux at 20 ° C for 1 h.
- the catalyst has a specific surface area of 105 m 2 /g and a pore volume of 0.45 cm 3 /g.
- the Ni particles are amorphous, and the Al 2 O 3 -SiO 2 layer forms Al-O-Si and is filled between the Ni particles.
- the catalyst number is 1#.
- the Al 2 O 3 carrier with a specific surface area of 110 m 2 /g and a pore volume of 0.5 cm 3 /g was vacuum treated at 150 ° C for 30 min, and then cooled to room temperature for use; a nickel sulfate having a nickel content of 0.2 g/mL was prepared.
- a nickel salt aqueous solution 130 mL of the above prepared nickel salt aqueous solution, impregnated onto 100 g of the aforementioned Al 2 O 3 support, allowed to stand for 120 min, heated to 150 ° C for 24 h; and calcined under nitrogen atmosphere at 10 ° C / min to 500 ° C, constant temperature 24 h; a NiO / Al 2 O 3 precursor having an Al 2 O 3 : Ni mass ratio of 100:26 was obtained.
- Al:Si molar ratio of 0.08:1 aluminum n-butoxide and methyl orthosilicate were weighed to prepare ethanol of aluminum and silicon precursor with a concentration of 0.0015 g/mL as Al 2 O 3 -SiO 2 -
- the molar ratio of ethanol to water in the aqueous solution, ethanol-water solution is 100:1, and the pH value is adjusted to 8.5 with ammonia water; before the preparation of NiO/Al 2 O 3 with a mass ratio of Al 2 O 3 : Ni of 100:26
- the suspension was suspended in 2000 mL of aluminum and silicon precursor in ethanol-water solution, and stirred under reflux at 60 ° C for 24 h.
- the Ni particles are present in a highly dispersed state on the surface of the carrier Al 2 O 3 , the grain size is 8 nm, and the Al 2 O 3 -SiO 2 layers An Al-O-Si bond is formed and filled between the Ni particles.
- the catalyst number is 2#.
- Al:Si molar ratio of 0.1:1 aluminum nitrate and methyl orthosilicate were weighed to prepare an ethanol-water solution of aluminum and silicon precursor with a concentration of 0.0001 g/mL as Al 2 O 3 -SiO 2 .
- the molar ratio of ethanol:water in the ethanol-water solution is 10:1, and the pH value is adjusted to 8.2 with ammonia water; the suspension of NiO/Al 2 O 3 with the mass ratio of Al 2 O 3 : Ni prepared above is 100: 4 .
- Ni-Al 2 O 3 @Al 2 O 3 -SiO 2 catalyst Al:Si molar in Al 2 O 3 -SiO 2 layer
- the ratio is 0.1:1
- the specific surface area of the catalyst is 245 m 2 /g
- the pore volume is 1.10 cm 3 /g.
- the Ni particles are present on the surface of the carrier Al 2 O 3 in an amorphous state, and the Al 2 O 3 -SiO 2 layer forms Al-O. -Si key, fill Filled between Ni particles.
- the catalyst number is 3#.
- the Al 2 O 3 carrier with a specific surface area of 160 m 2 /g and a pore volume of 0.75 cm 3 /g was heated in a 150 ° C blast oven for 10 h, and then cooled to room temperature for use; the nickel content was 0.10 g/mL.
- Nickel nitrate aqueous solution of nickel nitrate taking 95 mL of the above prepared nickel salt aqueous solution, immersed in 100 g of the above Al 2 O 3 carrier, allowed to stand for 80 min, heated to 120 ° C for 12 h; and calcined at 2 ° C / min in an air atmosphere The temperature was raised to 400 ° C and the temperature was kept at 5 h; a NiO/Al 2 O 3 precursor having an Al 2 O 3 : Ni mass ratio of 100:9.5 was obtained.
- Al:Si molar ratio of 0.05:1 aluminum isopropoxide and ethyl orthosilicate were weighed to prepare ethanol of aluminum and silicon precursor with a concentration of 0.0008 g/mL as Al 2 O 3 -SiO 2 -
- the molar ratio of ethanol to water in the aqueous solution, ethanol-water solution is 20:1, and the pH value is adjusted to 8.4 with ammonia water; before the preparation of NiO/Al 2 O 3 with a mass ratio of Al 2 O 3 : Ni of 100:9.5
- the suspension was suspended in an ethanol-water solution of 1300 mL of aluminum and silicon precursor, and stirred under reflux at 20 ° C for 24 h.
- the molar ratio is 0.05:1, the specific surface area of the catalyst is 145 m 2 /g, and the pore volume is 0.61 cm 3 /g.
- the Ni particles are present in a highly dispersed state on the surface of the carrier Al 2 O 3 with a grain size of 6.3 nm; Al 2 O 3 - SiO 2
- the layer forms an Al-O-Si bond and is filled between the Ni particles.
- the catalyst number is 4#.
- the Al 2 O 3 carrier having a specific surface area of 210 m 2 /g and a pore volume of 1.0 cm 3 /g was heated in a blast oven at 130 ° C for 5 h, and then cooled to room temperature for use; and nickel nitrate having a nickel content of 0.15 g/mL was prepared.
- An aqueous solution of nickel salt 110 mL of the above-prepared aqueous solution of nickel salt, impregnated onto 100 g of the above-mentioned Al 2 O 3 carrier, allowed to stand for 20 min, heated to 100 ° C for 3 h, and calcined in an air atmosphere at a temperature of 10 ° C / min to 500 °C, constant temperature 1h; a NiO/Al 2 O 3 precursor having an Al 2 O 3 : Ni mass ratio of 100:16.5 was obtained.
- Al:Si molar ratio of 0.07:1 aluminum n-butoxide and ethyl orthosilicate were weighed to prepare ethanol of aluminum and silicon precursor with a concentration of 0.0012 g/mL as Al 2 O 3 -SiO 2 -
- the molar ratio of ethanol to water in the aqueous solution, ethanol-water solution is 4:1, and the pH value is adjusted to 8.0 with ammonia water; before the preparation of NiO/Al 2 O 3 with a mass ratio of Al 2 O 3 : Ni of 100:16.5
- the suspension was suspended in 1700 mL of aluminum and silicon precursor in ethanol-water solution, and stirred under reflux at 20 ° C for 24 h.
- the catalyst structure was characterized by XRD, IR and XPS techniques using the above catalysts #1 to ##.
- the FT-IR chart of each catalyst is shown in Fig.
- the atomic ratio of Ni/Al before the introduction of the SiO 2 -Al 2 O 3 layer on the catalyst is very close to the atomic ratio of Ni/(Al + Si) after the introduction of SiO 2 -Al 2 O 3 , which is further determined.
- the introduced SiO 2 -Al 2 O 3 layer is selectively deposited on the surface of Al 2 O 3 to form a Si-O-Al bond, forming a cladding structure as shown in FIG.
- the catalyst is used for the catalytic synthesis of 1,4-butanediol by high-pressure hydrogenation of 1,4-butynediol, the water content of the raw material is about 64wt%-72wt%, and the content of 1,4-butanediol in the organic phase is 90wt%-91.5wt.
- the content of 1,4-butanediol in the organic phase after hydrogenation is 96.44 wt% to 97.76. Wt%; butanol content 1.3wt% to 2.5% by weight; 4-hydroxybutyraldehyde content 0.03wt% to 0.08wt%; 1,4-butynediol content 0.01wt% to 0.05wt%; 1,4-butyl
- the content of the olefinic diol is 0.03 wt% to 0.07 wt%; the content of the cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran is 0.01 wt% to 0.03 wt%; the number of carbonyl groups is 0.03 mg (KOH) / g - 0.05 Mg (KOH) / g.
- Table 2. The catalytic hydrogenation reaction conditions are shown in Table 3.
- the composition of the materials after hydrogenation evaluation of each catalyst is shown in Table 3.
- reaction condition reaction The temperature is from 105 ° C to 150 ° C, the hydrogen pressure is from 10 MPa to 22 MPa, the liquid space velocity is from 1.0/h to 1.7/h, and the cycle ratio is from 18 to 22:1.
- the content of 1,4-butanediol in the organic phase of the hydrogenated product is ⁇ 96wt%, the butanol content of the by-product is ⁇ 1.2wt%, the unsaturated chromogenic material 1,4-butynediol, 1,4-butene
- the total content of diol, 4-hydroxybutanal, hemiacetal and acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran is ⁇ 0.06wt%, and the rest is macromolecular polymer.
- the carbonyl number of the material is 0.03mg. (KOH) / g ⁇ 0.05 mg (KOH) / g.
- the specific reaction conditions and results are shown in Table 5.
- the Al-O-Si structure formed by the Al 2 O 3 -SiO 2 layer in the catalyst of the present invention has a specific surface acid property and can promote the cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran. Hydrolysis to 4-hydroxybutanal, followed by hydrogenation to 1,4-butanediol under the catalysis of adjacent high activity exposed hydrogenation center Ni.
- the synergistic action of the acidic center and the hydrogenation active center in the catalyst achieves efficient conversion of the cyclic acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran, and finally reduces the cyclic acetal 2-(4'- The content of hydroxybutoxy)-tetrahydrofuran improves the product quality of 1,4-butanediol and achieves the purpose of reducing the color of the product.
- the content of 1,4-butanediol in the organic phase of the hydrogenated product is ⁇ 96wt%, the butanol content of the by-product is ⁇ 1.2wt%, the unsaturated chromogenic material 1,4-butynediol, 1,4-butene
- the total content of diol, 4-hydroxybutanal, hemiacetal and acetal 2-(4'-hydroxybutoxy)-tetrahydrofuran is ⁇ 0.06wt%, and the rest is macromolecular polymer.
- the carbonyl number of the material is 0.03mg. (KOH) / g ⁇ 0.05 mg (KOH) / g.
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Abstract
一种包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂,其比表面积为98m 2/g~245m 2/g,孔容为0.25cm 3/g~1.1cm 3/g,载体Al 2O 3与活性组分Ni的质量比为Al 2O 3:Ni=100:4~26,载体Al 2O 3与包覆层Al 2O 3-SiO 2的质量比为Al 2O 3:Al 2O 3-SiO 2=100:0.1~3,包覆层Al 2O 3-SiO 2中Al:Si摩尔比为0.01~1,Ni颗粒以无定形或高分散状态存在于载体Al 2O 3表面,晶粒尺寸小于或等于8nm,填充于Ni颗粒之间。该催化剂具有制备简单,选择性好的优点。
Description
本发明属于一种包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂及制备方法及应用。
环状缩醛2-(4′-羟基丁氧基)-四氢呋喃是Reppe法1,4-丁炔二醇加氢制备1,4-丁二醇反应过程中难以避免的副产物,其本身无法通过直接加氢的方法脱除,而且与1,4-丁二醇形成共沸物,用常规的蒸馏法难以分离。缩醛2-(4′-羟基丁氧基)-四氢呋喃的残留严重影响1,4-丁二醇产品的纯度与色度,直接影响1,4-丁二醇品质及其在下游领域中的应用。
US6137016描述了一种通过加氢纯化含有少量环状缩醛2-(4′-羟基丁氧基)-四氢呋喃的1,4-丁二醇的方法,由于所使用加氢催化剂为通用型加氢催化剂,其加氢效果并不理想。CN 102145286 B公开了一种Ni-SiO
2/Al
2O
3催化剂及制备方法,该催化剂可有效实现环状缩醛2-(4′-羟基丁氧基)-四氢呋喃的水解、加氢转化,但其制备过程较为繁锁。
发明内容
本发明的目的是提供一种制备简单,选择性好的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂及制备方法和应用。
为了达到上述目的,本发明提供了一种包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂,催化剂中活性组分Ni颗粒以无定形或高分散状态存在于载体Al
2O
3表面,晶粒尺寸小于或等于8nm,载体Al
2O
3与包覆层Al
2O
3-SiO
2的质量比为Al
2O
3∶Al
2O
3-SiO
2=100∶0.1~3,包覆层Al
2O
3-SiO
2中Al∶Si摩尔比为0.01~0.1∶1,包覆层填充于Ni颗粒之间。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂,其中,所述催化剂比表面积优选为98m
2/g~245m
2/g,孔容优选为0.25cm
3/g~1.1cm
3/g,催化剂中载体Al
2O
3与活性组分Ni的质量比优选为Al
2O
3∶Ni=100∶4~26。
为了达到上述目的,本发明还提供了上述包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的一制备方法,包括以下步骤:
浸渍步骤:以浸渍法在Al
2O
3载体上引入活性组分Ni,Ni分布于氧化铝表面的四面体、八面体空穴,并以此为核生长成为微晶颗粒;
沉积步骤:在浸渍步骤中得到的Ni/Al
2O
3催化剂表面,以沉积的方式引入Al
2O
3-SiO
2层,Al
2O
3-SiO
2仅沉积在Ni颗粒间隙暴露的氧化铝表面;以及
洗涤步骤:沉积完成后的样品,经过洗涤,去除残留于催化剂表面的弱吸附组分。
为了达到上述目的,本发明还提供了上述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的另一制备方法,包括以下步骤:
(1)将Al
2O
3载体经100℃~150℃处理后降至室温备用;
(2)配制镍含量0.05g/mL~0.2g/mL的镍盐水溶液;
(3)按每100g Al
2O
3载体取80mL~130mL镍盐水溶液的比例,将步骤(2)配制的镍盐水溶液浸渍到步骤(1)的载体上,静置,烘干,焙烧,得到NiO/Al
2O
3前体;
(4)配制铝前驱物、硅前驱物的乙醇-水溶液,以Al
2O
3和SiO
2计,其总浓度为0.0001g/mL~0.0015g/mL,以氨水调节其pH值在8.0~8.5之间;其中Al∶Si摩尔比为0.01~0.1∶1;
(5)按步骤(3)NiO/Al
2O
3前体中每100g Al
2O
3取1000~2000mL铝前驱物、硅前驱物的乙醇-水溶液的量,将步骤(3)得到的NiO/Al
2O
3前体悬浮于步骤(4)配制的溶液中,恒温搅拌回流,过滤后分别以无水乙醇、稀硝酸、去离子水离心洗涤,烘干;
(6)将步骤(5)所得的样品焙烧,之后氢气还原,得到Ni-Al
2O
3@Al
2O
3-SiO
2催化剂。
为了达到上述目的,本发明还提供了上述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的更一制备方法,包括以下步骤:
(1)将Al
2O
3载体经100℃~150℃抽真空处理10min~30min,或直接在100℃~150℃加热1h~10h,后降至室温备用;
(2)配制镍含量0.05g/mL~0.2g/mL的镍盐水溶液;
(3)按每100g Al
2O
3载体取80mL~130mL镍盐水溶液的比例,将步骤(2)配制的镍盐水溶液浸渍到步骤(1)所述的载体上,静置20min~120min;然后升温至100℃~150℃烘干2h~24h,在空气或氮气气氛下焙烧,以2℃ /min~10℃/min升温至350℃~500℃,恒温1h~24h;得到NiO/Al
2O
3前体;(4)配制铝前驱物、硅前驱物的乙醇-水溶液,以Al
2O
3和SiO
2计,其总浓度为0.0001g/mL~0.0015g/mL,以氨水调节其pH值在8.0~8.5之间;其中Al∶Si摩尔比为0.01~0.1∶1;
(5)按步骤(3)NiO/Al
2O
3前体中每100g Al
2O
3取1000~2000mL铝前驱物、硅前驱物的乙醇-水溶液的量,将步骤(3)得到的NiO/Al
2O
3前体悬浮于步骤(4)配制的溶液中,于20℃~60℃恒温搅拌回流1h~24h,过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤3次~5次,样品于80℃~150℃烘干2h~24h;
(6)将步骤(5)所得的样品在空气或氮气气氛下焙烧,以2℃/min~10℃/min升温至400℃~550℃,恒温1h~24h;后经氢气在空速500/h~2000/h条件下于350℃~650℃还原1h~24h;得到Ni-Al
2O
3@Al
2O
3-SiO
2催化剂。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,其中,步骤(1)所述的Al
2O
3载体的比表面积优选为110m
2/g~260m
2/g,孔容优选为0.5cm
3/g~1.3cm
3/g。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,其中,步骤(2)所述镍盐水溶液中的镍盐优选为硝酸镍、硫酸镍或氯化镍中的一种。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,其中,步骤(3)所述的烘干时间优选为3h~12h。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,其中,步骤(3)中硅前驱物优选为正硅酸乙酯、正硅酸甲酯中的一种。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,其中,所述的硅前驱物进一步优选为正硅酸乙酯。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,其中,步骤(3)所述的铝前驱物优选为异丙醇铝、正丁醇铝、硝酸铝中的一种。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,其中,所述的铝前驱物进一步优选为硝酸铝。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,其中,步骤(3)所述的乙醇-水溶液中乙醇∶水的摩尔比优选为4~100∶1。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,其中,步骤 (5)所述的烘干时间优选为3h~12h。
为了达到上述目的,本发明更提供了上述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的应用,该催化剂用于1,4-丁炔二醇加氢催化合成1,4-丁二醇。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的应用,其中优选的是,包括如下步骤A:
催化剂用于1,4-丁炔二醇高压加氢催化合成1,4-丁二醇,原料中含水64wt%~72wt%;有机相中1,4-丁二醇含量90wt%~91.5wt%;丁醇含量1wt%~2wt%;4-羟基丁醛含量1.3wt%~1.8wt%;1,4-丁炔二醇含量1.5wt%~2wt%;1,4-丁烯二醇含量2.7wt%~3.2wt%;环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量0.8wt%~1.2wt%;羰基数:8mg(KOH)/g~12mg(KOH)/g,在反应温度100℃~150℃,压力10MPa~20MPa,空速1.1/h~1.7/h条件下进行加氢。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的应用,其中,步骤A加氢后有机相产品中1,4-丁二醇含量96.44wt%~97.76wt%;丁醇含量1.3wt%~2.5wt%;4-羟基丁醛含量0.03wt%~0.08wt%;1,4-丁炔二醇含量0.01~0.05wt%;1,4-丁烯二醇含量0.03wt%~0.07wt%;环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量0.01wt%~0.03wt%;羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的应用,其中优选的是,包括如下步骤B:
催化剂用于原料为含25wt%~35wt%的1,4-丁炔二醇的水溶液的直接加氢转化,采用外循环加氢反应工艺,进料方式:上进下出;反应条件:反应温度105℃~150℃,氢气压力10MPa~22MPa,液体空速1.0/h~1.7/h,循环比18~22∶1。
本发明所述的包覆Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的应用,其中,步骤B加氢后的物料有机相中1,4-丁二醇含量≥96wt%,副产物丁醇含量≤1.2wt%,不饱和生色物质总含量≤0.06wt%,其余为大分子聚合物,该物料羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。
本发明与现有技术相比具有的优点:
1、以浸渍法在氧化铝载体上引入活性组分Ni,Ni分布于氧化铝表面的四面体、八面体空穴,并以此为核生长成为微晶颗粒,该颗粒具有高的分散度。
2、在Ni/Al
2O
3催化剂表面,以沉积沉淀的方式引入Al
2O
3-SiO
2层,由于 SiO
2与NiO间不发生反应,且相互作用极弱,Al
2O
3-SiO
2仅沉积在NiO颗粒间隙暴露的氧化铝表面,随Al
2O
3-SiO
2含量的增加,当暴露的氧化铝表面全部被单层Al
2O
3-SiO
2覆盖后,将在暴露的单层Al
2O
3-SiO
2表面进一步生长二、三、四……层的Al
2O
3-SiO
2。
3、沉积完成后的样品,先后经过无水乙醇、0.01M的稀硝酸、去离子水洗涤,有效去除了嫁接过程中残留于催化剂表面的弱吸附组分,特别是在NiO表面弱吸附的Al
2O
3-SiO
2物种,保证了活性组分Ni物种的有效暴露。
4、传统催化剂制备过程中,由于NiO与Al
2O
3间强的相互作用,往往需要在较高的温度下才能将NiO还原为活性金属Ni,而高的还原温度又促使了金属Ni的迁移聚集,降低表面活性位点的数目,加氢活性也相应降低。本发明中,Al
2O
3-SiO
2层存在于NiO颗粒的间隙,通过限域效应可以有效阻止高温还原过程中金属Ni的迁移聚集,使活性金属镍保持高的分散度,从而使催化剂表现出高的加氢活性。
5、Al
2O
3-SiO
2层形成的Al-O-Si结构,使其具有了特定的表面酸性质,可以促使环状缩醛2-(4′-羟基丁氧基)-四氢呋喃水解为4-羟基丁醛,后在相邻高活性暴露加氢中心Ni的催化作用下加氢转化为1,4-丁二醇。该催化剂中酸性中心与加氢活性中心的协同作用,实现了环状缩醛2-(4′-羟基丁氧基)-四氢呋喃的高效转化,最终达到降低环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量,提高1,4-丁二醇的产品品质,达到降低产品色度的目的。
6、Al
2O
3-SiO
2层包覆于氧化铝表面,阻止了水对氧化铝载体的进攻,抑制了载体氧化铝的水合脱结构,有效提高了催化剂在含水体系中的水热稳定性,延长了催化剂使用寿命。
图1是本发明Ni-Al
2O
3@Al
2O
3-SiO
2催化剂结构示意图;
图2是本发明催化剂的XRD图;
图3是本发明催化剂的FT-IR图。
以下对本发明的实施例作详细说明:本实施例在以本发明技术方案为前提 下进行实施,给出了详细的实施方式和过程,但本发明的保护范围不限于下述的实施例,下列实施例中未注明具体条件的实验方法,通常按照常规条件。
本发明催化剂比表面积98m
2/g~245m
2/g,孔容0.25cm
3/g~1.1cm
3/g,催化剂中载体Al
2O
3与活性组分Ni的质量比为Al
2O
3∶Ni=100∶4~26,Ni颗粒以无定形或高分散状态存在于载体Al
2O
3表面,晶粒尺寸小于8nm,载体Al
2O
3与包覆层Al
2O
3-SiO
2的质量比为Al
2O
3∶Al
2O
3-SiO
2=100∶0.1~3,包覆层Al
2O
3-SiO
2中Al∶Si摩尔比为0.01~0.1∶1,填充于Ni颗粒之间。
本发明提供的Ni-Al
2O
3@Al
2O
3-SiO
2催化剂的制备方法,包括以下步骤:
(1)将Al
2O
3载体经100℃~150℃抽真空处理10min~30min,或直接在100℃~150℃加热1h~10h,后降至室温备用;
(2)配制镍含量0.05g/mL~0.2g/mL的镍盐水溶液;
(3)按每100g Al
2O
3载体取80mL~130mL镍盐水溶液的比例,将步骤(2)配制的镍盐水溶液浸渍到步骤(1)所述的载体上,静置20min~120min;然后升温至100℃~150℃烘干2h~24h,优选3h~12h;在空气或氮气气氛下焙烧,以2℃/min~10℃/min升温至350℃~500℃,恒温1h~24h;得到NiO/Al
2O
3前体;
(4)配制铝前驱物、硅前驱物的乙醇-水溶液,溶液中以Al
2O
3和SiO
2计,总浓度为0.0001g/mL~0.0015g/mL,以氨水调节其pH值在8.0~8.5之间;
(5)按步骤(3)NiO/Al
2O
3前体中每100g Al
2O
3取1000mL~2000mL铝、硅前驱物的乙醇-水溶液的量,将步骤(3)得到的NiO/Al
2O
3前体悬浮于步骤(4)配制的溶液中,于20℃~60℃恒温搅拌回流1h~24h,过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤3次~5次,样品于80℃~150℃烘干2h~24h,优选3h~12h;
(6)将步骤(5)所得的样品在空气或氮气气氛下焙烧,以2℃/min~10℃/min升温至400℃~550℃,恒温1h~24h;后经氢气在空速500/h~2000/h条件下于350℃~650℃还原1h~24h;得到Ni-Al
2O
3@Al
2O
3-SiO
2催化剂。
步骤(1)所述的Al
2O
3的比表面积为110m
2/g~260m
2/g,孔容为0.5cm
3/g~1.3cm
3/g。
步骤(2)所述的镍盐选自硝酸镍、硫酸镍或氯化镍中的一种。
步骤(4)所述的硅前驱物为正硅酸乙酯、正硅酸甲酯中的一种,优选正硅酸乙酯;所述的铝前驱物为异丙醇铝、正丁醇铝、硝酸铝中的一种,优选硝酸铝;所述的乙醇-水溶液中乙醇∶水的摩尔比为4~100∶1。
本发明催化剂的应用包括如下步骤:
催化剂用于1,4-丁炔二醇高压加氢催化合成1,4-丁二醇,原料中含水64wt%~72wt%,有机相中1,4-丁二醇含量90wt%~91.5wt%;丁醇含量1wt%~2wt%;4-羟基丁醛含量1.3wt%~1.8wt%;1,4-丁炔二醇含量1.5wt%~2wt%;1,4-丁烯二醇含量2.7wt%~3.2wt%;环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量0.8wt%~1.2wt%;羰基数:8mg(KOH)/g~12mg(KOH)/g,在反应温度100℃~150℃,压力10MPa~20MPa,空速1.1/h~1.7/h条件下进行加氢,经加氢后有机相中1,4-丁二醇含量96.44wt%~97.76wt%;丁醇含量1.3wt%~2.5wt%;4-羟基丁醛含量0.03wt%~0.08wt%;1,4-丁炔二醇含量0.01~0.05wt%;1,4-丁烯二醇含量0.03wt%~0.07wt%;环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量0.01wt%~0.03wt%;羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。
该催化剂也可适用于原料为含25wt%~35wt%的1,4-丁炔二醇的水溶液的直接加氢转化,采用外循环加氢反应工艺,进料方式:上进下出;反应条件:反应温度105℃~150℃,氢气压力10MPa~22MPa,液体空速1.0/h~1.7/h,循环比18~22∶1。加氢后的物料有机相中1,4-丁二醇含量≥96wt%,副产物丁醇含量≤1.2wt%,不饱和生色物质1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)-四氢呋喃等总含量≤0.06wt%,其余为大分子聚合物,该物料羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。
实施例1
(1)取比表面积为110m
2/g,孔容为0.5cm
3/g的Al
2O
3载体经100℃抽真空处理10min,后降至室温备用;配制镍含量0.05g/mL的硝酸镍水溶液;取80mL上述配制的镍盐水溶液,浸渍到100g前述的Al
2O
3载体上,静置20min,升温至100℃烘干2h;在空气气氛下焙烧以2℃/min升温至350℃,恒温1h;得到Al
2O
3∶Ni质量比为100∶4的NiO/Al
2O
3前体。
按Al∶Si摩尔比为0.01∶1,称取异丙醇铝与正硅酸乙酯,配制以Al
2O
3-SiO
2计算其浓度为0.0001g/mL的铝、硅前驱物的乙醇-水溶液,乙醇-水溶液中乙 醇∶水的摩尔比为4∶1,以氨水调节其pH值在8.0;取上述制备的Al
2O
3∶Ni质量比为100∶4的NiO/Al
2O
3前体悬浮于1000mL铝、硅前驱物的乙醇-水溶液中,20℃恒温搅拌回流1h,过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤3次,样品于80℃烘干2h;所得的样品置于焙烧炉中,在空气气氛下焙烧:以2℃/min升温至400℃,恒温1h;后经氢气在空速500/h条件于350℃还原1h;得到质量组成为Al
2O
3∶Al
2O
3-SiO
2∶Ni=100∶0.1∶4的Ni-Al
2O
3@Al
2O
3-SiO
2催化剂,其中Al
2O
3-SiO
2层中Al∶Si摩尔比为0.01∶1。该催化剂比表面积105m
2/g,孔容0.45cm
3/g,Ni颗粒以无定形,Al
2O
3-SiO
2层形成Al-O-Si,填充于Ni颗粒之间。该催化剂编号为1#。
实施例2
(1)取比表面积为110m
2/g,孔容为0.5cm
3/g的Al
2O
3载体经150℃抽真空处理30min,后降至室温备用;配制镍含量0.2g/mL的硫酸镍的镍盐水溶液;取130mL上述配制的镍盐水溶液,浸渍到100g前述的Al
2O
3载体上,静置120min,升温至150℃烘干24h;在氮气气氛下焙烧以10℃/min升温至500℃,恒温24h;得到Al
2O
3∶Ni质量比为100∶26的NiO/Al
2O
3前体。
按Al∶Si摩尔比为0.08∶1,称取正丁醇铝与正硅酸甲酯,配制以Al
2O
3-SiO
2计算其浓度为0.0015g/mL的铝、硅前驱物的乙醇-水溶液,乙醇-水溶液中乙醇∶水的摩尔比为100∶1,以氨水调节其pH值在8.5;取上述制备的Al
2O
3∶Ni质量比为100∶26的NiO/Al
2O
3前体悬浮于2000mL铝、硅前驱物的乙醇-水溶液中,60℃恒温搅拌回流24h,过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤5次,样品于150℃烘干24h;所得的样品置于焙烧炉中,在氮气气氛下焙烧:以10℃/min升温至550℃,恒温24h;后经氢气在空速2000/h条件下于650℃还原24h;得到质量组成为Al
2O
3∶Al
2O
3-SiO
2∶Ni=100∶3∶26的Ni-Al
2O
3@Al
2O
3-SiO
2催化剂,Al
2O
3-SiO
2层中Al∶Si摩尔比为0.08∶1,该催化剂比表面积98m
2/g,孔容0.25cm
3/g,Ni颗粒以高分散状态存在于载体Al
2O
3表面,晶粒尺寸8nm,Al
2O
3-SiO
2层形成Al-O-Si键,填充于Ni颗粒之间。该催化剂编号为2#。
实施例3
(1)取比表面积为260m
2/g,孔容为1.3cm
3/g的Al
2O
3载体100℃鼓风烘箱中加热1h,后降至室温备用;配制镍含量0.05g/mL的氯化镍的镍盐水 溶液;取80mL上述配制的镍盐水溶液,浸渍到100g前述的Al
2O
3载体上,静置80min,升温至120℃烘干3h;在空气气氛下焙烧以8℃/min升温至450℃,恒温18h;得到Al
2O
3∶Ni质量比为100∶4的NiO/Al
2O
3前体。
按Al∶Si摩尔比为0.1∶1,称取硝酸铝与正硅酸甲酯,配制以Al
2O
3-SiO
2计算其浓度为0.0001g/mL的铝、硅前驱物的乙醇-水溶液,乙醇-水溶液中乙醇∶水的摩尔比为10∶1,以氨水调节其pH值在8.2;取上述制备的Al
2O
3∶Ni质量比为100∶4的NiO/Al
2O
3前体悬浮于1000mL铝、硅前驱物的乙醇-水溶液中,40℃恒温搅拌回流12h,过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤4次,样品于150℃烘干3h;所得的样品置于焙烧炉中,在氮气气氛下焙烧:以8℃/min升温至500℃,恒温12h;后经氢气在空速1000/h条件下于550℃还原10h;得到质量组成为Al
2O
3∶Al
2O
3-SiO
2∶Ni=100∶0.1∶4的Ni-Al
2O
3@Al
2O
3-SiO
2催化剂,Al
2O
3-SiO
2层中Al∶Si的摩尔比为0.1∶1,该催化剂比表面积245m
2/g,孔容1.10cm
3/g,Ni颗粒以无定形状态存在于载体Al
2O
3表面,Al
2O
3-SiO
2层形成Al-O-Si键,填充于Ni颗粒之间。该催化剂编号为3#。
实施例4
(1)取比表面积为160m
2/g,孔容为0.75cm
3/g的Al
2O
3载体经150℃鼓风烘箱中加热10h,后降至室温备用;配制镍含量0.10g/mL的硝酸镍的镍盐水溶液;取95mL上述配制的镍盐水溶液,浸渍到100g前述的Al
2O
3载体上,静置80min,升温至120℃烘干12h;在空气气氛下焙烧以2℃/min升温至400℃,恒温5h;得到Al
2O
3∶Ni质量比为100∶9.5的NiO/Al
2O
3前体。
按Al∶Si摩尔比为0.05∶1,称取异丙醇铝与正硅酸乙酯,配制以Al
2O
3-SiO
2计算其浓度为0.0008g/mL的铝、硅前驱物的乙醇-水溶液,乙醇-水溶液中乙醇∶水的摩尔比为20∶1,以氨水调节其pH值在8.4;取上述制备的Al
2O
3∶Ni质量比为100∶9.5的NiO/Al
2O
3前体悬浮于1300mL铝、硅前驱物的乙醇-水溶液中,20℃恒温搅拌回流24h,过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤3次,样品于100℃烘干12h;所得的样品置于焙烧炉中,在氮气气氛下焙烧:以10℃/min升温至400℃,恒温1h;后经氢气在1500/h空速下于450℃还原24h;得到质量组成为Al
2O
3∶Al
2O
3-SiO
2∶Ni=100∶1.04∶9.5的Ni-Al
2O
3@Al
2O
3-SiO
2催化剂,Al
2O
3-SiO
2层中Al∶Si的摩尔比为0.05∶1,该催 化剂比表面积145m
2/g,孔容0.61cm
3/g,Ni颗粒以高分散状态存在于载体Al
2O
3表面,晶粒尺寸6.3nm;Al
2O
3-SiO
2层形成Al-O-Si键,填充于Ni颗粒之间。该催化剂编号为4#。
实施例5
取比表面积为210m
2/g,孔容为1.0cm
3/g的Al
2O
3载体经130℃鼓风烘箱中加热5h,后降至室温备用;配制镍含量0.15g/mL的硝酸镍的镍盐水溶液;取110mL上述配制的镍盐水溶液,浸渍到100g前述的Al
2O
3载体上,静置20min,升温至100℃烘干3h;在空气气氛下焙烧以10℃/min升温至500℃,恒温1h;得到Al
2O
3∶Ni质量比为100∶16.5的NiO/Al
2O
3前体。
按Al∶Si摩尔比为0.07∶1,称取正丁醇铝与正硅酸乙酯,配制以Al
2O
3-SiO
2计算其浓度为0.0012g/mL的铝、硅前驱物的乙醇-水溶液,乙醇-水溶液中乙醇∶水的摩尔比为4∶1,以氨水调节其pH值在8.0;取上述制备的Al
2O
3∶Ni质量比为100∶16.5的NiO/Al
2O
3前体悬浮于1700mL铝、硅前驱物的乙醇-水溶液中,20℃恒温搅拌回流24h,过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤5次,样品于80℃烘干3h;所得的样品置于焙烧炉中,在空气气氛下焙烧:以2℃/min升温至400℃,恒温1h;后经氢气在空速1500/h条件下于350℃还原1h;得到质量组成为Al
2O
3∶Al
2O
3-SiO
2∶Ni=100∶2.04∶16.5的Ni-Al
2O
3@Al
2O
3-SiO
2催化剂,Al
2O
3-SiO
2层中Al∶Si的摩尔比为0.07∶1,该催化剂比表面积183m
2/g,孔容0.85cm
3/g,Ni颗粒以高分散状态存在于载体Al
2O
3表面,晶粒尺寸7.5nm;Al
2O
3-SiO
2层形成Al-O-Si键,填充于Ni颗粒之间。该催化剂编号为5#。
取上述1#~5#号催化剂借助XRD、IR及XPS技术对催化剂结构进行表征。还原后催化剂的XRD图示于图2,所有催化剂在2θ=37°、46°和66.5°均出现弥散的γ-Al
2O
3特征衍射峰,2θ=44.5°、51.7°和76.4°处出现金属Ni的特征峰。采用2θ=51.7°处的Ni(200)晶面衍射峰的半高宽,利用Scherrer公式计算Ni晶粒尺寸,列于表1,可以看出,Ni物种高度分散,晶粒尺寸在8nm以下。各催化剂的FT-IR图示于图3,可以看出,在1024cm
-1处出现了新的红外吸收峰,归属为Si-O-Al键的振动吸收峰。这一结果表明,引入的SiO
2与Al
2O
3键合形成新的Si-O-Al键。进一步对催化剂进行了XPS分析,依据XPS数据计算得到了1#~5#催化剂表面的Ni/(Al+Si)原子比,为了对比,也计 算了未引入SiO
2-Al
2O
3层时,Ni/Al
2O
3催化剂中Ni/Al的原子比,结果列于表1。可以看出,催化剂上引入SiO
2-Al
2O
3层前的Ni/Al原子比,与引入SiO
2-Al
2O
3后的Ni/(Al+Si)的原子比极为接近,这进一步确定了引入的SiO
2-Al
2O
3层选择性沉积于Al
2O
3表面,形成Si-O-Al键,形成了如图1所示的包覆结构。
表1 Ni晶粒尺寸与表面Ni浓度
实施例6
催化剂用于1,4-丁炔二醇高压加氢催化合成1,4-丁二醇,原料中含水约64wt%~72wt%,有机相中1,4-丁二醇含量90wt%~91.5wt%;丁醇含量1wt%~2wt%;4-羟基丁醛含量1.3wt%~1.8wt%;1,4-丁炔二醇含量1.5wt%~2wt%;1,4-丁烯二醇含量2.7wt%~3.2wt%;环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量0.8wt%~1.2wt%;羰基数:8mg(KOH)/g~12mg(KOH)/g,在反应温度100℃~150℃,压力10MPa~20MPa,空速1.1/h~1.7/h条件下进行加氢,经加氢后有机相中1,4-丁二醇含量96.44wt%~97.76wt%;丁醇含量1.3wt%~2.5wt%;4-羟基丁醛含量0.03wt%~0.08wt%;1,4-丁炔二醇含量0.01wt%~0.05wt%;1,4-丁烯二醇含量0.03wt%~0.07wt%;环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量0.01wt%~0.03wt%;羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。各催化剂评价所用原料组成见表2,催化加氢反应条件见表3,各催化剂加氢评价后物料组成见表4。
表2 各催化剂评价所用原料组成
表3 催化加氢反应条件
表4 各催化剂加氢评价后物料组成
实施例7
取上述1#-5#号催化剂,以含25wt%~35wt%的1,4-丁炔二醇水溶液为原料,采用外循环加氢反应工艺,进料方式:上进下出;反应条件:反应温度105℃~150℃,氢气压力10MPa~22MPa,液体空速1.0/h~1.7/h,循环比18~22∶1。加氢后的物料有机相中1,4-丁二醇含量≥96wt%,副产物丁醇含量≤1.2wt%,不饱和生色物质1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)-四氢呋喃等总含量≤0.06wt%,其余为大分子聚合物,该物料羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。具体的反应条件及结果见表5。
表5 反应条件及加氢后物料组成
工业应用性
本发明催化剂中Al
2O
3-SiO
2层形成的Al-O-Si结构,使其具有了特定的表面酸性质,可以促使环状缩醛2-(4′-羟基丁氧基)-四氢呋喃水解为4-羟基丁醛,后在相邻高活性暴露加氢中心Ni的催化作用下加氢转化为1,4-丁二醇。该催化剂中酸性中心与加氢活性中心的协同作用,实现了环状缩醛2-(4′-羟基丁氧基)-四氢呋喃的高效转化,最终达到降低环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量,提高1,4-丁二醇的产品品质,达到降低产品色度的目的。
加氢后的物料有机相中1,4-丁二醇含量≥96wt%,副产物丁醇含量≤1.2wt%,不饱和生色物质1,4-丁炔二醇、1,4-丁烯二醇、4-羟基丁醛、半缩醛及缩醛2-(4′-羟基丁氧基)-四氢呋喃等总含量≤0.06wt%,其余为大分子聚合物,该物料羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。
当然,本发明还可有其它多种实施例,在不背离本发明精神及其实质的情况下,熟悉本领域的技术人员可根据本发明作出各种相应的改变和变形,但这些相应的改变和变形都应属于本发明权利要求的保护范围。
Claims (19)
- 一种包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂,其特征在于,催化剂中活性组分Ni颗粒以无定形或高分散状态存在于载体Al 2O 3表面,晶粒尺寸小于或等于8nm,载体Al 2O 3与包覆层Al 2O 3-SiO 2的质量比为Al 2O 3:Al 2O 3-SiO 2=100:0.1~3,包覆层Al 2O 3-SiO 2中Al:Si摩尔比为0.01~0.1:1,包覆层填充于Ni颗粒之间。
- 如权利要求1所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂,其特征在于,所述催化剂比表面积98m 2/g~245m 2/g,孔容0.25cm 3/g~1.1cm 3/g,催化剂中载体Al 2O 3与活性组分Ni的质量比为Al 2O 3:Ni=100:4~26。
- 权利要求1或2所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,包括以下步骤:浸渍步骤:以浸渍法在Al 2O 3载体上引入活性组分Ni,Ni分布于氧化铝表面的四面体、八面体空穴,并以此为核生长成为微晶颗粒;沉积步骤:在浸渍步骤中得到的Ni/Al 2O 3催化剂表面,以沉积的方式引入Al 2O 3-SiO 2层,Al 2O 3-SiO 2仅沉积在Ni颗粒间隙暴露的氧化铝表面;以及洗涤步骤:沉积完成后的样品,经过洗涤,去除残留于催化剂表面的弱吸附组分。
- 权利要求1或2所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,包括以下步骤:(1)将Al 2O 3载体经100℃~150℃处理后降至室温备用;(2)配制镍含量0.05g/mL~0.2g/mL的镍盐水溶液;(3)按每100g Al 2O 3载体取80mL~130mL镍盐水溶液的比例,将步骤(2)配制的镍盐水溶液浸渍到步骤(1)的载体上,静置,烘干,焙烧,得到NiO/Al 2O 3前体;(4)配制铝前驱物、硅前驱物的乙醇-水溶液,以Al 2O 3和SiO 2计,其总浓度为0.0001g/mL~0.0015g/mL,以氨水调节其pH值在8.0~8.5之间;其中Al:Si摩尔比为0.01~0.1:1;(5)按步骤(3)NiO/Al 2O 3前体中每100g Al 2O 3取1000~2000mL铝前驱物、硅前驱物的乙醇-水溶液的量,将步骤(3)得到的NiO/Al 2O 3前体悬浮于步骤(4)配制的溶液中,恒温搅拌回流,过滤后分别以无水乙醇、稀硝酸、 去离子水离心洗涤,烘干;(6)将步骤(5)所得的样品焙烧,之后氢气还原,得到Ni-Al 2O 3@Al 2O 3-SiO 2催化剂。
- 权利要求1或2所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,包括以下步骤:(1)将Al 2O 3载体经100℃~150℃抽真空处理10min~30min,或直接在100℃~150℃加热1h~10h,后降至室温备用;(2)配制镍含量0.05g/mL~0.2g/mL的镍盐水溶液;(3)按每100g Al 2O 3载体取80mL~130mL镍盐水溶液的比例,将步骤(2)配制的镍盐水溶液浸渍到步骤(1)所述的载体上,静置20min~120min;然后升温至100℃~150℃烘干2h~24h,在空气或氮气气氛下焙烧,以2℃/min~10℃/min升温至350℃~500℃,恒温1h~24h;得到NiO/Al 2O 3前体;(4)配制铝前驱物、硅前驱物的乙醇-水溶液,以Al 2O 3和SiO 2计,其总浓度为0.0001g/mL~0.0015g/mL,以氨水调节其pH值在8.0~8.5之间;其中Al:Si摩尔比为0.01~0.1:1;(5)按步骤(3)NiO/Al 2O 3前体中每100g Al 2O 3取1000~2000mL铝前驱物、硅前驱物的乙醇-水溶液的量,将步骤(3)得到的NiO/Al 2O 3前体悬浮于步骤(4)配制的溶液中,于20℃~60℃恒温搅拌回流1h~24h,过滤后分别以无水乙醇、0.01M的稀硝酸、去离子水离心洗涤3次~5次,样品于80℃~150℃烘干2h~24h;(6)将步骤(5)所得的样品在空气或氮气气氛下焙烧,以2℃/min~10℃/min升温至400℃~550℃,恒温1h~24h;后经氢气在空速500/h~2000/h条件下于350℃~650℃还原1h~24h;得到Ni-Al 2O 3@Al 2O 3-SiO 2催化剂。
- 如权利要求5所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,步骤(1)所述的Al 2O 3载体的比表面积为110m 2/g~260m 2/g,孔容为0.5cm 3/g~1.3cm 3/g。
- 如权利要求5所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,步骤(2)所述镍盐水溶液中的镍盐为硝酸镍、硫酸镍或氯化镍中的一种。
- 如权利要求5所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其 特征在于,步骤(3)所述的烘干时间为3h~12h。
- 如权利要求5所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,步骤(3)中硅前驱物为正硅酸乙酯、正硅酸甲酯中的一种。
- 如权利要求9所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,所述的硅前驱物为正硅酸乙酯。
- 如权利要求5所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,步骤(3)所述的铝前驱物为异丙醇铝、正丁醇铝、硝酸铝中的一种。
- 如权利要求11所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,所述的铝前驱物为硝酸铝。
- 如权利要求5所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,步骤(3)所述的乙醇-水溶液中乙醇:水的摩尔比为4~100:1。
- 如权利要求5所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的制备方法,其特征在于,步骤(5)所述的烘干时间为3h~12h。
- 权利要求1或2所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的应用,其特征在于,该催化剂用于1,4-丁炔二醇加氢催化合成1,4-丁二醇。
- 如权利要求15所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的应用,其特征在于,包括如下步骤:催化剂用于1,4-丁炔二醇高压加氢催化合成1,4-丁二醇,原料中含水64wt%~72wt%;有机相中1,4-丁二醇含量90wt%~91.5wt%;丁醇含量1wt%~2wt%;4-羟基丁醛含量1.3wt%~1.8wt%;1,4-丁炔二醇含量1.5wt%~2wt%;1,4-丁烯二醇含量2.7wt%~3.2wt%;环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量0.8wt%~1.2wt%;羰基数:8mg(KOH)/g~12mg(KOH)/g,在反应温度100℃~150℃,压力10MPa~20MPa,空速1.1/h~1.7/h条件下进行加氢。
- 如权利要求16所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的应用,其特征在于,加氢后有机相产品中1,4-丁二醇含量96.44wt%~97.76wt%;丁醇含量1.3wt%~2.5wt%;4-羟基丁醛含量0.03wt%~0.08wt%;1,4-丁炔二醇含量0.01~0.05wt%;1,4-丁烯二醇含量0.03wt%~0.07wt%;环状缩醛2-(4′-羟基丁氧基)-四氢呋喃含量0.01wt%~0.03wt%;羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。
- 如权利要求15所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的应用,其特征在于包括如下步骤:催化剂用于原料为含25wt%~35wt%的1,4-丁炔二醇的水溶液的直接加氢转化,采用外循环加氢反应工艺,进料方式:上进下出;反应条件:反应温度105℃~150℃,氢气压力10MPa~22MPa,液体空速1.0/h~1.7/h,循环比18~22:1。
- 如权利要求18所述的包覆Ni-Al 2O 3@Al 2O 3-SiO 2催化剂的应用,其特征在于,加氢后的物料有机相中1,4-丁二醇含量≥96wt%,副产物丁醇含量≤1.2wt%,不饱和生色物质总含量≤0.06wt%,其余为大分子聚合物,该物料羰基数:0.03mg(KOH)/g~0.05mg(KOH)/g。
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