CN117085684A - Catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation, preparation and application thereof - Google Patents
Catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation, preparation and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 107
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 title claims abstract description 63
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000013543 active substance Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 7
- 239000011734 sodium Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000004537 pulping Methods 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- 239000012065 filter cake Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 5
- 230000001276 controlling effect Effects 0.000 claims abstract description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 12
- 229920001223 polyethylene glycol Polymers 0.000 claims description 12
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 10
- 239000004115 Sodium Silicate Substances 0.000 claims description 7
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 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 4
- 230000032683 aging Effects 0.000 claims description 4
- 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 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229920002401 polyacrylamide Polymers 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 239000006227 byproduct Substances 0.000 abstract description 3
- 239000007789 gas Substances 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 8
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010009 beating Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- -1 sodium silicate pentahydrate Chemical class 0.000 description 3
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 229910000564 Raney nickel Inorganic materials 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- RWGFKTVRMDUZSP-UHFFFAOYSA-N cumene Chemical compound CC(C)C1=CC=CC=C1 RWGFKTVRMDUZSP-UHFFFAOYSA-N 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000000813 microbial effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- 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
- C07C29/143—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 ketones
- C07C29/145—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 ketones with hydrogen or hydrogen-containing gases
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation, a preparation method and application thereof. The method comprises the following steps: (1) Preparing a solution I comprising a nickel-containing salt, an aluminum-containing salt, an active agent and water and a solution II comprising a sodium-containing salt, a silicon-containing salt and water respectively; (2) Adding bottom water into the reaction kettle, regulating the pH value, and controlling the temperature of the reaction kettle; (3) Adding the solution I and the solution II in parallel, adjusting the flow to keep the pH value, and stirring for reaction after the parallel flow is finished; (4) After the reaction is finished, filtering and pulping, and performing first drying, crushing, forming, second drying and roasting on the obtained filter cake to obtain the nickel-based catalyst. The catalyst is suitable for the reaction of preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone, can greatly improve the treatment load of the catalyst, has higher activity, has high selectivity of alpha-phenethyl alcohol, and can effectively reduce the generation of byproducts.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation, a preparation method and application thereof.
Background
Alpha-phenethyl alcohol is an important chemical intermediate and is widely applied to the industries of medicines, spice manufacturing industry, foods, fine chemicals and the like. The existing method for synthesizing the alpha-phenethyl alcohol mainly comprises a plurality of methods such as natural extraction, microbial fermentation, organic synthesis and the like, wherein the sources of raw materials for the natural extraction are limited, the microbial fermentation is high in price, and the organic synthesis has the advantages of low production cost, few byproducts, high product yield, high product purity and the like.
The preparation of alpha-phenethyl alcohol by acetophenone hydrogenation has a plurality of side reactions, and has important application value in developing heterogeneous hydrogenation catalysts with high activity, high selectivity and easy separation. The hydrogenation catalyst mainly comprises noble metal catalysts such as platinum, palladium and rhodium and non-noble metal catalysts such as nickel and copper, and the non-noble metal catalysts have the advantage of low cost.
The catalyst for preparing the alpha-phenethyl alcohol by the hydrogenation of the acetophenone commonly used in the industry at present is a Raney nickel (Raney Ni) catalyst, the selectivity of the product alpha-phenethyl alcohol is only about 82 percent, and the hydrogenation selectivity can be improved to 89 percent by adding a proper amount of auxiliary Cr, but the heavy metal Cr has serious environmental pollution and increases the environmental protection pressure.
CN109529870a discloses a acetophenone hydrogenation catalyst and a preparation method thereof, wherein the catalyst adopts coprecipitation and extrusion molding methods to prepare a multicomponent catalyst containing 60-70wt% of copper oxide, 22-35wt% of silicon dioxide and simultaneously containing elements such as Mn, bi and Pb, and the like, and the multicomponent catalyst is used for catalyzing acetophenone hydrogenation reaction, and has the molar ratio of hydrogen to ketone of 2 at 80 ℃ and 2.5 MPa: 1 and liquid hourly space velocity of 0.3h -1 Under the condition that acetophenone conversion rate is highest99.3 percent of the catalyst, the selectivity of the alpha-phenethyl alcohol is 99.3 percent, but the catalyst has lower reaction load, the space-time yield of the product is low, and the production cost is high.
CN1557545A discloses an acetophenone hydrogenation amorphous nickel-boron catalyst and a preparation method thereof, wherein an impregnation method is adopted to prepare the amorphous catalyst (NiSn-B/SiO 2 ) By KBH 4 Or KBH 4 And B element is added to prepare the catalyst. When the catalyst is used for catalyzing acetophenone hydrogenation reaction, the selectivity of alpha-phenethyl alcohol can reach 97.5%, but the catalyst has complicated reduction steps and high cost.
CN115445629a discloses a catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation, a preparation method and application thereof, which adopts alumina as a carrier, cupric oxide as an active component and a catalyst prepared by using various rare metals as auxiliary agents, carries out selective hydrogenation reaction on acetophenone, wherein the reaction temperature is 72 ℃, the reaction raw material is a cumene solution of 25% alpha-acetophenone, and the molar ratio of hydrogen/alpha-acetophenone is 10 under the reaction pressure (gauge pressure) of 2 MPa: 1, liquid hourly space velocity of 0.4-0.8 g ACP ·g cat -1 ·h -1 The conversion rate of the alpha-acetophenone is over 98.5 percent, and the selectivity of the phenethyl alcohol is more than or equal to 99 percent. However, the catalyst has the problems of low operation load, large catalyst consumption and high production cost.
CN1911883a discloses a synthesis method of alpha-phenethyl alcohol, which adopts raney nickel as a catalyst and uses acetophenone, methanol and water as reaction raw materials according to a certain proportion. Under different proportions, the selectivity of the alpha-phenethyl alcohol can reach 94.3% at the highest, the acetophenone conversion rate is 72.38%, the conversion rate is lower, and the further improvement is needed.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation, and a preparation method and application thereof. The catalyst is suitable for the reaction of preparing alpha-phenethyl alcohol by selective hydrogenation of acetophenone, can greatly improve the treatment load of the catalyst, has higher activity, has high selectivity of alpha-phenethyl alcohol, and can effectively reduce the generation of byproducts.
The first aspect of the invention provides a preparation method of a catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation, which comprises the following steps:
(1) Preparing a solution I comprising a nickel-containing salt, an aluminum-containing salt, an active agent and water (preferably deionized water) and a solution II comprising a sodium-containing salt, a silicon-containing salt and water (preferably deionized water), respectively;
(2) Adding bottom water into the reaction kettle, regulating the pH value, and controlling the temperature of the reaction kettle;
(3) Adding the solution I and the solution II in parallel, adjusting the flow to maintain the pH value, and carrying out aging reaction under stirring after the parallel flow is finished;
(4) And after the reaction is finished, filtering and pulping, and performing first drying, crushing, forming, second drying and roasting on the obtained filter cake to obtain the catalyst.
In the present invention, in the step (1), the nickel-containing salt is at least one of nickel nitrate and nickel sulfate, preferably nickel nitrate; the aluminum-containing salt is at least one of aluminum nitrate and aluminum sulfate, and preferably aluminum nitrate; the sodium-containing salt is at least one of sodium carbonate and sodium bicarbonate, preferably sodium carbonate; the silicon-containing salt is at least one of sodium silicate and potassium silicate, preferably sodium silicate.
In the present invention, in the step (1), the active agent is at least one of polyvinyl alcohol (molecular weight 50000-150000), polyethylene glycol (molecular weight 2000-6000), methylcellulose, and polyacrylamide (molecular weight 500-1200 ten thousand).
In the present invention, in the step (1), preferably, the active agent includes both polyvinyl alcohol (molecular weight 50000-15000) and polyethylene glycol (molecular weight 2000-6000), and more preferably, the mass ratio of polyvinyl alcohol to polyethylene glycol is 1.0:0.5 to 1.5. In the invention, when the active agent adopts polyvinyl alcohol and polyethylene glycol simultaneously, the active agent has synergistic effect on improving the selectivity of alpha-phenethyl alcohol.
In the invention, in the solution I, the mass concentration of each substance is as follows: 10-20% of nickel-containing salt, 20-45% of aluminum-containing salt and 1-2% of active agent, wherein in the solution II, the mass concentration of each substance is as follows: 15-25% of sodium-containing salt and 1-10% of silicon-containing salt.
In the invention, in the step (1), the solution I or the solution II is preferably heated to 40-50 ℃ and stirred uniformly before being used.
In the invention, in the step (2), a proper amount of bottom water is added into the reaction kettle, for example, 1/10-1/5 of the effective volume of the kettle is occupied.
In the invention, in the step (2), the pH value is regulated to 7.0-10.0, preferably 8.0-10, and the temperature of the reaction kettle is controlled to be 60-95 ℃.
In the step (2), the pH value is regulated by adopting a sodium carbonate solution, and the mass concentration of the sodium carbonate solution is 10-20%.
In the invention, in the step (3), the parallel flow adding time of the solution I and the solution II is 1.5-2.5 h.
In the present invention, in the step (3), the flow rate is adjusted to maintain the pH value at 7.0 to 10.0, preferably at 8.0 to 10. After the parallel flow is finished, the temperature for aging reaction is 60-95 ℃ and the time is 1-3 hours under stirring.
In the step (4), the beating temperature is 60-95 ℃ and the beating time is 20-60 minutes each time.
In the present invention, in step (4), the beating is preferably carried out by filtration a plurality of times until the conductivity of the filtrate is <500ms/m.
In the present invention, in the step (4), the first drying condition is: drying at 100-120 deg.c for 5-8 hr; the second drying condition is that the drying is carried out for 5 to 8 hours at the temperature of 100 to 120 ℃; the conditions of the first drying and the second drying may be the same or different; the roasting conditions are as follows: the roasting temperature is 300-600 ℃, preferably 400-480 ℃; the calcination time is 4 to 8 hours, preferably 4 to 6 hours.
In the present invention, in the step (4), the molding is preferably extrusion molding. The extrusion is preferably carried out with the addition of a binder, such as a silicone binder.
In a second aspect, the present invention provides a catalyst prepared by the above method, said catalyst comprising the following components: 60 to 80wt% of alumina, 1 to 15wt% of silica, 10 to 39wt% of nickel (in terms of element), preferably 60 to 70wt% of alumina, 2 to 12wt% of silica, and 20 to 38wt% of nickel (in terms of element) based on the weight of the catalyst.
The third aspect of the invention provides an application of the catalyst prepared by the method in preparing alpha-phenethyl alcohol by acetophenone hydrogenation.
In the invention, the application is specifically as follows: adding a catalyst into a reactor, introducing acetophenone solution and hydrogen, wherein the reaction temperature is 40-120 ℃, the reaction pressure is 2-6 MPa, and the hydrogen volume space velocity is 100-2000 h -1 The volume space velocity of the reaction liquid is 1 to 20 hours -1 . Preferably, the reaction temperature is 60-90 ℃, the reaction pressure is 2-5 MPa, and the volume space velocity of the reaction liquid is 2.5-10 h -1 。
In the invention, the reactor is a fixed bed reactor. The center of the fixed bed reactor can be provided with a thermocouple for displaying the bed temperature, and the reaction temperature, the reaction pressure and the reaction liquid hourly space velocity are controlled by a program temperature controller. The catalyst is preferably filled in a constant temperature section of the catalyst, and the catalyst is introduced with H at 300-500 ℃ before being used 2 Reducing the gas of the catalyst for 3 to 8 hours and then cooling to the hydrogenation reaction temperature.
In the present invention, the reaction raw material is subjected to hydrogenation reaction in the presence of a solvent, and isopropanol is usually used as a solvent. Wherein the mass ratio of acetophenone to isopropanol is 1.5-2.5: 8.
compared with the prior art, the invention has the following advantages:
the catalyst has the advantages of simple preparation method and low raw material cost, can be used in the preparation of the alpha-phenethyl alcohol by acetophenone hydrogenation reaction, can greatly improve the treatment load of the catalyst, has higher activity, and has high selectivity.
Detailed Description
The following examples are given to illustrate the technical aspects of the present invention in detail, but the present invention is not limited to the following examples. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Example 1
Preparation of the catalyst:
(1) 150g of nickel nitrate hexahydrate, 500g of aluminum nitrate nonahydrate, 500g of water, 10g of polyvinyl alcohol (molecular weight 80000), 5g of polyethylene glycol (molecular weight 4000) were mixed and recorded as a solution I; 200g of sodium carbonate, 50g of sodium silicate pentahydrate and 800g of water are mixed and recorded as a solution II, the temperature is raised to 45 ℃ and stirred for half an hour;
(2) Adding 800g of water into a reaction kettle, stirring, adding 20wt% of sodium carbonate solution, adjusting the pH value to 8.0, keeping the temperature of the reaction kettle to 85 ℃, and stabilizing for 0.5h;
(3) Adding the solution I and the solution II in parallel, keeping the pH value at 8.0, adding the solution for 2 hours in parallel, keeping the temperature at 85 ℃ and stirring and ageing for 2 hours;
(4) Filtering and pulping for 3 times, wherein the pulping temperature is 80 ℃, the pulping time is 30 minutes each time, the filtrate is taken each time to measure the conductivity, and finally, the three-washing conductivity is kept to be less than 500ms/m; drying the finally obtained filter cake at 110 ℃ for 8 hours, and crushing the filter cake to powder of more than 100 meshes; 10g of silica gel containing 30wt% of silicon oxide and crushed particles are extruded and molded to obtain a strip-shaped catalyst, the catalyst is dried at 110 ℃ for 8 hours, and the dried catalyst is roasted in a muffle furnace at 450 ℃ for 4 hours to obtain a catalyst A. The catalyst A comprises the following components in percentage by weight: 61wt% of aluminum oxide, 9wt% of silicon oxide and 30wt% of nickel (calculated as element).
Application of the catalyst:
the catalyst A prepared above was used for preparing alpha-phenethyl alcohol by acetophenone hydrogenation, and 2mL of the catalyst (20-40 mesh) was charged into a stainless steel tube reactor.
H was used at a volumetric flow rate of 100mL/min under a pressure of 0.3MPa 2 And N 2 Mixture gas (95 v% H) 2 And 5v% N 2 ) Reducing; heating to 400 ℃ for constant-temperature reduction for 8 hours, and naturally cooling to finish the reduction process; switching H after evacuating the device gas 2 The hydrogen flow is 50mL/min, the reaction pressure is increased to 5MPa, acetophenone and isopropanol solution (the mass ratio of acetophenone to isopropanol is 2:8) is introduced, and the liquid volume space velocity is 2.5h -1 Slowly raise to 70 ℃, under the conditionThe acetophenone hydrogenation reaction was carried out to obtain p-alpha-phenethyl alcohol, the catalyst was evaluated, and the results obtained by analyzing the reaction condensate by a gas chromatograph are shown in table 1.
Example 2
Preparation of the catalyst:
the main difference compared with example 1 is that in the preparation of the solution I in the step (1), 100g of nickel nitrate hexahydrate was added, and the other steps were the same as in example 1. Catalyst B was obtained.
Based on the catalyst B, the catalyst B comprises the following components by weight: 68wt% of aluminum oxide, 12wt% of silicon oxide and 20wt% of nickel in terms of elements.
The conditions for the use of the catalyst were the same as in example 1, and catalyst B was evaluated, and the results obtained by analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Example 3
Preparation of the catalyst:
the difference compared to example 1 is only that the catalyst after drying in step (4) is calcined in a muffle furnace at 400 ℃ for 4 hours to give catalyst C comprising, on a weight basis: 61wt% of aluminum oxide, 9wt% of silicon oxide and 30wt% of nickel.
The conditions for the application of the catalyst were the same as in example 1, and the results of evaluating the catalyst C and analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Example 4
Preparation of the catalyst:
compared to example 1, the difference is mainly in step (1): in the preparation of solution I, 15g of polyvinyl alcohol (molecular weight 80000) was added, and polyethylene glycol was not added, and the other steps were the same as in example 1. Catalyst D was obtained.
Catalyst D comprises, on a weight basis: 61wt% of aluminum oxide, 9wt% of silicon oxide and 30wt% of nickel in terms of elements.
The conditions for the use of the catalyst were the same as in example 1, and the results of evaluating catalyst D and analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Example 5
Preparation of the catalyst:
compared to example 1, the difference is mainly in step (1): in the preparation of solution I, a solution containing 15g of polyethylene glycol (molecular weight 4000) was added without adding polyvinyl alcohol, and the procedure was the same as in example 1. Catalyst E was obtained.
Catalyst E comprises, by weight: 61wt% of aluminum oxide, 9wt% of silicon oxide and 30wt% of nickel in terms of elements.
The conditions for the use of the catalyst were the same as in example 1, and the results obtained by evaluating the catalyst E and analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Example 6
The same catalyst as that obtained in example 1 was used, except that the reaction temperature was lowered from 70℃to 60℃in the catalyst application. Other application conditions were the same as in example 1, and the results of evaluating the catalyst A and analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Example 7
The same catalyst as that obtained in example 1 was used, except that the reaction temperature was increased from 70℃to 80℃in the catalyst application. Other application conditions were the same as in example 1, and the results of evaluating the catalyst A and analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Example 8
The same catalyst as that obtained in example 1 was used, except that the space velocity of the reaction liquid at the time of the application of the catalyst was changed from 2.5 hours -1 Elevated for 5.0h -1 . Other application conditions were the same as in example 1, and the results of evaluating the catalyst A and analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Example 9
The same catalyst as that obtained in example 1 was used, except that the reaction pressure was changed from 5.0MPa to 4.0MPa. Other application conditions were the same as in example 1, and the results of evaluating the catalyst A and analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Example 10
Preparation of the catalyst:
compared to example 1, the difference is mainly in step (1): in the preparation of solution I, 150g of nickel nitrate hexahydrate, 500g of aluminum nitrate nonahydrate, 500g of water, 6g of polyvinyl alcohol (molecular weight 80000) and 9g of polyethylene glycol (molecular weight 4000) were added. The other steps were the same as in example 1. Catalyst F was obtained.
The catalyst F comprises, by weight: 61wt% of aluminum oxide, 9wt% of silicon oxide and 30wt% of nickel in terms of elements.
The conditions for the use of the catalyst were the same as in example 1, and the results of evaluating the catalyst F and analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Comparative example 1
Compared with example 1, the difference is mainly that step (1) is: 150g of nickel nitrate hexahydrate, 500g of aluminum nitrate nonahydrate and 500g of water were mixed and recorded as a solution I; 200g of sodium carbonate, 50g of sodium silicate pentahydrate and 800g of water were mixed and recorded as solution II, heated to 45℃and stirred for half an hour.
Other operating procedures were as in example 1 to give catalyst G comprising by weight: 61wt% of aluminum oxide, 9wt% of silicon oxide and 30wt% of nickel in terms of elements.
The conditions for the use of the catalyst were the same as in example 1, and catalyst G was evaluated, and the results obtained by analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Comparative example 2
Compared with example 1, the difference is mainly that step (1) is: 114g of copper nitrate hexahydrate, 500g of aluminum nitrate nonahydrate, 500g of water, 10g of polyvinyl alcohol (molecular weight 80000), 5g of polyethylene glycol (molecular weight 4000) were designated as solution I; 200g of sodium carbonate, 50g of sodium silicate pentahydrate and 800g of water are mixed and recorded as a solution II, the temperature is raised to 45 ℃ and stirred for half an hour;
the other procedure was as in example 1 to give catalyst H. The catalyst H comprises the following components in percentage by weight: 61wt% of aluminum oxide, 9wt% of silicon oxide and 30wt% of copper in terms of elements.
The conditions for the use of the catalyst were the same as in example 1, and catalyst H was evaluated, and the results obtained by analyzing the reaction condensate by a gas chromatograph are shown in Table 1.
Table 1 results of evaluation of catalysts
| Acetophenone conversion/% | Alpha-phenethyl alcohol selectivity/% | |
| Example 1 | 96.73 | 97.62 |
| Example 2 | 95.76 | 95.45 |
| Example 3 | 98.83 | 94.93 |
| Example 4 | 96.02 | 88.38 |
| Example 5 | 95.40 | 89.90 |
| Example 6 | 93.26 | 99.21 |
| Example 7 | 98.68 | 94.96 |
| Example 8 | 92.23 | 96.65 |
| Example 9 | 94.85 | 94.81 |
| Example 10 | 95.34 | 92.53 |
| Comparative example 1 | 99.32 | 75.32 |
| Comparative example 2 | 73.68 | 84.72 |
The above describes in detail the specific embodiments of the present invention, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A preparation method of a catalyst for preparing alpha-phenethyl alcohol by acetophenone hydrogenation is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing a solution I comprising a nickel-containing salt, an aluminum-containing salt, an active agent and water and a solution II comprising a sodium-containing salt, a silicon-containing salt and water respectively;
(2) Adding bottom water into the reaction kettle, regulating the pH value, and controlling the temperature of the reaction kettle;
(3) Adding the solution I and the solution II in parallel, adjusting the flow to maintain the pH value, and carrying out aging reaction under stirring after the parallel flow is finished;
(4) And after the reaction is finished, filtering and pulping, and performing first drying, crushing, forming, second drying and roasting on the obtained filter cake to obtain the catalyst.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the nickel-containing salt is at least one of nickel nitrate and nickel sulfate, preferably nickel nitrate; the aluminum-containing salt is at least one of aluminum nitrate and aluminum sulfate, and preferably aluminum nitrate; the sodium-containing salt is at least one of sodium carbonate and sodium bicarbonate, preferably sodium carbonate; the silicon-containing salt is at least one of sodium silicate and potassium silicate, preferably sodium silicate.
3. The method of manufacturing according to claim 1, characterized in that: in the step (1), the active agent is at least one of polyvinyl alcohol with the molecular weight of 50000-150000, polyethylene glycol, molecular weight of 2000-6000, methylcellulose and polyacrylamide with the molecular weight of 500-1200 ten thousand; the active agent preferably comprises polyvinyl alcohol and polyethylene glycol at the same time, and more preferably the mass ratio of the polyvinyl alcohol to the polyethylene glycol is 1.0:0.5 to 1.5.
4. The method of manufacturing according to claim 1, characterized in that: in the solution I, the mass concentration of each substance is as follows: 10-20% of nickel-containing salt, 20-45% of aluminum-containing salt and 1-2% of active agent, wherein in the solution II, the mass concentration of each substance is as follows: 15-25% of sodium-containing salt and 1-10% of silicon-containing salt.
5. The method of manufacturing according to claim 1, characterized in that: in the step (1), the temperature of the solution I or the solution II is raised to 40-50 ℃ before the use, and the solution I or the solution II is stirred uniformly.
6. The method of manufacturing according to claim 1, characterized in that: in the step (2), the pH value is regulated to 7.0-10.0, preferably 8.0-10.0, and the temperature of the reaction kettle is controlled to be 60-95 ℃.
7. The method of manufacturing according to claim 1, characterized in that: in the step (3), the parallel flow adding time of the solution I and the solution II is 1.5-2.5 h; and/or adjusting the flow rate to keep the pH value to be 7.0-10.0, preferably 8.0-10.0, and after the parallel flow is finished, carrying out aging reaction at the temperature of 60-95 ℃ for 1-3 hours under stirring.
8. The method of manufacturing according to claim 1, characterized in that: in the step (4), the first drying condition is: drying at 100-120 deg.c for 5-8 hr; the second drying condition is that the drying is carried out for 5 to 8 hours at the temperature of 100 to 120 ℃; the roasting conditions are as follows: the roasting temperature is 300-600 ℃, preferably 400-480 ℃; the calcination time is 4 to 8 hours, preferably 4 to 6 hours.
9. A catalyst prepared according to the preparation method of any one of claims 1 to 8, characterized in that: the catalyst comprises the following components: based on the weight of the catalyst, 60 to 80wt% of alumina, 1 to 15wt% of silicon oxide, 10 to 39wt% of nickel based on elements, preferably 60 to 70wt% of alumina, 2 to 12wt% of silicon oxide, and 20 to 38wt% of nickel based on elements.
10. Use of a catalyst prepared according to any one of the preparation methods of claims 1-8 or a catalyst according to claim 9 in the hydrogenation of acetophenone to produce alpha-phenethyl alcohol.
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