CN108722396B - A kind of preparation method of 5- hydroxyl -1-tetralone - Google Patents
A kind of preparation method of 5- hydroxyl -1-tetralone Download PDFInfo
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- CN108722396B CN108722396B CN201810540321.9A CN201810540321A CN108722396B CN 108722396 B CN108722396 B CN 108722396B CN 201810540321 A CN201810540321 A CN 201810540321A CN 108722396 B CN108722396 B CN 108722396B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- YPPZCRZRQHFRBH-UHFFFAOYSA-N 5-hydroxy-3,4-dihydro-2h-naphthalen-1-one Chemical compound O=C1CCCC2=C1C=CC=C2O YPPZCRZRQHFRBH-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 239000002077 nanosphere Substances 0.000 claims abstract description 80
- 239000003054 catalyst Substances 0.000 claims abstract description 75
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 67
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 66
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 66
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 66
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 66
- 239000002905 metal composite material Substances 0.000 claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000013528 metallic particle Substances 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 34
- 239000001257 hydrogen Substances 0.000 claims description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 16
- 150000002940 palladium Chemical class 0.000 claims description 15
- 239000012266 salt solution Substances 0.000 claims description 15
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 150000003388 sodium compounds Chemical class 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000004475 Arginine Substances 0.000 claims description 9
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 3
- 239000011806 microball Substances 0.000 claims description 3
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 239000011805 ball Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims 4
- ODKSFYDXXFIFQN-BYPYZUCNSA-P L-argininium(2+) Chemical compound NC(=[NH2+])NCCC[C@H]([NH3+])C(O)=O ODKSFYDXXFIFQN-BYPYZUCNSA-P 0.000 claims 2
- 230000001404 mediated effect Effects 0.000 claims 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims 1
- 239000004809 Teflon Substances 0.000 claims 1
- 229920006362 Teflon® Polymers 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000007853 buffer solution Substances 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 125000004494 ethyl ester group Chemical group 0.000 claims 1
- 238000003760 magnetic stirring Methods 0.000 claims 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims 1
- 235000012239 silicon dioxide Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 51
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000009903 catalytic hydrogenation reaction Methods 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000001802 infusion Methods 0.000 abstract 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 29
- 229910052763 palladium Inorganic materials 0.000 description 27
- 239000000047 product Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 239000000706 filtrate Substances 0.000 description 13
- 150000002431 hydrogen Chemical class 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- XHLHPRDBBAGVEG-UHFFFAOYSA-N 1-tetralone Chemical compound C1=CC=C2C(=O)CCCC2=C1 XHLHPRDBBAGVEG-UHFFFAOYSA-N 0.000 description 11
- 239000007791 liquid phase Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000001953 recrystallisation Methods 0.000 description 7
- 235000017550 sodium carbonate Nutrition 0.000 description 6
- 229940001593 sodium carbonate Drugs 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000003643 water by type Substances 0.000 description 5
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000009833 condensation Methods 0.000 description 4
- 230000005494 condensation Effects 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- 229910002666 PdCl2 Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- RZPFVRFSYMUDJO-UHFFFAOYSA-N 2h-naphthalen-1-one Chemical compound C1=CC=C2C(=O)CC=CC2=C1 RZPFVRFSYMUDJO-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- -1 5- methylol -1-tetralone 5- hydroxyl -1-tetralone Chemical compound 0.000 description 1
- GBIMFPWUXKRZHL-UHFFFAOYSA-N 5-(hydroxymethyl)-3,4-dihydro-2h-naphthalen-1-one Chemical compound O=C1CCCC2=C1C=CC=C2CO GBIMFPWUXKRZHL-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- IXHBTMCLRNMKHZ-LBPRGKRZSA-N levobunolol Chemical compound O=C1CCCC2=C1C=CC=C2OC[C@@H](O)CNC(C)(C)C IXHBTMCLRNMKHZ-LBPRGKRZSA-N 0.000 description 1
- 229960000831 levobunolol Drugs 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying 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
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/006—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydrogenation of aromatic hydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of nanosphere-metal composite catalysts, including SiO2Nanosphere and it is supported on SiO2The Pd metallic particles on nanosphere surface.Catalyst catalytic activity with higher and selectivity, being capable of efficient catalytic hydrogenation；The present invention also provides the preparation methods of the catalyst, and catalyst of the invention can be prepared by infusion process, and preparation method is simple, easy to operate, at low cost；Using nanosphere provided by the invention-metal composite catalyst catalysis 1,5- dihydroxy naphthlene hydrogenation, reaction selectivity is high, 5- hydroxyl -1-tetralone high income.
Description
Technical field
The present invention relates to the technical field of medicine intermediate, in particular to a kind of nanosphere-metal composite catalyst and
Preparation method and a kind of 5- hydroxyl -1-tetralone preparation method.
Background technique
5- hydroxyl -1-tetralone is a kind of important medicine intermediate, is widely used in the doctor such as Levobunolol Hydrochorid
In the synthesis of medicine.Hydroxyl -1- tetrahydro can be made by the oxidation to raw material 1,2,3,4- tetrahydro -1- naphthalenone in existing preparation method
Naphthalenone, but reaction requires to carry out in the presence of a peroxide；It can also hydrolyze to obtain by 5- methylol -1-tetralone
5- hydroxyl -1-tetralone, but reaction raw materials 5- methylol -1- tetralone itself is not readily synthesized.
It is more universal that 5- hydroxyl -1-tetralone method is prepared by the reduction to 1,5- bisnaphthol, wherein has 1
Russian document [Russian Journal ofOrganic Chemistry 2000,36,1474] and 1 Russian patent are reported respectively
Road lewis acid reduction [Russian patent 2356883,2009], but reaction process needs to use a large amount of alchlor
And alchlor, and all do not refer in paper and patent using which kind of reducing agent.Also by Metal Palladium or nickel catalytic hydrogenation
Original, the feasible and process of reaction is more green, and still, due to raw material 1,5- bisnaphthol and product 5- hydroxyl -1-tetralone exist
Over reduction reaction is all easy to happen under catalytic hydrogenation conditions, so reaction process is selectively poor, yield is no more than 60%.
Summary of the invention
In view of this, it is an object of that present invention to provide a kind of catalytic activity, nanosphere-metal good, that selectivity is high is multiple
Catalyst is closed, 5- hydroxyl -1- naphthane can be improved using the catalyst with efficient catalytic 1, the hydro-reduction of 5- bisnaphthol hydrogenation
The yield of ketone.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
A kind of nanosphere-metal composite catalyst, including SiO2Nanosphere and it is supported on SiO2Nanosphere surface
Pd metallic particles.
Preferably, the SiO2The partial size of nanosphere is 30~300nm.
Preferably, the Pd metallic particles is in SiO2The load capacity on nanosphere surface is 3~10wt%.
The present invention provides nanosphere-metal composite catalyst preparation methods described in above scheme, including following step
It is rapid:
By SiO2Nanosphere is impregnated in palladium salt solution, is obtained immersed with SiO2The palladium salt solution of nanosphere；
It will be immersed with SiO2The palladium salt solution of nanosphere is heated to doing, and obtains SiO2Nanosphere-palladium salt compound；
By the SiO2Nanosphere-palladium salt compound carries out hydrogen reducing, obtains nanosphere-metal composite catalysis
Agent.
Preferably, the temperature of the hydrogen reducing is 300~400 DEG C；The time of the hydrogen reducing is 3~5h.
The present invention provides preparation methods described in nanosphere-metal composite catalyst described in above scheme or above scheme
Application of the nanosphere-metal composite catalyst of preparation in catalytic hydrogenation.
The present invention provides a kind of using described in nanosphere-metal composite catalyst or above scheme described in above scheme
Nanosphere-metal composite catalyst of preparation method preparation prepares 5- hydroxyl -1-tetralone method, including following step
It is rapid:
Hydrogen is passed through after 1,5- dihydroxy naphthlene, inorganic sodium compound, nanosphere-metal composite catalyst and solvent are mixed
Gas carries out hydrogenation, obtains 5- hydroxyl -1-tetralone.
Preferably, the quality of the nanosphere-metal composite catalyst is the 1~10% of 1,5- dihydroxy naphthlene quality.
Preferably, the inorganic sodium compound includes sodium hydroxide, sodium chloride, sodium carbonate, sodium sulphate, sodium bisulfate, carbon
The mixture of one or more of sour hydrogen sodium and sodium methoxide；
The quality of the inorganic sodium compound is the 0.05~10% of 1,5- dihydroxy naphthlene quality.
Preferably, the pressure of the hydrogenation is 3~40Kg；
The temperature of the hydrogenation is 60~170 DEG C；
The time of the hydrogenation is 1.5~15h.
The present invention provides a kind of nanosphere-metal composite catalysts, including SiO2Nanosphere and it is supported on SiO2It receives
The Pd metallic particles of rice microsphere surface.Nanosphere-metal composite catalyst provided by the invention is with SiO2Nanosphere is to carry
Body, SiO2Nanosphere have the characteristics that regular appearance orderly, large specific surface area, thus catalyst provided by the invention have compared with
High catalytic activity and selectivity；Catalyst provided by the invention can efficient catalytic hydrogenation, and regenerating easily, Ke Yiyou
Effect reduces the loss of raw material and the energy.
5- hydroxyl -1-tetralone side is prepared using nanosphere-metal composite catalyst the present invention provides a kind of
Method, comprising the following steps: mix 1,5- dihydroxy naphthlene, inorganic sodium compound, nanosphere-metal composite catalyst and solvent
After be passed through hydrogen carry out hydrogenation, obtain 5- hydroxyl -1-tetralone.The present invention is catalyzed using nanosphere-metal composite
Agent is catalyzed the hydrogenation of 1,5- dihydroxy naphthlene, and reaction selectivity is high, 5- hydroxyl -1-tetralone high income.Embodiment knot
Fruit shows that 5- hydroxyl -1-tetralone purity of preparation method preparation provided by the invention is greater than 99%, and yield is up to
84.2%.
Detailed description of the invention
Fig. 1 is 200 Nano-meter SiO_2s prepared by the embodiment of the present invention 12The TEM of microballoon schemes；
Fig. 2 is 5%Pd/SiO prepared by the embodiment of the present invention 22The TEM of 200 nanosphere catalyst schemes.
Specific embodiment
The present invention provides a kind of nanosphere-metal composite catalysts, including SiO2Nanosphere and it is supported on SiO2It receives
The Pd metallic particles of rice microsphere surface.
In the present invention, the SiO2The partial size of nanosphere is preferably 30~300nm, more preferably 50~250nm,
Most preferably 100~200nm；The SiO2The specific surface area of nanosphere is preferably 20~150m2/ g, more preferably 50~
80m2/g；The partial size of the Pd metallic particles is preferably 10~100nm, more preferably 20~50nm；The Pd metallic particles exists
SiO2The load capacity on nanosphere surface is preferably 3~10wt%, more preferably 5~8wt%.Catalyst provided by the invention
With SiO2Nanosphere is carrier, has the characteristics that specific surface is big and regular appearance is orderly, thus catalyst provided by the invention
Catalytic activity and selectivity with higher.
The present invention provides nanosphere-metal composite catalyst preparation methods described in above scheme, including following step
It is rapid:
By SiO2Nanosphere is impregnated in palladium salt solution, is obtained immersed with SiO2The palladium salt solution of nanosphere；
It will be immersed with SiO2The palladium salt solution of nanosphere is heated to doing, and obtains SiO2Nanosphere-palladium salt compound；
By the SiO2Nanosphere-palladium salt compound carries out hydrogen reducing, obtains nanosphere-metal composite catalysis
Agent.
The present invention is by SiO2Nanosphere is impregnated in palladium salt solution, is obtained immersed with SiO2The palladium salt solution of nanosphere.
The present invention is to the SiO2The source of nanosphere does not have particular/special requirement, uses method system well known to those skilled in the art
It is standby, in a specific embodiment of the present invention, preferably according to Ryota Watanabe, Toshiyuki et
al.Extension of size of monodisperse silica nanospheres and their well-
Ordered assembly [J] .Journal of Colloid and Interface Science, 360 (2011): 1~7.
Disclosed in technical solution preparation.
In the present invention, the palladium salt solution is preferably palladium chloride solution or palladium nitrate solution, and more preferably palladium chloride is molten
Liquid；The concentration of the palladium salt solution is preferably 0.02~0.06mol/L, more preferably 0.05mol/L；The SiO2Nanometer is micro-
The mass ratio of ball and palladium salt solution is preferably 1:14~18, more preferably 1:16；The time of the immersion is preferably 0.5~1h,
More preferably 0.6~0.8h；The present invention preferably impregnates at room temperature, without carrying out additional heating or cooling.
After the completion of immersion, the present invention will be immersed with SiO2The palladium salt solution of nanosphere is heated to doing, and obtains SiO2Nanometer
Microballoon-palladium salt compound.In the present invention, the temperature of the heating is preferably 200~300 DEG C, and more preferably 250~280 DEG C；
Solvent in solution can be passed through completely heating removal to dry required time is heated to without particular/special requirement by the present invention,
In specific embodiments of the present invention, the time of the heating is preferably 2~3h；The present invention preferably adds under agitation
Heat, the revolving speed of the stirring are preferably 200~800rpm, more preferably 500rpm.
Be heated to it is dry after, the present invention is by the SiO2Nanosphere-palladium salt compound carries out hydrogen reducing, is received
Meter Wei Qiu-metal composite catalyst.In the present invention, the temperature of the hydrogen reducing is preferably 300~400 DEG C, more preferably
330~380 DEG C；The time of the hydrogen reducing is preferably 3~5h, more preferably 4h.The present invention will be adhered to by hydrogen reducing
In SiO2The palladium ion on nanosphere surface is reduced to porpezite metal particles.
The present invention provides preparation methods described in nanosphere-metal composite catalyst described in above scheme or above scheme
Application of the nanosphere-metal composite catalyst of preparation in catalytic hydrogenation.Nanosphere-metal provided by the invention
Composite catalyst catalytic activity is high, and selectivity with higher can be used for efficient catalytic hydrogenation.
The present invention provides a kind of using described in nanosphere-metal composite catalyst or above scheme described in above scheme
Nanosphere-metal composite catalyst of preparation method preparation prepares 5- hydroxyl -1-tetralone method, including following step
It is rapid:
Hydrogen is passed through after 1,5- dihydroxy naphthlene, inorganic sodium compound, nanosphere-metal composite catalyst and solvent are mixed
Gas carries out hydrogenation, obtains 5- hydroxyl -1-tetralone.
In the present invention, the inorganic sodium compound preferably includes sodium hydroxide, sodium chloride, sodium carbonate, sodium sulphate, sulfuric acid
The mixture of one or more of hydrogen sodium, sodium bicarbonate and sodium methoxide；The quality of the inorganic sodium compound is preferably 1,5-
The 0.05~10% of dihydroxy naphthlene quality, the 2~8% of more preferably 1,5- dihydroxy naphthlene quality.The present invention is inorganic by being added
Sodium compound further increases the selectivity of hydrogenation.
In the present invention, the solvent is preferably methanol, ethyl alcohol, acetone, hexamethylene, in ethyl acetate and tetrahydrofuran
One or more of mixtures, more preferably methanol, ethyl alcohol or acetone；The mass ratio of the solvent and 1,5- dihydroxy naphthlene is preferred
For 5~15:1, more preferably 8~12:1.
In the present invention, the nanosphere-metal composite catalyst quality be preferably 1,5- dihydroxy naphthlene quality 1~
The 3~8% of 10%, more preferably 1,5- dihydroxy naphthlene quality.
In the present invention, the pressure of the hydrogenation is preferably 3~40Kg, more preferably 10~30Kg, and the present invention is logical
Cross the pressure of the intake control reaction of control hydrogen；The temperature of the hydrogenation is preferably 60~170 DEG C, more preferably
100~150 DEG C；The time of the hydrogenation is preferably 1.5~15h, more preferably 5~10h.The present invention is preferably anti-in high pressure
It answers and carries out hydrogenation in kettle, the present invention does not have particular/special requirement to the volume of the autoclave, in specific reality of the invention
It applies in example, the volume of reaction kettle is preferably determined according to the dosage of reaction raw materials.
After the completion of hydrogenation, the present invention preferably post-processes hydrogenation liquid, obtains 5- hydroxyl -1- naphthane
Ketone.In the present invention, the post-processing preferably includes following steps:
Hydrogenation liquid is filtered, filtrate is obtained；
The filtrate is distilled, crude product is obtained；
Will be dry after crude product recrystallization, obtain 5- hydroxyl -1-tetralone.
The present invention does not have particular/special requirement to the specific method of the filtering, uses filtering side well known to those skilled in the art
Method, it is specific as filtered；The present invention does not have particular/special requirement to the specific method of the distillation, uses those skilled in the art
Well known distillating method can completely remove the solvent in filtrate, specific such as rotary evaporation.
In the present invention, the recrystallization is preferably the mixed solution of isopropyl alcohol and water with solvent, in the mixed solution
The volume ratio of isopropyl alcohol and water is preferably 1~5:1, more preferably 3:1；The present invention does not have special want to the specific method of recrystallization
It asks, is recrystallized using method well known to those skilled in the art.
In the present invention, the temperature of the drying is preferably 60~130 DEG C, and the time of the drying is preferably 80 DEG C, institute
State dry preferably vacuum drying.
In the present invention, the nanosphere-metal composite catalyst can be separated from reaction solution by filtering, point
It is reusable after catalyst regeneration from after；Catalyst after separation is preferably successively carried out high-temperature oxydation and hydrogen by the present invention
Reduction, to complete the regeneration of catalyst；In the present invention, the temperature of the high-temperature oxydation is preferably 300~600 DEG C, more preferably
It is 450 DEG C, the time of the high-temperature oxydation is preferably 1~6h, more preferably 3h；The temperature of the hydrogen reducing is preferably 50
~300 DEG C, more preferably 150 DEG C, the time of the hydrogen reducing is preferably 1~3h, more preferably 2h.
Below with reference to embodiment to nanosphere-metal composite catalyst provided by the invention and its preparation method and application
And 5- hydroxyl -1-tetralone preparation method is described in detail, but they cannot be interpreted as protecting the present invention
Protect the restriction of range.
Embodiment 1
SiO2The preparation of nanosphere seed:
It weighs 0.1756 gram of arginine to be placed in 250mL round-bottomed flask, is added 170.05 grams of deionized waters, after stirring and dissolving
It is added 10.4139 grams of tetraethyl orthosilicates, heating reaches 70 DEG C, and holdings revolving speed is 460rpm, and flask is suitable for reading plus plug, and 70 DEG C
It is stirred 24 hours under oil bath.It is transferred to after having reacted in the water heating kettle of 1000 mL polytetrafluoroethylliner liners, the water in 100 DEG C of baking ovens
Heat 20 hours.It is then transferred to opening in crystallising dish and is put into 100 DEG C of drying in baking oven, 600 DEG C of roastings in Muffle furnace are put into after drying
It burns 4 hours, obtains SiO2Nanosphere seed, the filament shape that product is translucent.
200 Nano-meter SiO_2s2The preparation of microballoon:
It weighs 41.4 grams of deionized waters to be placed in 250mL round-bottomed flask, 0.1360 gram of seed solution, 133.6 grams of second is added
10.41 grams of tetraethyl orthosilicates are added after dissolution is stirred at room temperature in alcohol, 0.2613 gram of arginine, and heating reaches 70 DEG C.Keep revolving speed be
460rpm, flask is suitable for reading to add spherical condensation tube, stirs 24 hours under 70 DEG C of oil baths.Flask is taken out after having reacted, and is transferred to knot
Opening, which is put into baking oven, in brilliant ware dries, and is put into Muffle furnace and roasts 4 hours after drying for 600 DEG C, obtains 200 Nano-meter SiO_2s2It is micro-
Ball.The white sheet of product.
100 Nano-meter SiO_2s2The preparation of microballoon:
It weighs 41.4 grams of deionized waters to be placed in 250mL round-bottomed flask, 0.5230 gram of seed solution, 133.6 grams of second is added
10.39 grams of tetraethyl orthosilicates are added after dissolution is stirred at room temperature in alcohol, 0.1742 gram of arginine, and heating reaches 70 DEG C.Keep revolving speed be
460rpm, flask is suitable for reading to add spherical condensation tube, stirs 24 hours under 70 DEG C of oil baths.Flask is taken out after having reacted, and is transferred to knot
Opening, which is put into baking oven, in brilliant ware dries, and is put into Muffle furnace and roasts 4 hours after drying for 600 DEG C, obtains 100 Nano-meter SiO_2s2It is micro-
Ball.The white sheet of product.
30 Nano-meter SiO_2s2The preparation of microballoon:
It weighs 49.05 grams of deionized waters to be placed in 250mL round-bottomed flask, 10.30 grams of seed solutions, 125.5 grams of second is added
4.69 grams of tetraethyl orthosilicates are added after dissolution is stirred at room temperature in alcohol, 0.1742 gram of arginine, and heating reaches 70 DEG C.Keep revolving speed be
460rpm, flask is suitable for reading to add spherical condensation tube, stirs for 24 hours under 70 DEG C of oil baths.Flask is taken out after having reacted, and is transferred to crystallising dish
Middle opening, which is put into baking oven, dries, and is put into Muffle furnace and roasts 4 hours after drying for 600 DEG C, obtains 30 Nano-meter SiO_2s2Microballoon.Product
White sheet.
300 Nano-meter SiO_2s2The preparation of microballoon:
It weighs 41.4 grams of deionized waters to be placed in 250mL round-bottomed flask, 0.0354 gram of seed solution, 133.6 grams of second is added
10.41 grams of tetraethyl orthosilicates are added after dissolution is stirred at room temperature in alcohol, 0.2613 gram of arginine, and heating reaches 70 DEG C.Keep revolving speed be
460rpm, flask is suitable for reading to add spherical condensation tube, stirs for 24 hours under 70 DEG C of oil baths.Flask is taken out after having reacted, and is transferred to crystallization
Opening is put into baking oven and dries in ware, is put into Muffle furnace and roasts 4 hours after drying for 600 DEG C, obtains 300 Nano-meter SiO_2s2Microballoon.
The white sheet of product.
Embodiment 2
(1) 5%Pd/SiO2The preparation of 200 nanosphere catalyst:
Weigh 200 Nano-meter SiO_2s of the preparation of embodiment 12It 2.0 grams of nanosphere, is added 10 grams and contains 167 milligrams of PdCl2Solution,
By mixed liquor heating stirring to dry, the SiO that will be obtained after immersion 0.5h2Nanosphere-palladium salt compound is cooled to room temperature, most
Afterwards by dry SiO2Nanosphere-palladium salt compound leads to hydrogen reducing 4 hours under the conditions of 350 DEG C, and Pd load capacity is made and is
5% nanosphere-metal composite catalyst (5%Pd/SiO2200 nanosphere catalyst).
Using scanning electron microscope to 200 Nano-meter SiO_2s2Nanosphere is observed, and acquired results are as shown in Figure 1, can according to Fig. 1
To find out, gained SiO2Nanosphere uniform particle sizes, white sheet.
Using scanning electron microscope to gained 5%Pd/SiO2200 nanosphere catalyst are observed, acquired results such as Fig. 2 institute
Show, according to fig. 2 as can be seen that SiO2Nanosphere surface is attached with Pd metallic particles.
(2) 10%Pd/SiO2The preparation of 200 nanosphere catalyst:
By PdCl in (1)2The quality modification of solution is 20g, and other conditions are consistent with (1), obtains obtained Pd load capacity and is
10% nanosphere-metal composite catalyst (10%Pd/SiO2200 nanosphere catalyst).
(3) 3%Pd/SiO2The preparation of 300 nanosphere catalyst:
Weigh 300 Nano-meter SiO_2s of the preparation of embodiment 12It 2.0 grams of nanosphere, is added 10 grams and contains 100.2 milligrams of PdCl2It is molten
Liquid impregnates mixed liquor heating stirring to dry, the SiO that will be obtained after 1h2Nanosphere-palladium salt compound is cooled to room temperature, most
Afterwards by dry SiO2Nanosphere-palladium salt compound leads to hydrogen reducing 4 hours under the conditions of 350 DEG C, and Pd load capacity is made and is
3% nanosphere-metal composite catalyst (3%Pd/SiO2300 nanosphere catalyst).
(4) 5%Pd/SiO2The preparation of 100 nanosphere catalyst:
By 200 Nano-meter SiO_2s in (1)2Nanosphere replaces with 100 Nano-meter SiO_2s2Nanosphere, other conditions are consistent with (1),
It obtains that nanosphere-metal composite catalyst (5% Pd/SiO that Pd load capacity is 5% is made2100 nanosphere catalyst).
(5) 10%Pd/SiO2The preparation of 100 nanosphere catalyst:
By 200 Nano-meter SiO_2s in (1)2Nanosphere replaces with 100 Nano-meter SiO_2s2Nanosphere, PdCl2The quality of solution is repaired
It is changed to 20g, other conditions are consistent with (1), obtain that nanosphere-metal composite catalyst that Pd load capacity is 10% is made
(10%Pd/SiO2100 nanosphere catalyst).
(6) 5%Pd/SiO2The preparation of 30 nanosphere catalyst:
By 200 Nano-meter SiO_2s in (1)2Nanosphere replaces with 30 Nano-meter SiO_2s2Nanosphere, other conditions are consistent with (1),
It obtains that nanosphere-metal composite catalyst (5% Pd/SiO that Pd load capacity is 5% is made230 nanosphere catalyst).
Embodiment 3
In the pressure reaction still of 2L, be added 64 grams of 1,5- dihydroxy naphthlenes, 960 grams of ethyl acetate, 0.32 gram of sodium carbonate and
The 3%Pd/SiO prepared in 6.4 grams of embodiments 22300 nanosphere catalyst, system are passed through hydrogen, and control reaction pressure is
3Kg, reaction temperature are 60 DEG C, and reaction stops after 12 hours, are filtered while hot, and filtrate is recrystallized after being evaporated with isopropyl alcohol and water, very
It is empty dry that product 5- hydroxyl -47.4 grams of 1-tetralone, liquid phase purity are greater than 99%, yield 75%.
Embodiment 4
In the pressure reaction still of 2L, 64 grams of 1,5- dihydroxy naphthlenes, 320 grams of ethyl acetate and acetone, 6.4 grams of carbonic acid are added
The 10%Pd/SiO prepared in sodium and 0.64 gram of embodiment 22200 nanosphere catalyst, system are passed through hydrogen, control reaction pressure
Power is 40Kg, and reaction temperature is 170 DEG C, and reaction stops after 15 hours, filters while hot, filtrate is tied after being evaporated with isopropyl alcohol and water again
Crystalline substance is dried in vacuo to obtain product 5- hydroxyl -48.7 grams of 1-tetralone, and liquid phase purity is greater than 99%, yield 77.1%.
Embodiment 5
In the pressure reaction still of 2L, 64 grams of 1,5- dihydroxy naphthlenes, 640 grams of methanol and acetone, 1.2 grams of bicarbonates are added
The 10%Pd/SiO prepared in sodium and sodium methoxide, 6.4 grams of embodiments 22100 nanosphere catalyst, system are passed through hydrogen, control
Reaction pressure is 40Kg, and reaction temperature is 170 DEG C, and reaction stops after 1.5 hours, filters while hot, filtrate uses isopropanol after being evaporated
It is recrystallized with water, is dried in vacuo to obtain product 5- hydroxyl -52.4 grams of 1-tetralone, liquid phase purity is greater than 99%, yield 82.9%.
Embodiment 6
In the pressure reaction still of 2L, 64 grams of 1,5- dihydroxy naphthlenes, 640 grams of ethyl acetate, 1.2 grams of sodium carbonate, carbon are added
The mixture of sour hydrogen sodium and sodium methoxide, the 5%Pd/SiO prepared in 1.8 grams of embodiments 22200 nanosphere catalyst, system
It is passed through hydrogen, control reaction pressure is 15Kg, and reaction temperature is 100 DEG C, and reaction stops after 4 hours, filters while hot, and filtrate is steamed
It is recrystallized after dry with isopropyl alcohol and water, is dried in vacuo to obtain product 5- hydroxyl -53.2 grams of 1-tetralone, liquid phase purity is greater than
99%, yield 84.2%.
Embodiment 7
In the pressure reaction still of 2L, 64 grams of 1,5- dihydroxy naphthlenes, 640 grams of ethyl acetate and ethyl alcohol, 1.2 grams of hydrogen-oxygens are added
Change the mixture of sodium and sodium bicarbonate, the 5%Pd/SiO prepared in 1.8 grams of embodiments 22200 nanosphere catalyst systems are logical
Enter hydrogen, control reaction pressure is 15Kg, and reaction temperature is 100 DEG C, and reaction stops after 4 hours, filters while hot, filtrate is evaporated
It being recrystallized afterwards with isopropyl alcohol and water, is dried in vacuo to obtain product 5- hydroxyl -51.0 grams of 1-tetralone, liquid phase purity is greater than 99%,
Yield 80.7%.
Embodiment 8
In the pressure reaction still of 2L, 64 grams of 1,5- dihydroxy naphthlenes, 640 grams of tetrahydrofurans and ethyl alcohol, 1.2 grams of hydrogen-oxygens are added
Change the mixture of sodium and sodium bicarbonate, the 5%Pd/SiO prepared in 1.8 grams of embodiments 2230 nanosphere catalyst, system are logical
Enter hydrogen, control reaction pressure is 15Kg, and reaction temperature is 100 DEG C, and reaction stops after 4 hours, filters while hot, filtrate is evaporated
It being recrystallized afterwards with isopropyl alcohol and water, is dried in vacuo to obtain product 5- hydroxyl -50.2 grams of 1-tetralone, liquid phase purity is greater than 99%,
Yield 79.4%.
Embodiment 9
In the pressure reaction still of 2L, 64 grams of 1,5- dihydroxy naphthlenes, 640 grams of tetrahydrofurans, 1.5 grams of sodium hydroxides are added
With the mixture of sodium bicarbonate, the 5%Pd/SiO prepared in 2.4 grams of embodiments 22100 nanosphere catalyst, system are passed through
Hydrogen, control reaction pressure are 10Kg, and reaction temperature is 110 DEG C, and reaction stops after 4 hours, filters while hot, filtrate is used after being evaporated
Isopropyl alcohol and water recrystallization is dried in vacuo to obtain product 5- hydroxyl -49.9 grams of 1-tetralone, and liquid phase purity is greater than 99%, yield
79.0%.
Embodiment 10
In the pressure reaction still of 2L, 64 grams of 1,5- dihydroxy naphthlenes, 640 grams of tetrahydrofurans, 1.5 grams of sodium bisulfates are added
With the mixture of sodium bicarbonate, the 5%Pd/SiO prepared in 6.4 grams of embodiments 22200 nanosphere catalyst, system are passed through
Hydrogen, control reaction pressure are 10Kg, and reaction temperature is 110 DEG C, and reaction stops after 4 hours, filters while hot, filtrate is used after being evaporated
Isopropyl alcohol and water recrystallization is dried in vacuo to obtain product 5- hydroxyl -50.2 grams of 1-tetralone, and liquid phase purity is greater than 99%, yield
79.4%.
Embodiment 11
In the pressure reaction still of 2L, 64 grams of 1,5- dihydroxy naphthlenes, 640 grams of tetrahydrofurans, 1.5 grams of sodium bicarbonates are added
With the mixture of sodium chloride, the 5%Pd/SiO prepared in 1.5 grams of embodiments 2230 nanosphere catalyst, system are passed through hydrogen,
Control reaction pressure is 10Kg, and reaction temperature is 110 DEG C, and reaction stops after 4 hours, filters while hot, filtrate uses isopropyl after being evaporated
Alcohol and water recrystallization is dried in vacuo to obtain product 5- hydroxyl -50.0 grams of 1-tetralone, and liquid phase purity is greater than 99%, yield
79.1%.
Embodiment 12
In the pressure reaction still of 2L, be added 64 grams of 1,5- dihydroxy naphthlenes, 640 grams of hexamethylenes, 1.0 grams of sodium bicarbonates and
The mixture of sodium chloride, the 5%Pd/SiO prepared in 3.2 grams of embodiments 22200 nanosphere catalyst, system are passed through hydrogen,
Control reaction pressure is 15Kg, and reaction temperature is 120 DEG C, and reaction stops after 4 hours, filters while hot, filtrate uses isopropyl after being evaporated
Alcohol and water recrystallization is dried in vacuo to obtain product 5- hydroxyl -52.5 grams of 1-tetralone, and liquid phase purity is greater than 99%, yield
83.1%.
As seen from the above embodiment, nanosphere provided by the invention-metal composite catalyst catalytic activity is high, selectivity
Height, can be with efficient catalytic 1, the hydrogenation of 5- dihydroxy naphthlene, gained 5- hydroxyl -1-tetralone purity is high, yield height.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of 5- hydroxyl -1-tetralone, comprising the following steps:
Will 1,5- dihydroxy naphthlene, inorganic sodium compound, nanosphere-metal composite catalyst and solvent mix after be passed through hydrogen into
Row hydrogenation obtains 5- hydroxyl -1-tetralone；Nanosphere-the metal composite catalyst, including SiO2Nanosphere
Be supported on SiO2The Pd metallic particles on nanosphere surface；The quality of the nanosphere-metal composite catalyst is 1,5-
The 1~10% of dihydroxy naphthlene quality；The quality of the inorganic sodium compound is the 0.05~10% of 1,5- dihydroxy naphthlene quality；
The SiO2The specific surface area of nanosphere is 20~150m2/g；The SiO2Nanosphere is monodisperse SiO2Nanometer is micro-
Ball；The SiO2Nanosphere is prepared using seed mediated growth method；SiO in the seed mediated growth method2Nanosphere seed point
SiO in dispersion liquid2Nanosphere seed carries out in the uniform buffer solution containing tetraethyl orthosilicate, water, arginine and ethyl alcohol
Regrowth；Under the premise of keeping total tetraethyl orthosilicate usage amount constant, SiO is used to prepare by control2Nanosphere seed
The ratio of the amount of the tetraethyl orthosilicate added in the amount and regrowth process of the tetraethyl orthosilicate of dispersion liquid regulates and controls SiO2Nanometer is micro-
The particle size range of ball is 14~550nm；
The SiO2Nanosphere seeded dispersion liquid is prepared by the following method to obtain: arginine is dissolved under agitation
In water, it is added in arginine aqueous solution under the conditions of tetraethyl orthosilicate is stirred at room temperature, obtains mixture；Silicic acid four in mixture
The molar ratio of ethyl ester, arginine and water is 1:0.02:194；Mixture 343K at a temperature of, using with 15 × Φ 7mm
The magnetic stirring apparatus of teflon coatings stirring rod for 24 hours, obtains the monodisperse SiO that partial size is 14nm with the revolving speed stirring of 1000rpm2
Nanosphere seeded dispersion liquid.
2. preparation method according to claim 1, which is characterized in that the SiO2The partial size of nanosphere be 30~
300nm。
3. preparation method according to claim 1, which is characterized in that the Pd metallic particles is in SiO2Nanosphere surface
Load capacity be 3~10wt%.
4. preparation method according to any one of claims 1 to 3, which is characterized in that the nanosphere-metal composite
The preparation method of catalyst the following steps are included:
By SiO2Nanosphere is impregnated in palladium salt solution, is obtained immersed with SiO2The palladium salt solution of nanosphere；
It will be immersed with SiO2The palladium salt solution of nanosphere is heated to doing, and obtains SiO2Nanosphere-palladium salt compound；
By the SiO2Nanosphere-palladium salt compound carries out hydrogen reducing, obtains nanosphere-metal composite catalyst.
5. the preparation method according to claim 4, which is characterized in that the temperature of the hydrogen reducing is 300~400 DEG C；
The time of the hydrogen reducing is 3~5h.
6. preparation method according to claim 1, which is characterized in that the inorganic sodium compound includes sodium hydroxide, chlorine
Change the mixture of one or more of sodium, sodium carbonate, sodium sulphate, sodium bisulfate and sodium bicarbonate.
7. preparation method according to claim 1, which is characterized in that the pressure of the hydrogenation is 3~40kg；
The temperature of the hydrogenation is 60~170 DEG C；
The time of the hydrogenation is 1.5~15h.
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