CN110368946A - The method that carried non-crystal alloy catalysis hydrogenation of acetophenone prepares alpha-phenyl ethyl alcohol - Google Patents
The method that carried non-crystal alloy catalysis hydrogenation of acetophenone prepares alpha-phenyl ethyl alcohol Download PDFInfo
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- CN110368946A CN110368946A CN201910716191.4A CN201910716191A CN110368946A CN 110368946 A CN110368946 A CN 110368946A CN 201910716191 A CN201910716191 A CN 201910716191A CN 110368946 A CN110368946 A CN 110368946A
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- catalyst
- nickel
- acetophenone
- copper
- amorphous alloy
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- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 27
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 title claims description 8
- 229910045601 alloy Inorganic materials 0.000 title description 8
- 239000000956 alloy Substances 0.000 title description 8
- 239000013078 crystal Substances 0.000 title description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 68
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 239000012876 carrier material Substances 0.000 claims abstract description 6
- 229910000570 Cupronickel Inorganic materials 0.000 claims abstract description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000001257 hydrogen Substances 0.000 claims description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 239000002904 solvent Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 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 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000004480 active ingredient Substances 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- MFWPBGUEAHRINS-UHFFFAOYSA-N [Cu].[B].[Ni] Chemical compound [Cu].[B].[Ni] MFWPBGUEAHRINS-UHFFFAOYSA-N 0.000 claims 2
- 239000002243 precursor Substances 0.000 claims 2
- 150000003839 salts Chemical class 0.000 claims 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052810 boron oxide Inorganic materials 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims 1
- 239000012467 final product Substances 0.000 claims 1
- 229910052738 indium Inorganic materials 0.000 claims 1
- 229940078494 nickel acetate Drugs 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000012047 saturated solution Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- NUHFQRCBVYYWOT-UHFFFAOYSA-N 2-phenylethanol;1-phenylethanone Chemical compound CC(=O)C1=CC=CC=C1.OCCC1=CC=CC=C1 NUHFQRCBVYYWOT-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 229910052681 coesite Inorganic materials 0.000 description 6
- 229910052906 cristobalite Inorganic materials 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 229960001866 silicon dioxide Drugs 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 229910052682 stishovite Inorganic materials 0.000 description 6
- 229910052905 tridymite Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000006467 substitution reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- -1 aromatic alcohol Compound Chemical class 0.000 description 3
- 239000000969 carrier Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GJSJZQZEDAUFBH-UHFFFAOYSA-N benzene;pentan-3-one Chemical compound CCC(=O)CC.C1=CC=CC=C1 GJSJZQZEDAUFBH-UHFFFAOYSA-N 0.000 description 2
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 2
- 229910010277 boron hydride Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- HEFNNWSXXWATRW-UHFFFAOYSA-N Ibuprofen Chemical compound CC(C)CC1=CC=C(C(C)C(O)=O)C=C1 HEFNNWSXXWATRW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 230000000202 analgesic effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000341 volatile oil Substances 0.000 description 1
- 239000002699 waste material Substances 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
-
- 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
- C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to chemical technology fields, and in particular to a kind of method that carried copper-base amorphous alloy catalyst hydrogenation of acetophenone produces alpha-phenyl ethyl alcohol.Amorphous alloy catalyst is made of copper, nickel, boron and porous carrier materials Z.Wherein, copper mainly exists in the form of Cu-Ni-B amorphous alloy, and preparation method includes by active component cupro-nickel BH4 ‑Reduction is on carrier.The catalyst raw material is cheap, using safe, in reaction applied to hydrogenation of acetophenone benzyl carbinol, with stability more higher than traditional nickel-base catalyst and selectivity, when acetophenone conversion reaches 98% or more, alpha-phenyl ethyl alcohol selectivity reacts 300h rear catalyst activity and is still maintained at higher level up to 97%.
Description
Technical field
The present invention relates to fragrance and medicine intermediate synthesis technical field, and specifically one kind is about support type Cu-Ni-
B amorphous alloy catalyst hydrogenation of acetophenone prepares the preparation method of alpha-phenyl ethyl alcohol.
Background technique
Aromatic alcohol is the important chemical products of manufacture medicine and synthetic perfume.Alpha-phenyl ethyl alcohol is most represented in aromatic alcohol
Compound is important intermediate in pharmaceutical synthesis, such as in the synthesis of this on-steroidal ntipyretic analgesic medicine of brufen,
Alpha-phenyl ethyl alcohol is important raw material；It is widely used in fragrance in fragrance production to reconcile, as various essential oils due to flowery odour
Main component.The effective ways of alpha-phenyl ethyl alcohol synthesis are usually to be changed into benzyl carbinol by hydrogenation of acetophenone reduction.Due to benzene second
The inductive effect of phenyl ring and c h bond and carbonyl keep carbonyl electronegativity higher, are easily accepted by there is σ-π hyperconjugation in ketone
Proton, therefore carbonyl hydrogen is easier to carry out.The by-product of hydrogenation of acetophenone is mainly ethylbenzene and benzene ring hydrogenation product.
Catalyst is the key that whole process in hydrogenating reduction, and common heterogeneous catalysis has with Pt, Ru, Pd, Rh etc.
For the noble metal catalyst of active component, nickel-base catalyst, copper-based catalysts etc..Compared to first two catalyst, cupper-based catalyst
Agent activated adoption hydrogen number is less, while it has greater activity to C=O, and lower to C-C key activity, largely presses down
The hydrogenolysis for having made acetophenone improves the selectivity of alpha-phenyl ethyl alcohol.Patent CN107999082A provides a kind of by adding
Enter auxiliary agent salt compounds to improve activity, selectivity and the copper system hydrogenation of acetophenone catalyst to prolong the service life, reaction
2000h acetophenone conversion still is able to be maintained at 98% or more, but needs that the rare earths such as La, Ce gold is added in catalyst preparation process
Belong to, it is at high cost.EP1701877B1 is modified to copper silicon hydrogenation catalyst by alkali and alkaline earth metal ions, limits the pairs such as ethylbenzene
The generation of product, silicon source is added in the form of fumed silica or diatomite causes active component and carrier interaction weak,
It is unfavorable to catalyst strength.CN108043414A proposes a kind of system of the copper-based catalysts of acetophenone liquid-phase hydrogenatin alpha-phenyl ethyl alcohol
Preparation Method significantly suppresses the side reactions such as hydrogenolysis, improves catalytic activity and selectivity, but catalyst need to be passed through difference before
The H of ratio2、N2Gaseous mixture is activated, cumbersome.Therefore development technology is simple, green is cheap, stability and high efficiency plus hydrogen is urged
Agent substitutes traditional hydrogenation catalyst, has important economic value and social benefit.
Amorphous alloy possesses the characteristics such as the easy modulation of structure, coordination height unsaturation, chemical uniformity, eliminates traditional crystalline substance
The activity difference of state catalysis material difference crystal plane structure, keeps active center distribution uniform, property is identical.Amorphous catalysts add hydrogen living
Property than the crystal alloy of same composition be higher by hundred times, and show highly selective, greatly improve the Atom economy of raw material, reduce
The generation of waste, becomes novel environment friendly catalysis material.It is reported in Chinese patent CN1557545A and utilizes chemical reduction method
The amorphous state Ni-Sn-B/SiO of preparation2It is catalyzed hydrogenation of acetophenone alpha-phenyl ethyl alcohol, selectively reaches as high as 97.5%, however nickel
Base noncrystal alloy catalyst is easily oxidized inactivation, is not easy to store；And China's nickel resources only account for the 3.7% of global gross reserves, nickel source
Price is relatively high, is unfavorable for large-scale industrial production.Therefore, exploitation amorphous state copper-based catalysts meet current Chemical Manufacture
Development trend simplifies production process to reduced cost, and it is significant to improve production security.
Summary of the invention
The carried non-crystal of cheap, simple process that the purpose of the present invention is to provide a kind of raw materials and safety and stability is copper-based
The preparation method and application of hydrogenation of acetophenone catalyst, cu-base amorphous alloy state catalyst hydrogenation activity made from the method is high, is adding hydrogen
The hydrogenolysis of benzyl carbinol can be significantly inhibited in the process, improve selectivity.
The present invention with methanol, ethyl alcohol, isopropanol, toluene, pentane, hexamethylene etc. for solvent, with support type Cu-Ni-B amorphous
State alloy makees catalyst, and catalysis hydrogenation of acetophenone produces alpha-phenyl ethyl alcohol.
Above-mentioned reaction can be carried out intermittently or serially in autoclave or fixed bed reactors.Reaction temperature be 60~
200 DEG C, preferably 60~120 DEG C；Hydrogen Vapor Pressure is 0.1~5.0MPa, is preferably carried out under the conditions of 1.0~3.0MPa；It is used
Catalyst be support type cu-base amorphous alloy state alloy catalyst.
Carried copper-base amorphous alloy catalyst for hydrogenation of acetophenone alpha-phenyl ethyl alcohol be by Cu, Ni and B and
Selected from porous carrier materials Z such as active carbon, silica gel, aluminium oxide, zirconium oxide, titanium oxide, diatomite, zeolite or various molecular sieves
Composition.The mass percentage of each component is as follows in catalyst:
Cu:Ni:B:Z=0~30:0~20:0.01~10:40~99
In catalyst preparation process provided by the invention, mantoquita used is hydrochloride, acetate, sulfate, wherein most
It is sulfate, acetate well；Nickel salt used is hydrochloride, acetate, sulfate, wherein preferably acetate, sulfate；Institute
The boron hydride stated is potassium borohydride or sodium borohydride.In the Cu-Ni-B amorphous alloy, B/ (Cu+Ni) molar ratio is 1
~15, wherein preferably 4~9；Ni/ (Cu+Ni) molar ratio is 0~1, preferably 0.2~0.8.
Catalyst activity component mainly exists in the form of Cu-B or Cu-Ni-B amorphous alloy, amorphous structure feature
It can be determined by X-ray powder diffraction, diffraction pattern has a wide in range diffraction maximum at 2 θ=45 °, spreads out for the feature of amorphous alloy
Penetrate peak.The dosage of carried copper-base amorphous alloy catalyst in the reaction is the 1%~40% of acetophenone quality.
The specific embodiment of the invention is as follows:
In stainless steel autoclave, the acetophenone, solvent and the carried non-crystal of preparation of measuring requirement are sequentially added
Alloy catalyst.Autoclave is closed, it is passed through nitrogen leak test rear substitution 4~5 times, removes the air in kettle.Pour hydrogen displacement
And reaction pressure is risen to, stirring is opened, speed of agitator is 500~1200rpm, and heating is reacted.Hydrogen is logical in reaction process
It crosses gas flowmeter to be monitored, when reacting after a certain period of time, stops reaction.It is cooling, reaction product is removed into reactor, is filtered
Catalyst out.Catalyst can be recycled, and take a little fluid sample for gas chromatographic analysis.
In fixed bed device, the center stainless steel tubular reactor (10 × 1000mm of Ф) has a thermocouple to show bed
Layer temperature, by programmable temperature control instrument control system between 60~200 DEG C, carried copper-base amorphous alloy catalyst loads reaction temperature
Amount is 4~10mL, is loaded in the constant temperature zone in the middle part of reactor.The mixed solution of solvent and acetophenone is squeezed into instead through metering pump
Device is answered, then is mixed with hydrogen, through gas-liquid separation after conversion zone is hydrogenated to alpha-phenyl ethyl alcohol, collects liquid, timing sampling gas
Analysis of hplc.Acetophenone 20~40wt% of content, reaction temperature are 60~150 DEG C, and pressure is 1~3MPa, and liquid hourly space velocity (LHSV) is
0.3~2h-1, hydrogen ketone is than 1~30.
Prepare the conventional method of carried copper-base amorphous alloy catalyst are as follows: soak after roasting screened carrier material
The saturated salt solution of a certain amount of active component of stain, vacuum drying；Under stiring in being higher than solution freezing point at a temperature of 100 DEG C
Active component is restored with boron hydride, obtains carried non-crystal alloy catalyst after foreign ion is cleaned.
Specific embodiment
Embodiment 1
(1) a certain amount of saturation CuCl is added in 550 DEG C of Muffle kiln roasting 5h in 20~80 mesh silica-gel carriers2·2H2O is molten
Liquid incipient impregnation 2h, then 100 DEG C of vacuum drying.The NaOH solution of the sodium borohydride of 2M is slowly dropped to leaching in ice-water bath
Have on the silica-gel carrier of copper chloride, stirring to bubble-free is released.Gained catalyst is washed with distilled water, and is saved after being impregnated with ethyl alcohol
In closed containers for future use.In catalyst made from the present embodiment, by mass percentage, active ingredient copper accounts for 30%.
(2) in 50mL stainless steel autoclave, 10mL ethyl alcohol, 3g acetophenone and 0.9g step (1) preparation are sequentially added
Support type Cu-B/SiO2Amorphous alloy catalyst.Nitrogen leak test rear substitution is passed through 4~5 times for autoclave is closed, to remove kettle
In air.It is passed through hydrogen again to set gas and rise to reaction pressure, opens stirring, speed of agitator 800rpm is warming up to 80 DEG C, protects
Holding reaction pressure is 1.5MPa.Reaction process is monitored by gas mass flow meter, after reacting 4h, stops reaction, cooling,
Reaction product is removed into reactor, filters out catalyst.Liquid is through gas chromatographic detection, acetophenone conversion 85.7%, α-benzene
Ethanol selectivity is 98.6%.
Embodiment 2~13
(1) a certain amount of saturation Cu (CH is added in 550 DEG C of Muffle kiln roasting 5h in different carriers material3COO)2·H2O
With Ni (CH3COO)2·4H2The mixed solution incipient impregnation 8h of O, then 110 DEG C of vacuum drying.While stirring will in ice-water bath
The NaOH solution of the potassium borohydride of 2M is slowly dropped on the carrier containing copper and mickel, and reaction to bubble-free is released.Gained catalysis
Agent is washed with distilled water, and closed containers for future use is put into after being impregnated with ethyl alcohol.In catalyst made from the present embodiment, by quality
Percentages, active component cupro-nickel account for 10%.Catalyst Cu/ (Cu+Ni) atomic ratio in preparation process, B/ (Cu+Ni) atomic ratio
And the selection of carrier is listed in table 1.
(2) in 50mL stainless steel autoclave, 10mL etoh solvent, 3g acetophenone and 0.9g step (1) are sequentially added
The support type Cu-Ni-B amorphous alloy catalyst of preparation.Nitrogen leak test rear substitution is passed through 4~5 times for autoclave is closed, to remove
Air in kettle.It is passed through hydrogen again and replaces and rise to reaction pressure, opens stirring, speed of agitator 800rpm is warming up to 80 DEG C,
Holding reaction pressure is 1.5MPa.Reaction process is monitored by gas mass flow meter, after reacting 4h, stops reaction, cold
But, reaction product is removed into reactor, filters out catalyst.Liquid is through gas chromatographic detection, according to gas-chromatography spectrogram each group
Content is divided to calculate hydrogenation conversion and selectivity of product.Feed change difference composition and proportion obtain (embodiment 2~13) amorphous
State support type Cu-Ni-B catalyst hydrogenation of acetophenone result is shown in table 1.
The hydrogenation reaction result of the different composition catalyst of table 1 (embodiment 2~13)
Embodiment 14
(1) by 20~60 mesh silica gel in Muffle furnace 550 DEG C of roasting 5h, the NiCl of a certain amount of saturation is added2·6H2O solution
Incipient impregnation for 24 hours, is then dried in vacuo for 120 DEG C.The NaOH solution of the potassium borohydride of 2M is slowly dropped under room temperature and is soaked with
On the active carbon of nickel chloride, stirring to bubble-free is released.Gained catalyst is washed with distilled water, and is put into after being impregnated with ethyl alcohol closed
Containers for future use.In catalyst made from the present embodiment, by mass percentage, active component nickel accounts for 40%
(2) hydrogen is added to prepare alpha-phenyl ethyl alcohol by the same method and condition of 1 step of embodiment (2), it is non-that catalyst is changed to 0.9g
Crystalline state Ni-B/SiO2, adding hydrogen result is acetophenone conversion 96.3%, alpha-phenyl ethyl alcohol selectivity 60.6%.
Embodiment 15
(1) 20~80 mesh silica-gel carriers after roasting are dried in an oven, the CuSO of a certain amount of saturation is added4·5H2O and
NiSO4·6H2The mixed solution incipient impregnation 12h of O, then 100 DEG C of vacuum drying.While stirring by the potassium borohydride of 2M
NaOH solution is slowly dropped on the silica-gel carrier for being soaked with copper and mickel, until bubble-free is released.Gained catalyst is washed with distilled water,
Closed containers for future use is put into after being impregnated with ethyl alcohol.In catalyst made from the present embodiment, by mass percentage, active group
Point cupro-nickel accounts for 15%.
(2) hydrogen is added to prepare alpha-phenyl ethyl alcohol by the same method and condition of 1 step of embodiment (2), it is non-that catalyst is changed to 0.9g
Crystalline state Cu-Ni-B/SiO2, adding hydrogen result is acetophenone conversion 99.7%, alpha-phenyl ethyl alcohol selectivity 89.6%.By the catalyst
It reuses 3 times, product yield does not have significant change.
Embodiment 16~25
In 50mL stainless steel autoclave, 10mL solvent, 3g acetophenone and a certain amount of by 15 step of embodiment are sequentially added
Suddenly the Cu-Ni-B/SiO of (1) preparation2Amorphous alloy catalyst.Nitrogen leak test rear substitution is passed through 4~5 times for autoclave is closed, with
Remove the air in kettle.It is passed through hydrogen again and rises to reaction pressure, stirring is opened after heating, speed of agitator 800rpm adds hydrogen
Constant reaction pressure is kept in the process.Solvent selects ethyl alcohol, methanol, isopropanol, toluene, pentane, hexamethylene in the present embodiment, instead
Hydrogen consumption is monitored by gas mass flow meter during answering, and reaction after a certain period of time, stops reaction, cooling, will be anti-
It answers product to remove reactor, filters out catalyst.Liquid is through gas chromatographic detection, according to gas-chromatography spectrogram each component content meter
Calculate hydrogenation conversion and selectivity of product.Change different condition and obtains (embodiment 16~25) amorphous Cu-Ni-B/SiO2Catalysis
Hydrogenation of acetophenone result is shown in table 2.
The different hydrogenation conditions (embodiment 16~25) of table 2 plus hydrogen effect expedition
Embodiment 26
In fixed bed device, the Cu- that 6mL presses 15 step of embodiment (1) preparation is loaded into stainless steel tubular reactor
Ni-B/SiO2Amorphous alloy catalyst.Adjusting temperature of reactor is 100 DEG C, Hydrogen Vapor Pressure used is 2.0MPa, adjusts hydrogen
Flow is 80mL/min inflow reactor, while by acetophenone: the mixture of ethyl alcohol=1:3 (V/V) is pumped with HPLC, when appraising and deciding liquid
Air speed 0.8h-1, direction identical with hydrogen stream is injected reactor and is reacted.Through cold after conversion zone is hydrogenated to alpha-phenyl ethyl alcohol
Solidifying gas-liquid separation, collects liquid, timing sampling gas chromatographic analysis.The average response result of reaction 50~100 hours is benzene
Ethyl ketone conversion ratio 99.6%, alpha-phenyl ethyl alcohol selectivity 97.4%.After continuously hydrogen adding reacts 300 hours, sampling analysis result is benzene
Ethyl ketone conversion ratio 98.3%, alpha-phenyl ethyl alcohol selectivity 98.7%.
By Activity evaluation it is found that Cu-Ni-B/SiO2Amorphous alloy catalyst is used for hydrogenation of acetophenone α-benzene second
Alcohol, catalytic activity with higher and the selectivity to alpha-phenyl ethyl alcohol, when acetophenone conversion reaches 98% or more, benzyl carbinol choosing
Selecting property has obtained catalytic activity more higher than carried non-crystal Cu-B, Ni-B catalyst and hydrogenation selectivity up to 97%.
The foregoing is merely present pre-ferred embodiments, not to limit the present invention.In the range without departing from each embodiment
With in the case where spirit it is made replacement and improvement etc., be included within the scope of protection of the present invention.
Claims (9)
1. a kind of carried copper nickel-boron amorphous alloy catalyst is used for the method that acetophenone selective hydrogenation prepares alpha-phenyl ethyl alcohol.
It is characterized in that the support type cupro-nickel boron amorphous alloy catalyst is made of Cu, Ni and B and porous carrier materials Z；Catalysis
Active component (gross mass 100) each component weight proportion calculated by mass is Cu:Ni:B:Z=0~30:0~20 in agent:
0.01~10:40~99；Wherein copper mainly exists in the form of Cu-B and Cu-Ni-B amorphous alloy, and nickel is with metallic state and oxygen
Change state two states to exist, boron exists in the form of element state and boron oxide.
2. the carried copper nickel-boron amorphous alloy according to claim 1 for acetophenone selective hydrogenation benzyl carbinol
The preparation method of catalyst, it is characterised in that within the temperature range of being higher than solution freezing point to 100 DEG C, pass through under stiring
BH4 -NaOH solution reduction.
3. catalyst according to claim 1, it is characterised in that porous carrier materials Z is selected from active carbon, silica gel, oxidation
Aluminium, zirconium oxide, titanium oxide, diatomite, zeolite or various molecular sieves etc..
4. the preparation method of catalyst according to claims 1 and 2, it is characterised in that the load of the supported active presoma
Preparation step is as follows: after carrier material is immersed in mantoquita and 5min in nickel salt mixing saturated solution~for 24 hours, in 80~150
It is dried overnight at DEG C to obtain the final product.
5. the preparation method of catalyst as claimed in claim 2, it is characterised in that the precursor salt of active ingredient copper is selected from chlorination
One of copper, copper acetate or copper sulphate, the active component precursor salt of nickel in nickel chloride, nickel acetate or nickel sulfate one
Kind；BH4 -Selected from potassium borohydride or sodium borohydride.
6. amorphous alloy catalyst described in accordance with the claim 1, it is characterised in that the Cu-Ni-B amorphous alloy
In, B/ (Cu+Ni) molar ratio is that 1~15, Cu/ (Cu+Ni) molar ratio is 0~1.
7. the preparation method of benzyl carbinol as described in claim 1, it is characterised in that hydrogenation of acetophenone process with methanol, ethyl alcohol,
Isopropanol, toluene, pentane, hexamethylene etc. are solvent, and α-is intermittently or serially prepared in autoclave or fixed bed reactors
Benzyl carbinol.Reaction temperature is 60~200 DEG C, and Hydrogen Vapor Pressure is 0.1~5.0MPa.
8. the preparation method of the benzyl carbinol as described in claim 1 and 7, it is characterised in that acetophenone in fixed bed continuous reactor
20~40wt% of content, liquid hourly space velocity (LHSV) are 0.3~2h-1, hydrogen ketone is than 1~30.
9. the preparation method of the benzyl carbinol as described in claim 1 and 7, it is characterised in that reaction process catalyst amount is benzene second
The 1%~40% of ketone quality.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111892053A (en) * | 2020-07-08 | 2020-11-06 | 桂林理工大学 | Zirconium-loaded activated carbon high-activity material and preparation method and application thereof |
| CN112221508A (en) * | 2020-09-01 | 2021-01-15 | 河北工业大学 | Catalyst for preparing phenethyl alcohol by acetophenone hydrogenation and preparation and application methods thereof |
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| CN1196975A (en) * | 1997-04-24 | 1998-10-28 | 中国石油化工总公司 | Non-crystalline alloy catalyst containing Ni and B, its prepn. and application |
| CN1557545A (en) * | 2004-01-16 | 2004-12-29 | 复旦大学 | Amorphous nickel boron catalyst for hypnone hydrogenation and its preparation method |
| CN109926055A (en) * | 2017-12-16 | 2019-06-25 | 万华化学集团股份有限公司 | The method for preparing catalyst of hydrogenation of acetophenone alpha-phenyl ethyl alcohol and application |
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| CN1196975A (en) * | 1997-04-24 | 1998-10-28 | 中国石油化工总公司 | Non-crystalline alloy catalyst containing Ni and B, its prepn. and application |
| CN1557545A (en) * | 2004-01-16 | 2004-12-29 | 复旦大学 | Amorphous nickel boron catalyst for hypnone hydrogenation and its preparation method |
| CN109926055A (en) * | 2017-12-16 | 2019-06-25 | 万华化学集团股份有限公司 | The method for preparing catalyst of hydrogenation of acetophenone alpha-phenyl ethyl alcohol and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111892053A (en) * | 2020-07-08 | 2020-11-06 | 桂林理工大学 | Zirconium-loaded activated carbon high-activity material and preparation method and application thereof |
| CN111892053B (en) * | 2020-07-08 | 2022-09-27 | 桂林理工大学 | Zirconium-loaded activated carbon high-activity material and preparation method and application thereof |
| CN112221508A (en) * | 2020-09-01 | 2021-01-15 | 河北工业大学 | Catalyst for preparing phenethyl alcohol by acetophenone hydrogenation and preparation and application methods thereof |
| CN112221508B (en) * | 2020-09-01 | 2021-09-07 | 河北工业大学 | Catalyst for preparing phenethyl alcohol by acetophenone hydrogenation and preparation and application methods thereof |
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