CN114849679A - Solid superacid supported catalyst and preparation method of beta-phenethyl alcohol - Google Patents
Solid superacid supported catalyst and preparation method of beta-phenethyl alcohol Download PDFInfo
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- CN114849679A CN114849679A CN202210348756.XA CN202210348756A CN114849679A CN 114849679 A CN114849679 A CN 114849679A CN 202210348756 A CN202210348756 A CN 202210348756A CN 114849679 A CN114849679 A CN 114849679A
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- supported catalyst
- steel slag
- super acidic
- acid
- catalyst
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- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000007787 solid Substances 0.000 title claims abstract description 25
- 239000003930 superacid Substances 0.000 title claims description 22
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 41
- 239000010959 steel Substances 0.000 claims abstract description 41
- 239000002893 slag Substances 0.000 claims abstract description 40
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 27
- 230000002378 acidificating effect Effects 0.000 claims abstract description 27
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 27
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000010949 copper Substances 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- 239000001257 hydrogen Substances 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 8
- 238000006722 reduction reaction Methods 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- -1 Beta-phenethyl Chemical group 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 238000005470 impregnation Methods 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 125000006273 (C1-C3) alkyl group Chemical group 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 23
- 239000002994 raw material Substances 0.000 abstract description 9
- 150000003333 secondary alcohols Chemical class 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 abstract description 2
- 150000001879 copper Chemical class 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 229910052702 rhenium Inorganic materials 0.000 abstract 1
- 229910052703 rhodium Inorganic materials 0.000 abstract 1
- 238000007086 side reaction Methods 0.000 abstract 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 12
- 208000012839 conversion disease Diseases 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 239000003205 fragrance Substances 0.000 description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000686 essence Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000220317 Rosa Species 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- PEZDGNIESNXEDE-UHFFFAOYSA-N benzene;oxirane Chemical compound C1CO1.C1=CC=CC=C1 PEZDGNIESNXEDE-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- FUKUFMFMCZIRNT-UHFFFAOYSA-N hydron;methanol;chloride Chemical compound Cl.OC FUKUFMFMCZIRNT-UHFFFAOYSA-N 0.000 description 2
- 230000002045 lasting effect Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229940067107 phenylethyl alcohol Drugs 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 150000003254 radicals Chemical class 0.000 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 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 description 2
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 description 1
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241000208125 Nicotiana Species 0.000 description 1
- 235000002637 Nicotiana tabacum Nutrition 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000010669 acid-base reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001723 carbon free-radicals Chemical class 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003889 eye drop Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000010648 geranium oil Substances 0.000 description 1
- 235000019717 geranium oil Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 235000019198 oils Nutrition 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229960003424 phenylacetic acid Drugs 0.000 description 1
- 239000003279 phenylacetic acid Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000010666 rose oil Substances 0.000 description 1
- 235000019719 rose oil Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/053—Sulfates
- B01J27/055—Sulfates with alkali metals, copper, gold or silver
-
- 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
- B01J37/024—Multiple impregnation or coating
-
- 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
- C07C29/147—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 carboxylic acids or derivatives thereof
- C07C29/149—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 carboxylic acids or derivatives thereof 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
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a solid super acidic supported catalyst and a preparation method of beta-phenethyl alcohol. The solid super acidic supported catalyst comprises an active component copper and a carrier, wherein the carrier is a zirconium system/steel slag super acidic. The catalyst has the advantages of strong secondary alcohol selective hydrogenolysis capability, high product selectivity and the like, overcomes the defects of poor secondary alcohol hydrogenolysis capability of the existing copper catalyst, side reaction of benzene ring hydrogenation of Rh and Re modified copper catalysts and the like, and has the advantages of cheap and easily obtained raw materials, simple reaction steps, small environmental pollution, low cost, high yield, safety, easy product purification and suitability for industrial production compared with other methods when being used for preparing phenethyl alcohol.
Description
Technical Field
The invention relates to the field of catalysts and organic synthesis, in particular to a solid super acidic supported catalyst, a preparation method thereof and a method for preparing beta-phenethyl alcohol.
Background
Beta-phenylethyl alcohol (PEA), also known as 2-phenylethyl alcohol, phenylethyl alcohol and ethyl phenylethyl alcohol, is a simple aromatic primary alcohol, is colorless liquid at normal temperature, has elegant, fine and lasting rose fragrance, is originally discovered as a characteristic fragrant compound in fresh plant flowers, and naturally exists in fragrant oil such as orange flower oil, rose oil and geranium oil.
The beta-phenethyl alcohol is widely applied to various edible essences and tobacco essences because of having soft, pleasant and lasting rose fragrance, and is a main raw material for preparing rose-fragrance food additives and rose-fragrance essences. Beta-phenylethyl alcohol is used second to vanillin in an amount worldwide as a fragrance. Meanwhile, the beta-phenethyl alcohol is insoluble in water due to stable alkali action, and is often used in cosmetic water and perfumed soap. In addition, the beta-phenethyl alcohol has good antibacterial effect, and can be used in eye drop aqueous solution and skin care products.
At present, the beta-phenethyl alcohol on the market is basically chemically synthesized. The main chemical synthesis processes for beta-phenylethyl alcohol are the benzene-ethylene oxide process (Friedel-Crafts reaction) and the styrene oxide (STO) hydrogenation process. At present, the benzene-ethylene oxide method is basically eliminated, and a styrene oxide hydrogenation method is mainly adopted in the perfume industry, wherein the styrene oxide hydrogenation product accounts for about 72 percent. For the hydrogenation of styrene oxide to prepare beta-phenethyl alcohol, the disadvantages of large process investment, high risk and the like are caused by the involvement of flammable and explosive compounds.
In conclusion, the prior art has certain defects in different degrees, and if peroxide or an intermediate styrene oxide is required to be introduced as an explosive material, the safety is poor. Therefore, the development of a novel efficient and safe beta-phenylethyl alcohol process is of great significance for upgrading the preparation technology of the beta-phenylethyl alcohol.
Disclosure of Invention
The invention aims to provide a solid superacid supported catalyst and a preparation method of beta-phenethyl alcohol. Has the effects of low by-product and high selectivity, and can obtain the beta-phenethyl alcohol with high yield.
In order to achieve the technical purpose, the invention adopts the following method:
a solid super acidic supported catalyst comprises an active component copper and a carrier, wherein the carrier is zirconium system/steel slag super acidic.
Further, in the solid super acidic supported catalyst, the mass content of the active component copper (calculated as CuO) is 0.1-60%, preferably 1-30%, more preferably 5-25%, based on the total mass of the catalyst.
The preparation method of the zirconium system/steel slag super acid comprises the following steps:
1) ZrOCl 2 ·8H 2 Dissolving O in water, adding steel slag for impregnation, adding an ammonium carbonate aqueous solution, separating, washing and drying;
2) dipping with sulfuric acid, drying and roasting.
In the preparation method of the zirconium/steel slag super acid, in the step 1), the dipping time is 1-2 hours.
In the preparation method of the zirconium system/steel slag super acid, ZrOCl is adopted 2 ·8H 2 ZrOCl after O dissolved in water 2 The concentration of (B) is 0.001 to 0.2g/mL, preferably 0.01 to 0.1 g/mL.
In the preparation method of the zirconium system/steel slag super acid, the steel slag has the mass of ZrOCl 2 ·8H 2 2.5-3 times of the mass of O.
In the preparation method of the zirconium system/steel slag super acid, the concentration of the ammonium carbonate aqueous solution is 15-25 wt%.
In the preparation method of the zirconium system/steel slag super acid, the drying temperature is 100-120 ℃.
In the preparation method of the zirconium system/steel slag super acid, the concentration of the sulfuric acid is 1-2 mol/L.
In the preparation method of the zirconium system/steel slag super acid, in the step 2), the dipping time is 2-4 h.
In the preparation method of the zirconium system/steel slag super acid, in the step 2), the roasting temperature is 500-600 ℃, and the time is 2-4 hours.
In the preparation method of the zirconium system/steel slag super acid, in the step 2), the steel slag comprises, by mass, 2-8 wt% of iron oxide, 30-50 wt% of calcium oxide, 8-12 wt% of magnesium oxide, 7-9 wt% of aluminum oxide, 20-32 wt% of silicon dioxide, 2-5 wt% of manganese oxide, 1-4 wt% of phosphorus pentoxide, 0.8-3 wt% of titanium dioxide, 3-6 wt% of vanadium pentoxide and 0.05-1 wt% of the rest, based on 100% of the steel slag.
The zirconium system/steel slag superacid is prepared by loading zirconium system oxide on steel slag, then treating the zirconium system oxide with sulfuric acid to prepare a catalyst with high specific surface area and a certain pore structure, and can be used for manufacturing a zirconium system/steel slag superacid carrier with structural characteristics by utilizing the characteristics of high specific surface area, high mechanical strength and the like of the steel slag, so that the content of an active center of the catalyst is increased, the catalytic efficiency of the catalyst is improved, and the service life of the catalyst is prolonged. The carrier surface contains more Bronsted acid (B acid for short, giving proton) and Lewis acid (L acid for short, accepting electron) centers, and the carrier mainly contains L acid, so that the zirconium system/steel slag super acid carrier can provide a large amount of L acid centers, which is favorable for the adsorption of 1-hydroxy-1-phenyl-alkyl acetate on a hydrogenation catalyst and the catalytic hydrogenation of raw materials. In addition, the carrier can provide a certain amount of B acid. The B acid can effectively promote the hydrogenolysis of hydroxyl in the catalytic hydrogenation product to form a stable free radical intermediate (III), so that the selectivity of the phenethyl alcohol can be greatly improved. If the L acid content in the carrier is too large and the B acid content is too small, the hydrogenolysis reaction is not facilitated, so that the content of the 1-phenyl-1, 2-glycol in the product is higher, and the selectivity of the target product is not high; if the amount of the acid B in the carrier is too large and the amount of the acid L in the carrier is too small, the hydrogenation effect of the 1-hydroxy-1-phenyl-acetic acid alkyl ester is too low, meanwhile, the hydrogenolysis reaction is higher, and the conversion rate and the selectivity of the reaction are reduced. Therefore, the acid amount ratio of B acid to L acid is preferably 50 < L/B < 70.
The zirconium system/steel slag super acidic carrier can provide more empty tracks required by the active metal of the hydrogenation catalyst. In addition, the steel slag contains metal oxides such as calcium oxide, magnesium oxide, manganese oxide and the like, a large number of empty orbits exist due to the complex compound structure of the steel slag, electron pairs exist on ester groups in the raw materials, and the reaction selectivity of the catalyst is improved through the action between the raw materials and the steel slag.
The acid strength range H of the surface of the zirconium system/steel slag super acid carrier o <-12.36. The hydrogenation catalyst loaded with active metal and using the carrier of the invention has large surface area, strong acidity and hydrogenation performance, and is particularly suitable for hydrogenation hydrogenolysis reaction of the invention.
The zirconium system/steel slag super acidic carrier can provide a large amount of L acid centers and B acid centers, and can promote secondary alcohol to generate carbon free radical intermediate (III)
Due to the conjugated effect of the benzene ring in the structure, the free radical intermediate is easier to generate, and the target product phenethyl alcohol is obtained with high selectivity.
The acid strength of the zirconium system/steel slag super acidic carrier has a great relationship with the concentration of sulfuric acid and the roasting temperature, and the roasting temperature and the sulfuric acid concentration can be adjusted.
A preparation method of a solid super acidic supported catalyst comprises the following steps: cu (NO) 3 ) 2 The aqueous solution is mixed with a zirconium system/steel slag super acidic carrier, and the mixture is subjected to heat preservation, washing, drying, roasting, granulation and forming.
In the preparation method of the catalyst of the invention, Cu (NO) 3 ) 2 The concentration of the aqueous solution of (A) is 0.01 to 1mol/L, preferably 0.02 to 0.2 mol/L.
In the preparation method of the catalyst, the temperature for heat preservation is 60-90 ℃, and preferably 70-80 ℃.
In the preparation method of the catalyst, the heat preservation time is 18-30 h.
In the preparation method of the catalyst, the drying temperature is 100-150 ℃, and preferably 110-120 ℃.
In the preparation method of the catalyst, the roasting temperature is 350-500 ℃, preferably 350-450 ℃, and the roasting time is 5-18 hours, preferably 7-9 hours.
The solid super acidic supported catalyst has reaction activity only after reduction, the hydrogen pressure is 0-3 MPa, the reduction temperature is 180-350 ℃, and the reduction time is 6-12 hours.
A preparation method of beta-phenethyl alcohol comprises the following steps: a compound of formula II
The beta-phenethyl alcohol is subjected to hydrogenolysis reduction reaction with hydrogen in the presence of the solid super acidic supported catalyst to obtain the beta-phenethyl alcohol, wherein R represents C1-C3 alkyl.
As a preferable scheme, in the method for preparing β -phenylethyl alcohol according to the present invention, the reactor is a fixed bed reactor with an upper inlet and a lower outlet.
In the preparation method of the beta-phenethyl alcohol, the reaction temperature is 150-250 ℃, preferably 170-220 ℃, and the hydrogen pressure is 1-10 Mpa, preferably 3-7 Mpa. The molar ratio of the hydrogen to the intermediate (II) is 20-200: 1, preferably 50-100: 1; the catalyst treatment is 0.01 to 0.5g of alkyl 2-hydroxy-2-phenyl-acetate/(g of catalyst h), preferably 0.1 to 0.2g of alkyl 2-hydroxy-2-phenyl-acetate/(g of catalyst h).
In the preparation method of the beta-phenethyl alcohol, the solid super acidic supported catalyst needs to be reduced in a fixed bed before being used for catalytic hydrogenolysis reduction reaction, the reduction temperature is 200 ℃, and the hydrogen pressure is normal pressure or micro-positive pressure.
The preparation method of the compound of the formula II comprises the following steps:
1) benzaldehyde reacts with hydrocyanic acid under the action of organic amine to obtain the compound containing the formula I
A reaction solution;
2) adding the compound of formula I obtained in the step 1) into a solution containing alcohol and an acid catalyst for reaction, and then carrying out desalting treatment to obtain a compound of formula II
In the step 1), preferably, after benzaldehyde and organic amine are mixed, the temperature is kept at 10-30 ℃, hydrocyanic acid is dripped into a reaction system within 0.5-2 h or pumped into the reaction system by adopting a pump, the hydrocyanic acid is a highly toxic chemical and has a low boiling point, the hydrocyanic acid is not easy to seal in a reaction container, and the reaction speed of the hydrocyanic acid and benzaldehyde is high, so that the existence of the hydrocyanic acid in the reaction system can be reduced by adopting the sequence of adding the hydrocyanic acid into the benzaldehyde. After the hydrocyanic acid is added, keeping the temperature and continuously reacting for 0.5-1 h.
Preferably, the reaction solution obtained in the step 1) can be directly used for the next reaction.
The reaction process is as follows:
in the step 2), the compound of the formula I is preferably dropwise added into the hydrogen chloride alcohol solution at normal temperature, and after the dropwise addition is finished, the temperature is raised to the reflux temperature of the solvent, and the reflux reaction is carried out for 20-30 h.
The preparation method of the invention has the advantages that:
(1) the beta-phenethyl alcohol is obtained with low by-product, high selectivity (more than or equal to 90 percent) and high yield (more than or equal to 90 percent).
(2) The steel slag is used as a catalyst carrier, so that waste is turned into wealth, and the resource utilization rate is improved.
(3) The beta-phenethyl alcohol prepared by the method has the advantages of simple operation, small investment, high safety and easy industrial production.
Detailed Description
The present invention is further illustrated by the following examples, which should be construed as limiting the scope of the invention.
The main raw materials involved in the invention are as follows:
steel slag: the composition of the steel group comprises 5.2 wt% of ferric oxide, 39.5 wt% of calcium oxide, 9.5 wt% of magnesium oxide, 7.37 wt% of aluminum oxide, 24.48 wt% of silicon dioxide, 4.98 wt% of manganese oxide, 2.67 wt% of phosphorus pentoxide, 1.13 wt% of titanium dioxide, 4.38 wt% of vanadium pentoxide and 0.79 wt% of the rest. The particle size is 1-5 mm, and D50 is 2-4 mm.
Hydrogen chloride: zibowarida specialty gases Inc.
Benzaldehyde, triethylamine, methanol: chemical agents of the national drug group, ltd.
Hydrogen gas: dalian specialty gas Co.
4A molecular sieve: zhengzhou Tianxiang inorganic materials Co., Ltd.
CuCAT-2108T: shanghai Xuan.
The preparation of the hydrogenolysis raw material is a known process, the preparation of the hydrogenolysis raw material is divided into two steps of cyanohydrin and esterification, and the process of preparing the hydrogenolysis raw material by an experiment is as follows:
cyanohydrin: 107.19g (1.00mol, 99%) benzaldehyde and 1.02g triethylamine (0.01mol, 99%) were placed in a 250ml three-neck flask, the temperature was lowered to 10 ℃ by cold bath, and 28.41 was added by means of a advection pump
g (1.01mol, 96.09%) of hydrocyanic acid, the feed rate was 1ml/min, the reaction temperature was kept at 10 ℃, and the reaction was continued for 30min with the end of the feed, yielding 134.80g of reaction solution.
Esterification: putting 500g of methanol into a 1000ml three-neck flask, controlling the temperature of the system to be not higher than 20 ℃, slowly introducing HCl gas under stirring, and stopping introducing the HCl gas when bubbles are visible in the reaction system to obtain 815.79g of 38.71 percent hydrogen chloride methanol solution.
94.29g (containing 1.00mol of HCl) of prepared hydrogen chloride methanol solution and 106.71g of methanol are weighed and placed in a 500ml three-neck flask, 134.80g (1.00mol based on cyanohydrin) of reaction liquid obtained in the step 1) is dripped at normal temperature, after the dripping is finished, the temperature is raised to the reflux temperature of the solvent, and the reflux reaction is carried out for 24 hours.
Evaporating the above reaction solution to dryness at 70 deg.C under 0.02MPa, adding 500.00g dichloromethane, dispersing and pulping, filtering under reduced pressure under 0.03MPa with 50 μm filter, and distilling the filtrate to remove dichloromethane. 165.31g of the heavies containing the compound of formula II were obtained with a gas chromatography purity of greater than 98.5%.
The gas chromatography analysis used in the examples of the present invention was performed according to the following method: 30m DB-WAX, ID.: 0.32mm, FD.: 0.25 μm; 80-230 ℃, 3 ℃/min, nitrogen flow rate: 30mL/min, hydrogen flow rate: 40mL/min, air flow rate: 400 mL/min; sample introduction amount: 0.2. mu.L. GC was tested using Agilent7820 and samples were diluted 3-fold with chromatographic methanol.
Infrared was tested using Nicolet Nexus 470.
The acid amount ratio of B acid to L acid in the carrier (denoted as L/B) was determined by the following method: removing adsorbed water from the carrier to be detected, performing physical and chemical adsorption with pyridine, desorbing the physically adsorbed pyridine at 300 deg.C under vacuum, and measuring infrared spectrum and L acid center (1446.2 cm) -1 ) B acid center (1546.2 cm) -1 ) And L/B is the ratio of the peak areas of the infrared spectrogram.
Acid strength H o The measurement method (3) comprises: a small amount of an indicator B (m-nitrotoluene, a very weak base) is added to the sample to be measured, the conjugate acid BH formed after B binds to a proton + Having different colours, [ B ] at equilibrium according to acid-base reaction]/[BH + ]Value, then H can be obtained 0 ：H 0 ＝P K BH+ -lg([BH + ]/[B])
P K BH+ ＝-lg(K BH+ )
In the formula, K BH+ Is a chemical reaction BH + →B+H + Is constant.
Preparation of the carrier:
ZrOCl 2 ·8H 2 Dissolving O in water, adding steel slag or a 4A molecular sieve after the O is completely dissolved, and dipping; and then in a quantity of aqueous ammonium carbonate solution. The precipitate is filtered off with suction and washed with a large amount of distilled water until free from chloride ions and dried at 110 ℃. And (3) soaking the dried solid sulfuric acid, drying at 110 ℃, and roasting to obtain the zirconium system/steel slag super acidic carrier.
The preparation conditions and results for the different carriers are shown in table 1.
TABLE 1 preparation conditions and results for different supports
Catalyst preparation
According to the proportion in the table 2, the salt of the active metal is prepared into a solution, the active metal is impregnated on the carrier by adopting an impregnation method, then the carrier is dried for 24 hours, and is pressed into a strip for molding, and the carrier is dried for a period of time at a certain temperature for later use. Specific preparation conditions and results are shown in Table 2.
TABLE 2 catalyst preparation conditions and results
Example 1
The hydrogenolysis reaction is carried out in a fixed bed reactor, the reactor is a stainless steel tube type reactor, the inner diameter is 25mm, and the length is 1000 mm; the reactor was charged with 100ml (85.62g) of catalyst 1.
Introducing nitrogen under normal pressure, slowly heating to 200 ℃, then introducing hydrogen, controlling the ratio of nitrogen to hydrogen to be 500:1 at the initial stage of the activation stage, increasing the ratio of hydrogen to 400:1 after 2 hours, increasing the ratio of hydrogen to 300:1 after 4 hours, increasing the ratio of hydrogen to 200:1 after 6 hours, increasing the ratio of hydrogen to 100:1 after 7 hours, increasing the ratio of hydrogen to 50:1 after 8 hours, increasing the ratio of hydrogen to 20:1 after 9 hours, and finally closing the nitrogen, wherein no temperature rise indicates that the activation is finished, and the activation time is 10 hours.
Continuously feeding heavy components containing the compound of the formula II through a feed pump, wherein the liquid air speed WHSV is 0.10g/gcat/h, the molar ratio of hydrogen to the compound of the formula II is 50:1, the hydrogenation reaction temperature is 170 ℃, and the hydrogenation reaction pressure is 7 MPa. The reaction solution was sampled and subjected to GC analysis, and the reaction conversion rate reached 99.4% and the selectivity of beta-phenylethyl alcohol reached 96.3%.
Example 2
Hydrogenolysis step catalyst 2 was used and the catalyst was activated as in example 1. Continuously feeding heavy components containing the compound of the formula II through a feed pump, wherein the liquid air speed WHSV is 0.2g/gcat/h, the molar ratio of hydrogen to the compound of the formula II is 100:1, the hydrogenation reaction temperature is 220 ℃, and the hydrogenation reaction pressure is 7 MPa. The reaction solution was sampled and subjected to GC analysis, and the reaction conversion rate reached 99.7% and the selectivity of beta-phenylethyl alcohol reached 95.8%.
Example 3
The hydrogenolysis step catalyst was catalyst 3 and the catalyst activation was the same as in example 1. Continuously feeding heavy components containing the compound of the formula II through a feed pump, wherein the liquid air speed WHSV is 0.15g/gcat/h, the molar ratio of hydrogen to the compound of the formula II is 75:1, the hydrogenation reaction temperature is 200 ℃, and the hydrogenation reaction pressure is 5 MPa. The reaction solution was sampled and subjected to GC analysis, and the reaction conversion rate reached 99.0% and the selectivity of beta-phenylethyl alcohol reached 96.9%.
Example 4
Hydrogenolysis step catalyst 4 was used and the catalyst was activated as in example 1. Continuously feeding heavy components containing the compound of the formula II through a feed pump, wherein the liquid air speed WHSV is 0.15g/gcat/h, the molar ratio of hydrogen to the compound containing the formula II is 80:1, the hydrogenation reaction temperature is 180 ℃, and the hydrogenation reaction pressure is 7 MPa. The reaction solution was sampled and subjected to GC analysis, and the reaction conversion rate reached 99.2% and the selectivity of beta-phenylethyl alcohol reached 96.6%.
Example 5
Hydrogenolysis step catalyst 5 was used and the catalyst was activated as in example 1. Continuously feeding heavy components containing the compound of the formula II through a feed pump, wherein the liquid air speed WHSV is 0.2/gcat/h, the molar ratio of hydrogen to the compound containing the formula II is 100:1, the hydrogenation reaction temperature is 220 ℃, and the hydrogenation reaction pressure is 5 MPa. The reaction solution was sampled and subjected to GC analysis, and the reaction conversion rate reached 99.3% and the selectivity of beta-phenylethyl alcohol reached 96.1%.
Example 6
The hydrogenolysis step catalyst was catalyst 6 and the catalyst activation was the same as in example 1. Continuously feeding heavy components containing the compound shown in the formula II through a feed pump, wherein the liquid air speed WHSV is 0.1g/gcat/h, the molar ratio of hydrogen to the compound shown in the formula II is 50:1, the hydrogenation reaction temperature is 170 ℃, and the hydrogenation reaction pressure is 7 MPa. The reaction solution was sampled and subjected to GC analysis, and the reaction conversion rate reached 99.1% and the selectivity of beta-phenylethyl alcohol reached 95.9%.
Comparative example 1
Hydrogenolysis step the catalyst was comparative catalyst 1, and the catalyst was tested in the same manner as in example 1 to have a reaction conversion of 99.2% and a selectivity to beta-phenylethyl alcohol of 10.6%.
Comparative example 2
Hydrogenolysis step catalyst was comparative catalyst 2, and the catalyst was tested in the same manner as in example 1 to have a reaction conversion of 99.3% and a selectivity to beta-phenylethyl alcohol of 47.6%.
Comparative example 3
Hydrogenolysis step catalyst was comparative catalyst 3, which was tested in the same manner as in example 1 and had a reaction conversion of 99.0% and a selectivity to beta-phenylethyl alcohol of 86.5%.
Comparative example 4
The catalyst in the hydrogenolysis step was CuCAT-2108T, and the catalyst was tested according to the same method as in example 1, and the reaction conversion was 99.1% and the selectivity to β -phenylethyl alcohol was 3.7%.
Claims (10)
1. A solid super acidic supported catalyst comprises an active component copper and a carrier, wherein the carrier is zirconium system/steel slag super acidic.
2. The solid superacid supported catalyst according to claim 1, wherein the solid superacid supported catalyst comprises copper as an active component in an amount of 0.1 to 60% by mass, preferably 1 to 30% by mass, more preferably 5 to 25% by mass, calculated as CuO, based on the total mass of the catalyst.
3. The solid super acidic supported catalyst of claim 1 or 2, wherein the method for preparing the zirconium based/steel slag super acidic comprises the following steps:
1) ZrOCl 2 ·8H 2 Dissolving O in water, adding steel slag for impregnation, adding an ammonium carbonate aqueous solution, separating, washing and drying;
2) dipping with sulfuric acid, drying and roasting.
4. The solid superacid supported catalyst according to claim 3, wherein in the step 1), the impregnation time is 1 to 2 hours; said ZrOCl 2 ·8H 2 After O is dissolved in water, ZrOCl 2 The concentration of (b) is 0.001-0.2 g/mL, preferably 0.01-0.1 g/mL; the mass of the steel slag is ZrOCl 2 ·8H 2 2.5-3 times of the mass of O.
5. The solid superacid supported catalyst according to claim 3, wherein in the step 2), the concentration of the sulfuric acid is 1 to 2 mol/L; the dipping time is 2-4 h; the roasting temperature is 500-600 ℃, and the roasting time is 2-4 h.
6. The solid superacid supported catalyst according to claim 3, wherein in the step 2), the steel slag comprises, by mass, 100% of iron oxide 2-8 wt%, calcium oxide 30-50 wt%, magnesium oxide 8-12 wt%, aluminum oxide 7-9 wt%, silicon dioxide 20-32 wt%, manganese oxide 2-5 wt%, phosphorus pentoxide 1-4 wt%, titanium dioxide 0.8-3 wt%, vanadium pentoxide 3-6 wt%, and others 0.05-1 wt%.
7. The solid super acidic supported catalyst according to claim 3, wherein in the zirconium based/steel slag super acidic, the acid amount ratio of B acid to L acid is preferably 50 < L/B < 70; acid strength range H of surface o <-12.36。
8. The solid super acidic supported catalyst according to claim 1, wherein the method for preparing the solid super acidic supported catalyst comprises the steps of: cu (NO) 3 ) 2 The aqueous solution is mixed with a zirconium system/steel slag super acidic carrier, and the mixture is subjected to heat preservation, washing, drying, roasting, granulation and forming.
9. The solid superacid supported catalyst according to claim 8, characterized in that Cu (NO) 3 ) 2 The concentration of the aqueous solution of (a) is 0.01 to 1mol/L, preferably 0.02 to 0.2 mol/L; the temperature for heat preservation is 60-90 ℃, and preferably 70-80 ℃; the heat preservation time is 18-30 h; the roasting temperature is 350-500 ℃, preferably 350-450 ℃, and the roasting time is 5-18 hours, preferably 7-9 hours.
10. Beta-phenethyl alcoholThe preparation method comprises the following steps: a compound of formula II
Carrying out hydrogenolysis reduction reaction with hydrogen in the presence of the solid super acidic supported catalyst of any one of claims 1 to 9 to obtain beta-phenylethyl alcohol, wherein R represents C1-C3 alkyl.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU95107363A (en) * | 1995-05-06 | 1996-08-10 | Акционерное общество открытого типа "Научно-исследовательский и проектный институт мономеров с опытным заводом" | Modified nickel catalyst on carrier for hydrogenation and method of its production |
| CN101747150A (en) * | 2008-12-11 | 2010-06-23 | 中科合成油技术有限公司 | Method for producing 1,3-propanediol |
| US20130245348A1 (en) * | 2010-03-15 | 2013-09-19 | Total Research & Technology Feluy | Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis |
| US20140330047A1 (en) * | 2011-12-15 | 2014-11-06 | Council Of Scientific And Industrial Research | Hydrogenation of styrene oxide forming 2-phenyl ethanol |
| CN104557777A (en) * | 2015-01-09 | 2015-04-29 | 万华化学集团股份有限公司 | Preparation method of N-methyl piperazine |
| CN107486241A (en) * | 2017-07-05 | 2017-12-19 | 万华化学集团股份有限公司 | A kind of magnetic nano solid acid catalyst and preparation method thereof, the method that 1 benzyl carbinol dehydration prepares styrene is catalyzed using it |
| CN108473484A (en) * | 2015-10-01 | 2018-08-31 | 赛诺米克斯公司 | It can be used as the compound of TRPM8 conditioning agents |
| CN108654635A (en) * | 2017-03-29 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of support type trimetallic catalyst and preparation method thereof and hydrogenolysis catalysis of glycerin reaction method |
| CN112403487A (en) * | 2020-11-22 | 2021-02-26 | 浙江盛旺环境工程有限公司 | Medium-low temperature vanadium-free desulfurization and denitrification catalyst and preparation method thereof |
| CN114160116A (en) * | 2021-11-08 | 2022-03-11 | 万华化学集团股份有限公司 | Steel slag-based zirconium catalyst, preparation method and application of steel slag-based zirconium catalyst in preparation of 1, 4-butanediol and coproduction of methacrolein |
-
2022
- 2022-04-01 CN CN202210348756.XA patent/CN114849679B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU95107363A (en) * | 1995-05-06 | 1996-08-10 | Акционерное общество открытого типа "Научно-исследовательский и проектный институт мономеров с опытным заводом" | Modified nickel catalyst on carrier for hydrogenation and method of its production |
| CN101747150A (en) * | 2008-12-11 | 2010-06-23 | 中科合成油技术有限公司 | Method for producing 1,3-propanediol |
| US20130245348A1 (en) * | 2010-03-15 | 2013-09-19 | Total Research & Technology Feluy | Production of propylene via simultaneous dehydration and skeletal isomerisation of isobutanol on acid catalysts followed by metathesis |
| US20140330047A1 (en) * | 2011-12-15 | 2014-11-06 | Council Of Scientific And Industrial Research | Hydrogenation of styrene oxide forming 2-phenyl ethanol |
| CN104557777A (en) * | 2015-01-09 | 2015-04-29 | 万华化学集团股份有限公司 | Preparation method of N-methyl piperazine |
| CN108473484A (en) * | 2015-10-01 | 2018-08-31 | 赛诺米克斯公司 | It can be used as the compound of TRPM8 conditioning agents |
| CN108654635A (en) * | 2017-03-29 | 2018-10-16 | 中国石油化工股份有限公司 | A kind of support type trimetallic catalyst and preparation method thereof and hydrogenolysis catalysis of glycerin reaction method |
| CN107486241A (en) * | 2017-07-05 | 2017-12-19 | 万华化学集团股份有限公司 | A kind of magnetic nano solid acid catalyst and preparation method thereof, the method that 1 benzyl carbinol dehydration prepares styrene is catalyzed using it |
| CN112403487A (en) * | 2020-11-22 | 2021-02-26 | 浙江盛旺环境工程有限公司 | Medium-low temperature vanadium-free desulfurization and denitrification catalyst and preparation method thereof |
| CN114160116A (en) * | 2021-11-08 | 2022-03-11 | 万华化学集团股份有限公司 | Steel slag-based zirconium catalyst, preparation method and application of steel slag-based zirconium catalyst in preparation of 1, 4-butanediol and coproduction of methacrolein |
Non-Patent Citations (1)
| Title |
|---|
| 李谦和, 尹笃林: "氧化苯乙烯液相重排制苯乙醛的固体酸催化剂", 精细石油化工, no. 02, pages 40 - 43 * |
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