CN112473704A - Honeycomb metal ceramic bifunctional catalyst, application thereof and method for preparing hydroxycitronellal - Google Patents
Honeycomb metal ceramic bifunctional catalyst, application thereof and method for preparing hydroxycitronellal Download PDFInfo
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- CN112473704A CN112473704A CN202011294226.9A CN202011294226A CN112473704A CN 112473704 A CN112473704 A CN 112473704A CN 202011294226 A CN202011294226 A CN 202011294226A CN 112473704 A CN112473704 A CN 112473704A
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- Prior art keywords
- oxide
- catalyst
- hydroxycitronellal
- reaction
- dehydrogenation
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- WPFVBOQKRVRMJB-UHFFFAOYSA-N hydroxycitronellal Chemical compound O=CCC(C)CCCC(C)(C)O WPFVBOQKRVRMJB-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000000034 method Methods 0.000 title claims abstract description 35
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 29
- 239000002184 metal Substances 0.000 title claims abstract description 29
- 239000000919 ceramic Substances 0.000 title claims abstract description 25
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 229910052588 hydroxylapatite Inorganic materials 0.000 claims abstract description 10
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 9
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 9
- 238000001125 extrusion Methods 0.000 claims abstract description 8
- 238000005469 granulation Methods 0.000 claims abstract description 8
- 230000003179 granulation Effects 0.000 claims abstract description 8
- 239000007921 spray Substances 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- -1 platinum group metals Chemical class 0.000 claims description 17
- 239000002202 Polyethylene glycol Substances 0.000 claims description 16
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 16
- 229920001223 polyethylene glycol Polymers 0.000 claims description 16
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 10
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007791 liquid phase Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000005751 Copper oxide Substances 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 229910000431 copper oxide Inorganic materials 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- UPEMFLOMQVFMCZ-UHFFFAOYSA-N [O--].[O--].[O--].[Pm+3].[Pm+3] Chemical compound [O--].[O--].[O--].[Pm+3].[Pm+3] UPEMFLOMQVFMCZ-UHFFFAOYSA-N 0.000 claims description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000292 calcium oxide Substances 0.000 claims description 2
- 229920002301 cellulose acetate Polymers 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229920000609 methyl cellulose Polymers 0.000 claims description 2
- 239000001923 methylcellulose Substances 0.000 claims description 2
- 235000010981 methylcellulose Nutrition 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- 239000011787 zinc oxide Substances 0.000 claims description 2
- 239000011195 cermet Substances 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 10
- 230000018044 dehydration Effects 0.000 abstract description 9
- 238000006297 dehydration reaction Methods 0.000 abstract description 9
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- 230000008021 deposition Effects 0.000 abstract description 7
- 238000007086 side reaction Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 3
- 208000012839 conversion disease Diseases 0.000 abstract description 2
- NEHNMFOYXAPHSD-UHFFFAOYSA-N beta-citronellal Natural products O=CCC(C)CCC=C(C)C NEHNMFOYXAPHSD-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 13
- 229930003633 citronellal Natural products 0.000 description 12
- 235000000983 citronellal Nutrition 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 8
- QMVPMAAFGQKVCJ-UHFFFAOYSA-N Citronellol Natural products OCCC(C)CCC=C(C)C QMVPMAAFGQKVCJ-UHFFFAOYSA-N 0.000 description 7
- QMVPMAAFGQKVCJ-SNVBAGLBSA-N (R)-(+)-citronellol Natural products OCC[C@H](C)CCC=C(C)C QMVPMAAFGQKVCJ-SNVBAGLBSA-N 0.000 description 6
- JGQFVRIQXUFPAH-UHFFFAOYSA-N beta-citronellol Natural products OCCC(C)CCCC(C)=C JGQFVRIQXUFPAH-UHFFFAOYSA-N 0.000 description 6
- 235000000484 citronellol Nutrition 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 5
- 230000008016 vaporization Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003205 fragrance Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 235000013599 spices Nutrition 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000020477 pH reduction Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000012459 cleaning agent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 235000013355 food flavoring agent Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003509 tertiary alcohols Chemical group 0.000 description 1
Classifications
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- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
- B01J27/1802—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates
- B01J27/1806—Salts or mixtures of anhydrides with compounds of other metals than V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, e.g. phosphates, thiophosphates with alkaline or alkaline earth metals
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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- 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
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/894—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- 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
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- 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
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- Chemical & Material Sciences (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a honeycomb metal ceramic bifunctional catalyst, application thereof and a method for preparing hydroxycitronellal. The catalyst is prepared by mixing hydroxyapatite, a catalytic active component 1, a catalytic active component 2, rare earth oxide powder and a pore-forming agent according to a certain proportion, and performing spray granulation, extrusion molding and vacuum sintering. The catalyst has the characteristics of good heat resistance, multiple holes, large specific surface area and the like, and simultaneously couples dehydrogenation and oxidation reactions, so that the dehydrogenation reaction continuously moves in the positive direction, the occurrence of dehydration side reaction is avoided, and the reaction conversion rate and the selectivity are improved. The reaction can be carried out under normal pressure, and simultaneously the high-temperature steam generated by oxidation can effectively remove carbon deposition on the surface of the catalyst, thereby reducing the generation of high polymers and effectively prolonging the service life of the catalyst.
Description
Technical Field
The invention belongs to the field of organic synthesis, and particularly relates to a honeycomb metal ceramic bifunctional catalyst and a method for preparing hydroxycitronellal through dehydrogenization of hydroxycitronellal.
Background
Hydroxycitronellal is an important artificially synthesized spice, is colorless and viscous liquid, has sweet lily-of-the-valley-like fragrance, is a traditional and extremely valuable synthesized spice, has elegant and fresh fragrance, can interact with various fresh, sweet, fresh and delicate fragrance notes, is a main component for preparing the lily-of-the-valley-type spice, and is mainly applied to the fields of perfumes, cosmetics, food flavoring agents, cleaning agents and the like.
At present, the production process of the hydroxyl citronellal mainly comprises two major types, one is that the hydroxyl citronellal is prepared by taking the citronellal as a raw material through carbonyl protection, hydration and carbonyl deprotection; the other type is that the hydroxyl citronellal is prepared by catalytic dehydrogenation of the hydroxyl citronellol serving as a raw material.
The sodium bisulfite method and the diethanolamine method which take citronellal as raw materials are the main production methods at present in China, but the two methods both adopt sulfuric acid as an acidification catalyst in the acidification process, generate a large amount of waste water which is difficult to treat in the production process, and have serious environmental pollution; meanwhile, the corrosion to equipment is serious, and certain difficulty is brought to production.
The main catalyst for preparing hydroxycitronellal by catalytic dehydrogenation with hydroxycitronellal as raw material is metal and its oxide. U.S. Pat. No. 3, 3940446A reports a catalytic dehydrogenation method of hydroxycitronellal, which utilizes home-made copper oxide catalyst suspended in high boiling point solvent, and hydroxycitronellal is fed semi-continuously and reacted under the conditions of high temperature of 280 ℃ and vacuum of 15kPa, the reaction selectivity is 88.5%, and the conversion rate is 55.6%. However, the semi-continuous high-temperature operation of the method is only suitable for small-dose reaction, high polymers generated by the reaction are enriched in a solvent and catalyst system, the catalyst is easy to inactivate, and the post-treatment is complicated. Chinese patent CN108892607A reports a method for preparing hydroxycitronellal by dehydrogenation of hydroxycitronellal under the catalysis of zeolite-supported alkali metal oxide as dehydrogenation catalyst, wherein the method controls the reaction temperature to be 150-220 ℃, the vacuum degree of the reaction system to be 5-20kpa, the reaction conversion rate to be 88-97% and the selectivity to be 86-99%. Compared with the previously reported method, the method has the advantages that the conversion rate and the selectivity are improved, but the method still needs to carry out catalytic dehydrogenation under vacuum, the reaction conditions are harsh, and when the reaction temperature is increased, the conversion rate is increased, but the reaction selectivity is reduced, more byproducts are generated, and the subsequent separation operation and the aroma quality of the product are influenced. In the process of preparing the hydroxycitronellal by dehydrogenizing the hydroxycitronellal, main byproducts are citronellal, citronellol, rhodinol and high polymer, particularly when the catalyst is acidic or neutral, a tertiary alcohol part is easy to generate a dehydration side reaction, and the proportion of the byproducts is obviously increased.
The dehydrogenation reaction is a reversible reaction, so that the conversion rate of the dehydrogenation process reported at present is below 97%, dehydrogenation needs to be carried out under high-temperature and vacuum conditions, the operation conditions are severe, certain difficulty is brought to industrial production, and meanwhile, the generation of various dehydration byproducts is often accompanied in the dehydrogenation process, so that the aroma quality of products is greatly influenced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a honeycomb metal ceramic bifunctional catalyst, application thereof and a method for preparing hydroxycitronellal. The catalyst is coupled with the activities of dehydrogenation and oxidation reactions, so that the dehydrogenation reaction continuously moves in the positive direction, and the conversion rate and the selectivity of the reaction are improved. The high-temperature water vapor generated in the reaction system for preparing the hydroxycitronellal can effectively remove carbon deposition on the surface of the catalyst, prolong the service life of the catalyst and reduce the generation of high polymers.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a honeycomb metal ceramic bifunctional catalyst is prepared from the following raw materials in parts by mass:
the catalytic active component 1 is one or more of copper oxide, zinc oxide, chromium oxide, calcium oxide, zirconium oxide, sodium oxide and nickel oxide, preferably one or more of copper oxide, nickel oxide, zirconium oxide and chromium oxide.
The catalytic active component 2 of the invention is one or more of platinum group metals such as palladium, platinum, ruthenium and rhodium, preferably palladium and/or platinum.
The rare earth oxide powder is one or more of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide and promethium oxide, and lanthanum oxide and/or cerium oxide are preferred.
The pore-forming agent is one or more of polyethylene glycol, polyvinyl alcohol, methyl cellulose, cellulose acetate and graphite, and preferably polyethylene glycol and/or polyvinyl alcohol.
The preparation method of the honeycomb metal ceramic bifunctional catalyst comprises the following steps: mixing hydroxyapatite, a catalytic active component 1, a catalytic active component 2, rare earth oxide powder and a pore-forming agent according to the proportion, performing spray granulation after ball milling is uniform, performing extrusion forming, drying, performing vacuum liquid phase sintering at the sintering temperature of 700 plus materials and 900 ℃, preserving heat for 60-120min, and cooling to room temperature along with a furnace to obtain the honeycomb metal ceramic bifunctional catalyst.
The honeycomb metal ceramic bifunctional catalyst is used as a catalyst for preparing hydroxycitronellal from hydroxycitronellal.
A method for preparing hydroxycitronellal from hydroxycitronellal comprises the following steps: in a fixed bed filled with the honeycomb metal ceramic bifunctional catalyst, vaporized hydroxycitronellal, oxygen and nitrogen are mixed and then enter the fixed bed to perform dehydrogenation-oxidation reaction to obtain hydroxycitronellal.
The temperature of the dehydrogenation-oxidation reaction is 150-180 ℃.
The absolute pressure of the dehydrogenation-oxidation reaction system is controlled to be 0.95bar-1.05 bar.
The mass space velocity of the hydroxyl citronellol of the dehydrogenation-oxidation reaction is 1-20h-1Preferably 5-10h-1。
The molar ratio of the nitrogen to the hydroxycitronellal is 4:1-10: 1.
The molar ratio of the oxygen to the hydroxycitronellal is 1.05:1-1.25: 1.
The honeycomb metal ceramic bifunctional catalyst adopted by the invention has the characteristics of porous holes and large specific surface area, so that the surface area of the catalyst in unit volume is increased, the contact time of gas and the catalyst is greatly increased, and the reaction efficiency is improved; more importantly, the catalyst has dual functions of catalytic dehydrogenation and catalytic oxidation, the hydroxyl citronellol is subjected to catalytic dehydrogenation under the action of the catalytic active component 1 to generate hydroxyl citronellal and hydrogen, meanwhile, the generated hydrogen reacts with oxygen in a system to generate water under the catalysis of the catalytic active component 2, and the coupling of dehydrogenation-oxidation reaction enables the dehydrogenation reversible reaction to continuously move towards the direction of generating the hydroxyl citronellal, so that the conversion rate of the dehydrogenation reaction is greatly improved, and the catalytic efficiency of the process is greatly improved. The hydroxyapatite and the rare earth oxide have the functions of improving the catalytic oxidation performance of platinum group metals and stabilizing the catalyst framework structure, and the addition of the hydroxyapatite and the rare earth oxide improves the charge distribution and the alkaline environment on the surface of the catalyst, avoids the occurrence of dehydration side reaction, and improves the selectivity of the reaction while ensuring high conversion rate. The addition of nitrogen in the reaction system reduces the steam partial pressure of the hydroxycitronellal in the system, namely, the boiling point of the hydroxycitronellal in the system is reduced, so that the hydroxycitronellal can be completely vaporized when the reaction system is at normal pressure, the dehydrogenation reaction under normal pressure is realized, the temperature required by the reaction is also reduced, and the carbon deposition on the surface of the catalyst is reduced; meanwhile, the high-temperature steam generated by the reaction can effectively remove carbon deposition on the surface of the catalyst, the generation of high polymers is greatly reduced, the service life of the catalyst is effectively prolonged, and the catalyst does not lose carbon deposition when continuously running in a fixed bed for more than 3500 h.
The reaction equation is as follows:
compared with the prior art, the process method of the invention utilizes the honeycomb metal ceramic bifunctional catalyst to perform the hydroxyl citronellol dehydrogenation reaction to prepare the hydroxyl citronellal, and has the positive effects that:
1) the honeycomb metal ceramic bifunctional catalyst couples the activities of dehydrogenation and oxidation reactions, so that the dehydrogenation reaction continuously moves in the forward direction, the conversion rate of the dehydrogenation reaction is greatly improved, meanwhile, the addition of hydroxyapatite and rare earth oxide avoids the occurrence of dehydration side reaction, and the reaction selectivity is greatly improved; the conversion rate and the selectivity of the process method are respectively more than 99% and more than 99.5%.
2) The addition of nitrogen in the reaction system reduces the boiling point of the hydroxycitronellal, gets rid of the limitation of 'vacuum reaction conditions' in the traditional process, and realizes the preparation of hydroxycitronellal by the dehydrogenation reaction of the hydroxycitronellal under normal pressure.
3) The high-temperature steam generated in the reaction system can effectively remove carbon deposition on the surface of the catalyst, prolong the service life of the catalyst by more than 3500h, and greatly reduce the generation of high polymers.
4) The gas-solid reaction is simple to operate and can be continuously produced in large quantities; no solvent is added in the reaction, no waste water is generated, zero emission is realized, and the environment-friendly concept is met.
Detailed Description
The technical solutions of the present invention are further described below, but not limited thereto, and modifications or equivalent substitutions may be made to the technical solutions of the present invention without departing from the scope of the technical solutions of the present invention.
Gas chromatography conditions:
the chromatographic type is as follows: agilent WAX 1701.42249
Carrier gas: high purity nitrogen gas
Sample introduction mode: automatic sample injector
Nitrogen flow rate: 65.0ml/min
Vaporization chamber temperature: 230 deg.C
Split-flow sample introduction, split-flow ratio: 1: 40
Sample introduction amount: 0.1. mu.l
Column flow rate 2.0ml/min
Column temperature: first-order temperature programming, wherein the initial temperature is 80 ℃, the temperature is kept for 2 minutes, then the temperature is raised to 230 ℃ at the speed of 15 ℃/min, and the temperature is kept for 8 minutes; the total operation time is 20min
The detector temperature was 250 deg.C
And (4) selecting an external standard method for quantification.
Specific surface area test method: the measurement is carried out by adopting a low-temperature nitrogen adsorption method.
Pore volume test method: measured by Archimedes drainage method.
Example 1
Preparing a honeycomb metal ceramic bifunctional catalyst: mixing hydroxyapatite, copper oxide powder, palladium powder, lanthanum oxide powder and polyethylene glycol (PEG4000) according to the ratio of 40:50:10:5:6, performing spray granulation after ball milling is uniform, performing extrusion forming, drying, performing vacuum liquid phase sintering at the sintering temperature of 800 ℃, keeping the temperature for 60min, and cooling to room temperature along with the furnace to obtain the honeycomb metal ceramic dual-function catalyst, wherein the specific surface area of the catalyst is 31.2m2Pore volume 0.23 mL/g.
Preparing hydroxyl citronellal by dehydrogenation-oxidation reaction: 100g of honeycomb metal ceramic catalyst particles are filled in a fixed bed, heat conduction oil is used for heating the fixed bed to the reaction temperature of 150 ℃, and the pressure of a reaction system is regulated to be 1.00 bar. The method comprises the following steps of pumping hydroxyl citronellol into a vaporization chamber at the flow rate of 8.3g/min by using a metering pump for vaporization, feeding nitrogen into the vaporization chamber at the speed of 10.7L/min for preheating, feeding oxygen into the vaporization chamber at the speed of 1.1L/min for preheating, mixing the nitrogen, the nitrogen and the oxygen, feeding the mixture into the upper end of a fixed bed reactor, carrying out catalytic dehydrogenation-oxidation reaction in the fixed bed reactor, outputting materials from the lower end of the fixed bed reactor, cooling the materials by using a cooler to obtain a product hydroxyl citronellal, carrying out gas chromatography analysis on the product, and measuring that the conversion rate of raw materials is 99.5%, the selectivity of the product hydroxyl citronellal is 99.7%, no dehydration byproduct is generated, and the high.
Examples 2 to 6
The catalyst preparation and the hydroxycitronellal preparation were carried out according to the procedure of example 1, and the corresponding preparation parameters and reaction results are shown in tables 1 and 2, and in examples 2-6, no dehydration by-product was produced and the high polymer was < 0.01%.
TABLE 1 catalyst preparation conditions
Note: in examples 2-6, the polyethylene glycol was PEG4000 and the polyvinyl alcohol was PVA4000
TABLE 2 dehydrogenation reaction conditions and results
The life examination of the catalyst in example 6 shows that the catalyst can be continuously catalyzed and operated for 3500h in a fixed bed, the conversion rate and the selectivity of the catalytic reaction can still be maintained above 99.5 percent, and carbon deposition and inactivation can not be caused.
Comparative example 1
Preparing a honeycomb metal ceramic catalyst: mixing copper oxide powder, palladium powder, lanthanum oxide powder and polyethylene glycol (PEG4000) according to the proportion of 50:10:5:6, carrying out spray granulation after ball milling for 4 hours, carrying out extrusion forming, drying, carrying out vacuum liquid phase sintering at the sintering temperature of 800 ℃, keeping the temperature for 60min, and then cooling to room temperature along with a furnace to obtain the hydroxyapatite-free honeycomb metal ceramic catalyst.
The preparation of hydroxycitronellal was carried out according to the operating parameters of example 1 and the product was analyzed by gas chromatography, which showed a raw material conversion of 97.6%, a product hydroxycitronellal selectivity of 98.5%, a dehydration by-product of 0.3% and a high polymer of < 0.01%.
Comparative example 2
Preparing a honeycomb metal ceramic catalyst: mixing hydroxyapatite, palladium powder, lanthanum oxide powder and polyethylene glycol (PEG4000) according to the ratio of 40:10:5:6, carrying out spray granulation after ball milling for 4 hours, carrying out extrusion forming, drying, carrying out vacuum liquid phase sintering at the sintering temperature of 800 ℃, keeping the temperature for 60min, and then cooling to room temperature along with a furnace to obtain the honeycomb metal ceramic catalyst without the active component 1.
The preparation of hydroxycitronellal was carried out according to the operating parameters of example 1, and the product was analyzed by gas chromatography with a conversion of < 1% and no detection of the dehydrogenated product hydroxycitronellal.
Comparative example 3
Preparing a honeycomb metal ceramic catalyst: mixing hydroxyapatite, copper oxide powder, lanthanum oxide powder and polyethylene glycol (PEG4000) according to the proportion of 40:50:5:6, carrying out spray granulation after ball milling for 4 hours, carrying out extrusion forming, drying, carrying out vacuum liquid phase sintering at the sintering temperature of 800 ℃, keeping the temperature for 60min, and then cooling to room temperature along with a furnace to obtain the honeycomb metal ceramic catalyst without the active component 2.
The preparation of hydroxycitronellal was carried out according to the operating parameters of example 1 and the product was analyzed by gas chromatography, which showed a raw material conversion of 83.9%, a product hydroxycitronellal selectivity of 98.3% and a high polymer of 0.87%.
Comparative example 4
Preparing a honeycomb metal ceramic catalyst: mixing hydroxyapatite, copper oxide powder, palladium powder and polyethylene glycol (PEG4000) according to the proportion of 40:50:10:6, carrying out spray granulation after ball milling for 4 hours, carrying out extrusion forming, drying, carrying out vacuum liquid phase sintering at the sintering temperature of 800 ℃, keeping the temperature for 60min, and then cooling to room temperature along with a furnace to obtain the honeycomb metal ceramic catalyst without rare earth oxide.
The preparation of hydroxycitronellal was carried out according to the operating parameters of example 1 and the product was analyzed by gas chromatography, which showed a raw material conversion of 98.1%, a product hydroxycitronellal selectivity of 98.3%, a dehydration by-product of 0.5% and a high polymer of < 0.01%.
Claims (10)
1. A honeycomb metal ceramic bifunctional catalyst is prepared from the following raw materials in parts by mass:
the catalytic active component 1 is one or more of copper oxide, zinc oxide, chromium oxide, calcium oxide, zirconium oxide, sodium oxide and nickel oxide, preferably one or more of copper oxide, nickel oxide, zirconium oxide and chromium oxide;
the catalytic active component 2 is one or more of platinum group metals such as palladium, platinum, ruthenium and rhodium, and is preferably palladium and/or platinum.
2. The catalyst according to claim 1, wherein the rare earth oxide powder is one or more of lanthanum oxide, cerium oxide, praseodymium oxide, neodymium oxide, promethium oxide, preferably lanthanum oxide and/or cerium oxide.
3. The catalyst according to claim 1, wherein the pore-forming agent is one or more of polyethylene glycol, polyvinyl alcohol, methyl cellulose, cellulose acetate and graphite, preferably polyethylene glycol and/or polyvinyl alcohol.
4. A catalyst according to any one of claims 1 to 3, characterized in that the catalyst preparation process comprises the following steps: mixing hydroxyapatite, a catalytic active component 1, a catalytic active component 2, rare earth oxide powder and a pore-forming agent according to the proportion, performing spray granulation after ball milling is uniform, performing extrusion forming, drying, performing vacuum liquid phase sintering at the sintering temperature of 700-900 ℃, preserving heat for 60-120min, and cooling to room temperature along with the furnace.
5. Use of a catalyst according to any one of claims 1 to 4 for the preparation of hydroxycitronellal from hydroxycitronell.
6. A method for preparing hydroxycitronellal from hydroxycitronellal comprises the following steps: in a fixed bed filled with the honeycomb cermet bifunctional catalyst as claimed in any one of claims 1 to 4, vaporized hydroxycitronellal is mixed with oxygen and nitrogen and then introduced into the fixed bed to undergo dehydrogenation-oxidation reaction to obtain hydroxycitronellal.
7. The method as claimed in claim 6, wherein the dehydrogenation reaction is carried out at a reaction temperature of 150 ℃ to 180 ℃.
8. The process according to claim 6, wherein the mass space velocity of the dehydrogenation reaction is 1 to 20h-1Preferably 5-10h-1。
9. The method of claim 6, wherein the molar ratio of nitrogen to starting hydroxycitronellal is from 4:1 to 10: 1.
10. The method of claim 6, wherein the molar ratio of oxygen to starting hydroxycitronellal is from 1.05:1 to 1.25: 1.
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