CN114849769A - 合成百里香酚用催化剂及其制备方法与应用 - Google Patents
合成百里香酚用催化剂及其制备方法与应用 Download PDFInfo
- Publication number
- CN114849769A CN114849769A CN202210443773.1A CN202210443773A CN114849769A CN 114849769 A CN114849769 A CN 114849769A CN 202210443773 A CN202210443773 A CN 202210443773A CN 114849769 A CN114849769 A CN 114849769A
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- Prior art keywords
- catalyst
- thymol
- oxide
- molecular sieve
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000005844 Thymol Substances 0.000 title claims abstract description 45
- 229960000790 thymol Drugs 0.000 title claims abstract description 45
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002808 molecular sieve Substances 0.000 claims abstract description 30
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000001035 drying Methods 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 8
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 7
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 7
- 229920002472 Starch Polymers 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000008107 starch Substances 0.000 claims abstract description 7
- 235000019698 starch Nutrition 0.000 claims abstract description 7
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims abstract description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 5
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims abstract description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000005751 Copper oxide Substances 0.000 claims abstract description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 4
- 229960000892 attapulgite Drugs 0.000 claims abstract description 4
- 239000004927 clay Substances 0.000 claims abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229920000609 methyl cellulose Polymers 0.000 claims abstract description 4
- 239000001923 methylcellulose Substances 0.000 claims abstract description 4
- 235000010981 methylcellulose Nutrition 0.000 claims abstract description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 4
- DHRLEVQXOMLTIM-UHFFFAOYSA-N phosphoric acid;trioxomolybdenum Chemical compound O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.OP(O)(O)=O DHRLEVQXOMLTIM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000088 plastic resin Substances 0.000 claims abstract description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims abstract description 4
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 4
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011787 zinc oxide Substances 0.000 claims abstract description 4
- 238000001125 extrusion Methods 0.000 claims abstract description 3
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims description 40
- 238000006243 chemical reaction Methods 0.000 claims description 24
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 15
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 244000275012 Sesbania cannabina Species 0.000 claims description 3
- 239000004088 foaming agent Substances 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010687 lubricating oil Substances 0.000 claims description 3
- 239000012188 paraffin wax Substances 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- BEFDCLMNVWHSGT-UHFFFAOYSA-N ethenylcyclopentane Chemical compound C=CC1CCCC1 BEFDCLMNVWHSGT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000004334 sorbic acid Substances 0.000 claims description 2
- 229940075582 sorbic acid Drugs 0.000 claims description 2
- 235000010199 sorbic acid Nutrition 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- 241000219793 Trifolium Species 0.000 description 4
- 238000009776 industrial production Methods 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- NOOLISFMXDJSKH-KXUCPTDWSA-N (-)-Menthol Chemical compound CC(C)[C@@H]1CC[C@@H](C)C[C@H]1O NOOLISFMXDJSKH-KXUCPTDWSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- 241000208173 Apiaceae Species 0.000 description 1
- 240000007087 Apium graveolens Species 0.000 description 1
- 235000015849 Apium graveolens Dulce Group Nutrition 0.000 description 1
- 235000010591 Appio Nutrition 0.000 description 1
- 206010012504 Dermatophytosis Diseases 0.000 description 1
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 241001460074 Microsporum distortum Species 0.000 description 1
- 208000005141 Otitis Diseases 0.000 description 1
- 201000005702 Pertussis Diseases 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 208000002474 Tinea Diseases 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 206010044302 Tracheitis Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 201000007691 actinomycosis Diseases 0.000 description 1
- 230000002152 alkylating effect Effects 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 210000004081 cilia Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 208000019258 ear infection Diseases 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 210000004877 mucosa Anatomy 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 210000003437 trachea Anatomy 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 239000010457 zeolite 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
- B01J29/0308—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41
- B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/18—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type
- B01J29/26—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the mordenite type containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
-
- 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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Abstract
本发明提供一种合成百里香酚用催化剂及其制备方法，所述催化剂包括分子筛、助剂、粘结剂；所述助剂选自氧化锌、氧化铁、磷酸、磷钼酸、氧化硅、氧化铜、氧化钼、氧化镍、氧化银中的一种或几种的组合；所述粘结剂为硅溶胶、氧化铝、天然黏土、凹凸棒土、水玻璃、甲基纤维素、聚乙烯醇、淀粉、塑料树脂、松香中的一种或几种。本发明催化剂的催化活性高、稳定性好，成本低、符合绿色化学的理念。该催化剂的制备方法将配方组分混合均匀、经挤压成型、干燥焙烧即得，工艺简单，便于产业化。
Description
技术领域
本发明涉及合成百里香酚使用的催化剂、该催化剂的制备方法以及其应用。
背景技术
百里香酚又名百里酚、麝香草酚，化学名为2-异丙基-5-甲基苯酚。常温下为无色晶体或无色结晶粉末，有百里草或麝香草的气味，天然存在于唇形科植物百里香草、麝香草、牛至草、香青兰以及伞形科植物粗果芹的种子中。百里香酚具有特殊的香气，广泛应用在香料领域。其又因具有防腐性，常用于具有药用价值的卫生品中。此外，百里香酚还可作为抗氧剂、检定氮化钛用的特殊试剂。在医药领域，百里香酚具有良好的杀菌能力，毒性低，常用于口腔咽喉粘膜的消毒杀菌、治疗皮肤癣菌病，放射菌病及耳炎等病症；百里香酚又能促进气管纤毛运动，可用于治疗气管炎、百日咳等病症。同时，百里香酚也是重要的化工中间体，是世界销量最大香料之一L-薄荷醇的主要原料。
由于自然资源有限、提取的百里香酚的品质和量也受各种因素影响，天然提取百里香酚的成本逐渐升高。随着有机合成化学技术和催化化学的发展，有机合成百里香酚逐渐取代了从天然产物中提取的百里香酚。
目前百里香酚的合成主要是以间甲酚为原料，用间甲酚和各种异丙基化试剂(如丙烯，异丙醇，2-氯丙烷等)，通过傅-克烷基化反应得到百里香酚。
在专利申请US2286953中，Marion S C.等使用A1C13作催化剂，二氯乙烷为溶剂，合成百里香酚，该方法需要使用大量的溶剂和催化剂，处理复杂，环境污染严重。
参见Res.Chem.Intermed.，2001,27(3)：281～285，Grabowska H.等使用含Cr、Si、K的氧化物的铁作为催化剂催化间甲酚和异丙醇，在693K温度下反应合成了百里香酚，间甲酚的转化率为17％，百里香酚的选择性为60％。该反应原料间甲酚的转化率较低，反应的选择性也不理想。
CN103951546A采用质子酸-路易斯酸组合物(例如，浓硫酸和三氯化铝的组合物，多聚磷酸和三氯化铝的组合物，浓硫酸和氯化锌的组合物或是多聚磷酸和氯化锌的组合物)为催化剂，以间甲酚和丙烯为原料合成百里香酚，该反应为强酸体系，导致设备腐蚀严重，后处理繁琐，三废多。
CN106008169A公开了在掺杂钴为主的活性氧化铝催化剂的催化下反应合成百里香酚的工艺，所述活性氧化铝催化剂的结构为：Co&X@Al2O3，所述的X为除钴以外的第VIII族过渡金属，其含量小于钴。采用固定床反应器，以间甲酚和丙烯为原料合成百里香酚，催化效果较为理想，缺点是催化剂采用较为昂贵的金属，如钌、铑、钯、锇、铱、铂等，成本较高。
综上所述，现在用于间甲酚烷基化合成百里香酚的催化剂，存在反应性能差、成本高、寿命短、制备工艺复杂、反应条件苛刻、设备要求高、污染严重的若干或多个缺陷。
因此，目前亟需一种催化活性高、制备工艺简单、使用寿命长、易于再生的百里香酚连续化工业生产用催化剂。
发明内容
为了解决上述技术问题，本发明提供一种催化活性高、稳定性好、易于再生的百里香酚制备用催化剂，可实现百里香酚的连续工业化生产，绿色、无污染，并且该催化剂的制备工艺简单、成本低。
本发明实施例提供一种合成百里香酚用催化剂，其包括分子筛、助剂、粘结剂；
所述助剂选自氧化锌、氧化铁、磷酸、磷钼酸、氧化硅、氧化铜、氧化钼、氧化镍、氧化银中的一种或几种的组合；
所述粘结剂为硅溶胶、氧化铝、天然黏土、凹凸棒土、水玻璃、甲基纤维素、聚乙烯醇、淀粉、塑料树脂、松香中的一种或几种。
作为一种实施方式，所述分子筛选自HZSM-5，HMOR，Hβ、HY、HX、HMCM-41中的一种或几种。
作为一种实施方式，所述催化剂中分子筛的含量为25～89w％，助剂的含量为1～15w％，粘结剂的含量为10～60w％。
作为一种实施方式，分子筛的含量为55～75w％，助剂的含量为10～15w％，粘结剂的含量为15～30w％。
作为一种实施方式，所述分子筛的SiO2和Al2O3的摩尔比为1∶5～1∶300，比表面积为100～800m2/g，孔容为0.20～0.80cm3/g。
本发明还提供根据以上内容任一项所述催化剂的制备方法，包括：将分子筛、粘结剂、助剂和致孔剂粉碎并混合均匀，加入硝酸溶液或者去离子水，然后挤压成型、干燥，进行焙烧，得到所述催化剂。
作为一种实施方式，所述致孔剂选自田菁粉、甘油、润滑油、石墨、石蜡、松香、淀粉中的一种或几种。
作为一种实施方式，所述致孔剂的含量占总重量的1～15％。
作为一种实施方式，所述的制备方法中，预先采用有机酸溶液对分子筛进行酸洗处理。
作为一种实施方式，所述酸洗处理的步骤为：用5～10w％的有机酸溶液在90℃下预处理0.5～6h，有机酸溶液选自柠檬酸、山梨酸、酒石酸、丙烯酸或草酸的一种或几种组合。
作为一种实施方式，所述焙烧的温度为400～600℃，焙烧时间为1～3h。
本发明还提供所述催化剂在合成百里香酚中的应用，采用丙烯和惰性气体组成的混合气体为反应气氛，加入间甲酚，在所述催化剂的作用下反应制备百里香酚。
作为一种实施方式，反应压力为0.05～3.0MPa，反应温度120～400℃，丙烯与间甲酚的摩尔比为1∶0.1～5.0，液体重量空速为0.1～10h-1。
作为一种实施方式，所述惰性气体为氮气或氦气。
本发明的有益效果为：
1、本发明以分子筛为载体，进一步负载助剂，经过焙烧得到多孔的催化剂结构。制备催化剂的原料易得、价位低廉，制备方法简便，得到的催化剂为固体形态，便于重复使用，显著降低百里香酚的生产成本，适合工业化生产应用。
2、本发明催化剂采用分子筛作为主要活性成分，具有明显高于氧化铝型的比表面积，和其他类型的催化剂相比，显著延长了使用寿命，催化剂在500h的反应时间内，催化剂的活性和选择性基本上不发生明显的下降。
3、本发明催化剂的活性助剂与分子筛表面具有良好的化学相互作用，很好地解决了催化活性中心的流失而导致催化性能下降的问题。
4、本发明催化剂不使用贵金属或对环境污染严重的金属或者相关化合物，代替了传统的液体酸型催化剂，符合绿色化学的理念，并且降低生产成本。
5、本发明催化剂适于氮气与丙烯的混合反应气氛，减少了丙烯与间甲酚的摩尔比，显著减少了丙烯齐聚等副产物的生成，丙烯齐聚等副产物的生成量低于1％，提高催化剂的寿命和催化性能的稳定性，适合工业化生产应用。
6、本发明所提供的方法制备的催化剂，具有更多的活性位点和比表面积，为催化反应的发生提供了更多的微型反应空间和间甲酚与丙烯的碰撞机率，满足工业应用的需求，具有更高的间甲酚处理能力，拥有更好的催化稳定性和催化剂寿命。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面对本发明实施例的技术方案进行清楚、完整地描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
本发明的助剂选自氧化锌、氧化铁、磷酸、磷钼酸、氧化硅、氧化铜、氧化钼、氧化镍、氧化银中的一种或几种的组合。
本发明的粘结剂为硅溶胶、氧化铝、天然黏土、凹凸棒土、水玻璃、甲基纤维素、聚乙烯醇、淀粉、塑料树脂、松香中的一种或几种。
本发明的分子筛选自HZSM-5，HMOR，Hβ、HY、HX、HMCM-41中的一种或几种，SiO2和Al2O3的摩尔比为1∶5～1∶300，比表面积为100～800m2/g，孔容为0.20～0.80cm3/g。
本发明的致孔剂选自田菁粉、甘油、润滑油、石墨、石蜡、松香、淀粉中的一种或几种。
未作特别说明时，本发明采用的试剂均可从市场采购得到。
实施例1
合成百里香酚用催化剂，原料配方如下：
其中，HZSM-5型沸石分子筛和Hβ型分子筛的质量比为6∶4。
制备方法如下：
按照上述配方将各组分进行粉碎后混合均匀；
加入适量(便于捏合的量，根据实际操作控制)的5w％硝酸溶液，经捏合后在挤条机中成型，挤成直径1.3～1.5mm的四叶草型，在室温下晾干，然后放入烘箱中进行干燥，先在60℃条件下干燥2h，然后在150℃条件下干燥12h。最后转移至马弗炉中，540℃条件下焙烧2h，得到所述催化剂。
实施例2
合成百里香酚用催化剂，原料配方如下：
其中，HMOR分子筛和HY型分子筛的质量比8∶2。
制备方法如下：
按照上述配方将各组分进行粉碎后混合均匀；
加入适量的5w％硝酸溶液，经捏合、充分混合后在挤条机中成型，挤成直径1.3～1.5mm的四叶草型。然后在室温下晾干，然后放入烘箱中进行干燥，先在60℃条件下干燥2h，然后在150℃条件下干燥12h。最后，转移至马弗炉中，600℃条件下焙烧1h，得到所述催化剂。
实施例3
合成百里香酚用催化剂，原料配方如下：
其中，HMCM-41分子筛和Hβ型分子筛的质量比为7∶3。
制备方法如下：
按照上述配方将各组分进行粉碎后混合均匀；
加入适量的5w％硝酸溶液，经捏合、充分混合后在挤条机中成型，挤成直径1.3～1.5mm的四叶草型。然后在室温下晾干，然后放入烘箱中进行干燥，先在60℃条件下干燥2h，然后在150℃条件下干燥12h。最后，转移至马弗炉中，500℃条件下焙烧3h，得到所述催化剂。
实施例4
合成百里香酚用催化剂，原料配方如下：
其中，HZSM-5分子筛和HMOR分子筛的质量比7∶3，HMOR分子筛预先在10w％的柠檬酸中，90℃下浸泡4h。
制备方法如下：
将HMOR分子筛预先在10w％的柠檬酸中，90℃下浸泡4h备用，然后按照上述配方将各组分进行粉碎后混合均匀；
加入适量的5w％硝酸溶液充分混合后在挤条机中成型，挤成直径1.3～1.5mm的四叶草型。然后在室温下晾干，然后放入烘箱中进行干燥，先在60℃条件下干燥2h，然后在150℃条件下干燥12h。最后，转移至马弗炉中，540℃条件下焙烧3h，得到所述的催化剂。
对比例1
与实施例1相比，区别在于缺少分子筛，其他与实施例1一致。
对比例2
与实施例1相比，区别在于缺少助剂氧化镍、氧化钼，其他与实施例1一致。
试验例
分别取20g上述各实施例或对比例的催化剂，筛分成长度2mm的小颗粒，然后装填到固定床反应器的恒温段。
通入丙烯气氛或者氮气与丙烯的混合气氛，将反应系统升温至220～270℃，用质量计量泵将间甲酚送入反应系统中，在间甲酚的质量空速为2.0h-1、反应压力0.1MPa、丙烯/间甲酚的摩尔比为1.0的条件下，进行催化反应。反应粗品流经管道进入气液分离罐中进行气液分离，液体从分离罐的下端采出，连续反应两小时后，取一段时间内产生的样品进行气相色谱分析，得到间甲酚的转化率和百里香酚的选择性，如表1所示。
表1
虽然本发明所揭露的实施方式如上，但所述的内容仅为便于理解本发明而采用的实施方式，并非用以限定本发明。任何本发明所属领域内的技术人员，在不脱离本发明所揭露的精神和范围的前提下，可以在实施的形式及细节上进行任何的修改与变化，但本发明的专利保护范围，仍须以所附的权利要求书所界定的范围为准。
Claims (10)
1.合成百里香酚用催化剂，其特征在于，包括分子筛、助剂、粘结剂；
所述助剂选自氧化锌、氧化铁、磷酸、磷钼酸、氧化硅、氧化铜、氧化钼、氧化镍、氧化银中的一种或几种的组合；
所述粘结剂为硅溶胶、氧化铝、天然黏土、凹凸棒土、水玻璃、甲基纤维素、聚乙烯醇、淀粉、塑料树脂、松香中的一种或几种。
2.根据权利要求1所述的合成百里香酚用催化剂，其特征在于，所述分子筛选自HZSM-5，HMOR，Hβ、HY、HX、HMCM-41中的一种或几种。
3.根据权利要求1所述的合成百里香酚用催化剂，其特征在于，所述催化剂中分子筛的含量为25~89w%，助剂的含量为1~15w%，粘结剂的含量为10~60w%；
优选地，分子筛的含量为55~75w%，助剂的含量为10~15w%，粘结剂的含量为15~30w%。
4.根据权利要求1所述的合成百里香酚用催化剂，其特征在于，所述分子筛的SiO2和Al2O3的摩尔比为1:5~1:300，比表面积为100~800 m2/g，孔容为0.20~0.80 cm3/g。
5.根据权利要求1-4任一项所述合成百里香酚用催化剂的制备方法，其特征在于，所述制备方法包括：将分子筛、粘结剂、助剂和致孔剂粉碎并混合均匀，加入硝酸溶液或者去离子水，然后挤压成型、干燥，进行焙烧，得到所述催化剂。
6.根据权利要求5所述的制备方法，其特征在于，所述致孔剂选自田菁粉、甘油、润滑油、石墨、石蜡、松香、淀粉中的一种或几种；
可选地，所述致孔剂的含量占总重量的1~15%。
7.根据权利要求5所述的制备方法，其特征在于，预先采用有机酸溶液对分子筛进行酸洗处理；
可选地，所述酸洗处理的步骤为：用5~10w％的有机酸溶液在90℃下预处理0.5~6 h，有机酸溶液选自柠檬酸、山梨酸、酒石酸、丙烯酸或草酸的一种或几种组合。
8.根据权利要求6所述的制备方法，其特征在于，所述焙烧的温度为400~600℃，焙烧时间为1~3h。
9.权利要求1-4所述催化剂在合成百里香酚中的应用，其特征在于，采用丙烯和惰性气体组成的混合气体为反应气氛，加入间甲酚，在所述催化剂的作用下反应制备百里香酚。
10.根据权利要求9所述的应用，其特征在于，反应压力为0.05~3.0 MPa，反应温度120~400 ℃，丙烯与间甲酚的摩尔比为1：0.1~5.0，液体重量空速为0.1~10 h-1；
可选地，所述惰性气体为氮气或氦气。
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