CN106008169B - A kind of synthetic method of thymol - Google Patents
A kind of synthetic method of thymol Download PDFInfo
- Publication number
- CN106008169B CN106008169B CN201610473855.5A CN201610473855A CN106008169B CN 106008169 B CN106008169 B CN 106008169B CN 201610473855 A CN201610473855 A CN 201610473855A CN 106008169 B CN106008169 B CN 106008169B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- cobalt
- metacresol
- thymol
- synthetic method
- 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.)
- Active
Links
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 239000005844 Thymol Substances 0.000 title claims abstract description 51
- 229960000790 thymol Drugs 0.000 title claims abstract description 51
- 238000010189 synthetic method Methods 0.000 title claims abstract description 17
- 239000003054 catalyst Substances 0.000 claims abstract description 59
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- RLSSMJSEOOYNOY-UHFFFAOYSA-N m-cresol Chemical compound CC1=CC=CC(O)=C1 RLSSMJSEOOYNOY-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229940100630 metacresol Drugs 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 26
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 26
- 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 21
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 20
- 239000010941 cobalt Substances 0.000 claims abstract description 20
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 230000008569 process Effects 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 11
- 239000006200 vaporizer Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000012530 fluid Substances 0.000 claims description 5
- 238000002309 gasification Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000006004 Quartz sand Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 4
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 claims description 4
- 150000001869 cobalt compounds Chemical class 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- -1 transition metal salt compound Chemical class 0.000 claims description 4
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000008020 evaporation Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 230000005619 thermoelectricity Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 150000001768 cations Chemical class 0.000 abstract description 5
- 239000002841 Lewis acid Substances 0.000 abstract description 4
- 150000007517 lewis acids Chemical class 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 238000010924 continuous production Methods 0.000 abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000004587 chromatography analysis Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000002152 alkylating effect Effects 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 230000029936 alkylation Effects 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003205 fragrance Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000015689 metaplastic ossification Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 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
- GGKNTGJPGZQNID-UHFFFAOYSA-N (1-$l^{1}-oxidanyl-2,2,6,6-tetramethylpiperidin-4-yl)-trimethylazanium Chemical compound CC1(C)CC([N+](C)(C)C)CC(C)(C)N1[O] GGKNTGJPGZQNID-UHFFFAOYSA-N 0.000 description 1
- ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 2,3-dimethylbutane Chemical group CC(C)C(C)C ZFFMLCVRJBZUDZ-UHFFFAOYSA-N 0.000 description 1
- ZDUIHRJGDMTBEX-UHFFFAOYSA-N 3-methyl-5-propan-2-ylphenol Chemical class CC(C)C1=CC(C)=CC(O)=C1 ZDUIHRJGDMTBEX-UHFFFAOYSA-N 0.000 description 1
- VLJSLTNSFSOYQR-UHFFFAOYSA-N 3-propan-2-ylphenol Chemical class CC(C)C1=CC=CC(O)=C1 VLJSLTNSFSOYQR-UHFFFAOYSA-N 0.000 description 1
- 101710194905 ARF GTPase-activating protein GIT1 Proteins 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- NOOLISFMXDJSKH-UHFFFAOYSA-N DL-menthol Natural products CC(C)C1CCC(C)CC1O NOOLISFMXDJSKH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 102100029217 High affinity cationic amino acid transporter 1 Human genes 0.000 description 1
- 101710081758 High affinity cationic amino acid transporter 1 Proteins 0.000 description 1
- 241001183990 Mesosphaerum suaveolens Species 0.000 description 1
- 206010057190 Respiratory tract infections Diseases 0.000 description 1
- 206010046306 Upper respiratory tract infection Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940112822 chewing gum Drugs 0.000 description 1
- 235000015218 chewing gum Nutrition 0.000 description 1
- 235000019504 cigarettes Nutrition 0.000 description 1
- 150000001896 cresols Chemical class 0.000 description 1
- 238000009792 diffusion process Methods 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
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- ULYZAYCEDJDHCC-UHFFFAOYSA-N isopropyl chloride Chemical compound CC(C)Cl ULYZAYCEDJDHCC-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000137 polyphosphoric acid Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J23/8913—Cobalt and noble metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic methods of thymol.In current synthetic method, some selectivity are low；Some operating condition control difficulty are big；Catalyst be all extremely corrosive strong acid and generate the more lewis acid of the three wastes, and cannot recycle, be passed through into reaction kettle propylene can not continuous production, be unfavorable for industrializing.The present invention reacts, the structure of the activated alumina catalyst is using metacresol and propylene as raw material under the catalysis of the activated alumina catalyst based on cation doping prepared with sol-gal process：Co&X@Al2O3, the weight ratio of cobalt is 0.1~15%；The X is group VIII transition metal in addition to cobalt, and content is less than cobalt.Condition is easily controllable during the method synthesis target product that the present invention uses, and process is environmentally friendly, and catalyst stability is good, long lifespan, and selectivity is very high, and energy continuous production is conducive to industrialize.
Description
Technical field
The invention belongs to the preparation field of fine chemicals, specifically a kind of synthetic method of thymol.
Background technology
Thymol, also known as Thymol, thymol, the entitled thymol of English, the entitled 2- isopropyls -5- methylbenzenes of chemistry
Phenol, molecular formula C10H14O, molecular weight 150.22, No. CAS is 89-83-8.The chemical molecular structural formula of thymol is as follows：
Thymol has hundred inner grass or thymy special aroma, is mainly used for preparing cough drop as a kind of fragrance
The essence such as slurry, American mint chewing gum and spice, while be also one of additive for making cigarette.Thymol is also important
Fragrance intermediates are the important source materials for synthesizing l-menthol.In addition, thymol has bactericidal effect, especially to the upper respiratory tract
Infection and oral bacteria have inhibiting effect；It can be used to handle wound, store dissec；It can make preservative, and toxicity is less than benzene
Phenol；It is also high-efficiency antioxidant agent.
Before the forties in last century, thymol is mainly derived from nature.With the development of society, people are to thymol
Demand is increasing.It is but affected by various factors so that the cost of natural extraction thymol is very high.Therefore, nearly generation more than half
Since discipline, especially as the development of catalysis technique, synthesis thymol gradually replaces natural thymol.
The preparation of thymol is essentially all to be reacted using metacresol with a kind of alkylating reagent.According to alkylating reagent shape
The difference of formula is broadly divided into isopropyl halide method, propylene method and isopropanol method.United States Patent (USP) US2286953 uses isopropyl chloride
Make alkylating reagent and metacresol reaction, with methylene chloride as solvent, in AlCl3Under catalysis, Fu for being carried out at -10~0 DEG C
Gram reaction.Although the method can also obtain thymol, AlCl is used3Catalyst generates a large amount of three wastes, is unfavorable for industrial metaplasia
Production.Early in 1932, United States Patent (USP) US1886311 just reported the method that propylene makees alkylating reagent synthesis thymol, uses
Autoclave makees reactor, and temperature is 330~350 DEG C, and pressure is 30~40MPa, and metacresol conversion ratio and thymol selectively divide
Not Wei 40% and 50~60%, but the process conditions are harsh, low yield.
United States Patent (USP) US4086283 reports the technique of Beyer Co., Ltd, at a temperature of being mainly included in 350~365 DEG C,
The continuous alkylated reaction of metacresol and the liquid phase of propylene carried out under the pressure of 50bar.The gas phase collection of illustrative plates of crude product show including
60% thymol, 25% unconverted metacresol and 15% other products.Although the yield is relatively high, this technique is still wrapped
Containing following shortcoming：(1) operating condition is very harsh；(2) auxiliary agent-nitrogenous organic base of addition can pollute product.Afterwards
Come, the said firm continued to have delivered in 1991 patent US5030770, minimum using channel diameterZeolite molecular sieve urge
Changing metacresol, mutually continuous alkylation synthesis thymol, condition are 250 DEG C and normal pressure, wherein mordenite catalyst effect with propylene gas
Preferably, the conversion ratio of metacresol reaches 53%, and the selectivity of thymol reaches 84% in product.What zeolite catalyst generated crosses alkane
Base product is more, and the Thermodynamically stable isomers 3- isopropyl -5- methylphenols of thymol also generate more, are unfavorable for
Later separation.
Chinese patent CN201410201122.7 uses dense H2SO4And AlCl3Composition, polyphosphoric acids and AlCl3Group
Close object, dense H2SO4And ZnCl2Composition catalyst, propylene is continually fed into the reaction kettle containing metacresol can be relatively low
Thymol is obtained with 75~80% yield at 80~150 DEG C of temperature.The shortcomings that technique is that catalyst is all extremely corrosive
Strong acid and generate the more lewis acid of the three wastes, and cannot recycle, propylene is passed through into reaction kettle can not be continuous
Metaplasia is produced, and is unfavorable for industrializing.
Therefore at present there is an urgent need for one kind can continuous production, it is high that catalyst does not require nothing more than long lifespan and activity, especially right
Thymol is selectively good, and safe operation process is reliable, the low synthesis technology of production cost.
Invention content
The technical problems to be solved by the invention are to be furtherd investigate for the above-mentioned prior art, then provide one
The new synthetic method of kind thymol, uses the activated alumina catalyst based on the cation doping of sol-gal process preparation, no
Only reaction temperature is relatively low, and catalytic activity is high, and maximum bright spot is there is extra high selectivity to thymol, with big
It is big to improve production efficiency and simplify later separation step.
For this purpose, the present invention adopts the following technical scheme that：A kind of synthetic method of thymol, using metacresol and propylene as
Raw material reacts, the activity under the catalysis of the activated alumina catalyst based on cation doping prepared with sol-gal process
The structure of aluminium oxide catalyst is：Co&X@Al2O3, the weight ratio of cobalt is 0.1~15%；The X is the in addition to cobalt
VIII group transition metal, content are less than cobalt.
Its reaction equation is：
The activated alumina catalyst based on cation doping that the present invention is prepared by sol-gal process, not only strengthens acid
Property position simultaneously promotes catalytic activity, also improves the thermal stability of activated alumina.The specific pore passage structure especially formed
It is especially advantageous to selectively producing thymol.Different from the alkylation of benzene, the alkylation of metacresol is in phenyl ring unsubstituted four
The isomers generated on a site (2-, 4-, 5-, 6-) is all different, and four isomers of corresponding isopropylation are as follows：
By structure above it is found that only one of which isomers is thymol, so to selectively produce thymol is
Extremely challenging.The reaction mechanism of this technique is as shown in Figure 1.It flows through the metacresol of bed and propylene first passes through external diffusion arrival
The surface of catalyst granules, the microchannel of right trailing surface are inwardly diffused in the pore chamber in catalyst, rich on the hole wall of pore chamber
Containing abundant Lewis acid andSour site and abundant electron structure.Metacresol is lost after a proton with O originals
Son and Lewis acid activities site combine, this can cause the C atoms on phenyl ring spatially to have different positions, as shown in Figure 1.
Propylene would generally form isopropyl carbocationic intermediate and be attracted to hole wall surface after entering pore chamber, when close to by " Gu
It is fixed " metacresol when can initiate electrophilic attack to it.Due to " Gu oxygen " intensity of acidic site and the synergistic effect of three-dimensional effect, 2-
Number most readily accepted attack in position and generate thymol, be allowed to obtain excellent selectivity.In the thymol ultimately produced first passes through
Catalyst spheres outer surface is diffused to, then extends out and is scattered in product stream.
Further, the preparation method of the activated alumina catalyst is as follows：Weigh cobalt compound and in addition to cobalt
VIII group transition metal salt compound is added in butanediol and/or butanol, is then at room temperature added to aluminum isopropoxide
It states in the solution continuously stirred, gained mixed liquor is stood, 24~96h of natural aging, after gained gel is concentrated by evaporation
Be extruded into the bar of diameter 1.5-2.5mm, room temperature dry after 115-125 DEG C dry 12~for 24 hours, then in air atmosphere in
4~8h is roasted at 400~700 DEG C, catalyst obtained is finally crushed and screened into the particle of 1~2mm.
Further, the cobalt compound is CoCl2、Co(NO3)2、Co(SO4)2、CoAc2、Co(acac)3In one kind
Or a variety of, preferably Co (NO3)2、Co(acac)3, more preferable Co (acac)3。
Further, the material of main part of the catalyst is activated alumina, and BET specific surface area is 220~310m2/ g,
Most probable pore size ranging from 4.9~5.8nm, 0.71~0.73mL/g of Kong Rongwei.
Further, the group VIII transition metal in addition to cobalt is one in Fe, Ni, Ru, Rh, Pd, Os, Ir, Pt
Kind is two or more, and weight ratio is 0.1~3%, and the weight ratio of cobalt is preferably 0.5~10%, and more preferably 1~5%.
The present invention also includes the specific steps of following synthesis thymol：
1) by constant temperature zone of the catalyst filling among the fixed bed reactors, the upper/lower terminal difference of catalyst bed
Inert ceramic balls or quartz sand filler are filled with, wherein five sections of heating of reactor point carry out temperature control；Have among reactor one built in one
The temperature-measuring casing of thermocouple, to monitor catalyst bed each point actual temperature in real time；
2) respectively with fluid path and gas circuit quantitative feeding, fluid path squeezes into vaporizer, propylene by syringe pump for metacresol and propylene
Vaporizer is delivered to by gas mass flow gauge, the two is uniformly mixed in vaporizer, subsequently into fixed bed reactors；
3) completely reacted crude product carries out gas-liquid separation, and liquid mixture passes through rectification under vacuum, is recrystallized to give target product
Thymol, gas recycling Posterior circle use.
Inventor has found after carefully studying can be in very great Cheng than Conventional batch reactor using fixed bed reactors
Two substitutions and polysubstituted product are reduced on degree.Therefore other than the characteristic of catalyst in itself, the present invention uses serialization fixed bed
Reactor does the raising that reaction unit also promotes the selectivity of thymol.
Further, in step 1), the temperature for controlling catalyst bed is 200~240 DEG C, preferably 210~230 DEG C；Gas
It is 280~350 DEG C to change room temperature, and packing section temperature is 220~250 DEG C, and reaction carries out under normal pressure.
Further, in step 2), the molar ratio of the metacresol and isopropylating agent propylene is 1:0.5~1:6, it is excellent
It is selected as 1:1~1:4, more preferably 1:1~1:2.Metacresol 6- positions receive the 3- methyl -2- isopropyls of attack generation in reaction
The boiling point of phenol is close with thymol, its rectifying separation is very difficult, therefore the control of its amount is also extremely important.Between first
The reaction of phenol and isopropylating agent other than the metacresol of the single isopropyl substitution of generation, also occurred that alkylated reaction was given birth to
Into disubstituted metacresol even polysubstituted product.The processing of metacresol after being detached for rectifying is to return to be continuing with, and
The isomers of single isopropyl substitution is mainly that 3- isopropyl phenols and diisopropyl substituent can return again
It is reacted under catalyst of the present invention with metacresol, carries out turning alkyl or de- alkyl regenerates thymol.
Further, the raw material flow rate is to combine consideration with catalyst bed quality, i.e., with the quality of metacresol
Air speed characterizes, and value is 0.05~1.75h-1, preferably 0.1~1h-1, more preferably 0.3~0.6h-1。
Further, the continuous use service life of the catalyst is more than 720h, and the conversion ratio of metacresol is down to 70 after this
~80%, it is reactivated after this catalyst is roasted 6 hours under dry air atmosphere at 550 DEG C.
By using above-mentioned technical proposal, compared with prior art, beneficial effects of the present invention are as follows：
(1) activated alumina catalyst of cation doping and serialization fixed bed prepared by the sol-gal process of the present invention is combined
Reaction unit can cause the selectivity of thymol to be increased to 90~97%, after this not only greatly improves preparation efficiency but also is
Continuous separating step also creates great convenience, and the content for obtaining target product is up to more than 99.9%；In addition, using fixed bed device
It can be with serialization synthesis under normal pressure, production efficiency height.
(2) catalyst of the present invention substantially reduces the activation energy of metacresol alkylated reaction, reaction temperature control 210~
230 DEG C, reaction carries out under normal pressure, and the conversion ratio of metacresol is 90%, (the Bayer industry chemical industry compared with existing industrialization process
Skill,>350 DEG C, 50bar, US4086283), greatly reduce the energy consumption of production.
(3) present invention, which prepares thymol reaction, need to only use metacresol and propylene, not be related to other solvents, used catalyst
For the solid catalyst of stability and high efficiency, energy long-time Reusability not only reduces cost, and causes the discharge of the three wastes significantly
It reduces, it is environmentally friendly.
(4) so that mixed solvent natural aging, catalytic component is in butanediol/or fourth in catalyst preparation process of the present invention
It can tend to most stable of state under the solvent action of alcohol to be arranged, catalytic component obtained in this way is more evenly distributed, tightly
Close, stable, catalytic performance is more preferable.
Description of the drawings
Fig. 1 is the reaction mechanism figure of metacresol of the present invention and propylene.
Specific embodiment
For a better understanding of the present invention, present disclosure is further described below by way of specific example.But these
Example is only explanation of the invention, does not therefore generate any restrictions to protection scope of the present invention.
Embodiment 1-20
The method that sol-gal process prepares the activated alumina catalyst based on cobalt doped is as follows, weighs the cobalt of calculation amount
It closes object and group VIII transition metal salt compound is added in butanediol and/or butanol, then at room temperature by aluminum isopropoxide
It is added in the above-mentioned solution continuously stirred, which is stood, 24~96h of natural aging evaporates gained gel
Be extruded into the bar of diameter 2mm after concentration, room temperature dry after 120 DEG C dry 12~for 24 hours, then in air atmosphere in 400~
4~8h is roasted at 700 DEG C, catalyst obtained is finally crushed and screened into the particle of 1~2mm.
Activated alumina catalyst CAT-1~the CAT-20 weighed in batches based on the cobalt doped of sol-gal process preparation is each
10g is filled in the centre of fixed bed reactors constant temperature zone, and catalyst bed upper and lower end is respectively filled with quartz sand filler.Entire reaction
Device is heated using five-part form, has a diameter 3mm casing among reactor, a built-in thermocouple is each to monitor bed in real time
Point actual temperature.Before reaction, gasification room temperature is gradually risen to 300 DEG C under nitrogen flowing, the temperature of catalytic bed gradually rises to
220℃.After reaching set temperature, continue to purge 1h with nitrogen.Mass space velocity with syringe pump control metacresol is 0.6h-1, it is right
The propylene of 1.2 molar equivalents is answered to enter vaporizer after being measured with gas mass flow meter, metacresol is after vaporizer gasification with third
Alkene, which enters after being sufficiently mixed uniformly together in the catalyst bed of reactor, to react.Crude reaction flows through pipeline and enters gas-liquid separation
Gas-liquid separation is carried out in tank, liquid is produced from the lower end of knockout drum, and successive reaction takes the sample generated in a period of time after two hours
Product carry out gas chromatographic analysis, and the conversion ratio of metacresol and the selectivity of thymol are listed in Table 1 below.
Table 1
Embodiment 21-27
The cobalt doped activated alumina catalyst CAT-8 for weighing the preparation of 10g sol-gal processes is filled in fixed bed reactors
The centre of (i.e. pipeline) constant temperature zone, catalyst bed upper and lower end are respectively filled with quartz sand filling.Entire reactor is added using five-part form
Heat has a diameter 3mm casing, a built-in thermocouple, to monitor bed each point actual temperature in real time among reactor.Reaction
Before, gasification room temperature is gradually risen to 300 DEG C under nitrogen flowing, the temperature of catalytic bed gradually rises to 210~240 DEG C.It reaches
After set temperature, continue to purge 1h with nitrogen.Mass space velocity with syringe pump control metacresol is 0.6~1.2h-1, corresponding 1~4
The propylene of molar equivalent enters vaporizer after being measured with gas mass flow meter, metacresol is abundant with propylene after vaporizer gasification
Enter together after mixing in the catalyst bed of reactor and react.Crude reaction flow through pipeline enter in knockout drum into
Row gas-liquid separation, liquid are produced from the lower end of knockout drum, and successive reaction takes the sample generated in a period of time to carry out after two hours
Gas chromatographic analysis, the conversion ratio of metacresol and the selectivity of thymol are listed in Table 2 below.
Table 2
Embodiment 28
Using catalyst CAT-8, by above-described embodiment experimental method, propylene is changed to isopropanol, control isopropanol and
The molar ratio of cresols is 4, and isopropanol and metacresol exist the temperature control of catalyst bed after mixing by fluid path sample introduction
240 DEG C, successive reaction takes the sample generated in a period of time to carry out gas chromatographic analysis, the conversion ratio of metacresol after two hours
It is 82%, the selectivity of thymol is 88%.
Embodiment 29
It using catalyst CAT-8, and is ground into powder, propylene is changed to isopropanol, control isopropanol and metacresol
Molar ratio is 4；A certain amount of material and catalyst are disposably put into 0.5L autoclaves, nitrogen protection, reaction temperature control
At 220 DEG C, after continuously stirring reaction six hours, sampling carries out gas chromatographic analysis, and the conversion ratio of metacresol is 47%, thymol
Selectivity be 12%.
Embodiment 30
It using catalyst CAT-8, and is ground into powder, propylene is changed to isopropanol, control isopropanol and metacresol
Molar ratio is 4；A certain amount of material and catalyst are disposably put into 0.5L autoclaves, nitrogen protection, reaction temperature control
At 280 DEG C, after continuously stirring reaction six hours, sampling carries out gas chromatographic analysis, and the conversion ratio of metacresol is 67%, thymol
Selectivity be 78%.
Embodiment 31
The reaction crude product for collecting embodiment 8 carries out rectification under vacuum, and control system pressure is 100~150Pa, collect 78~
82 DEG C of fraction, is recrystallized with petroleum ether, obtains colourless transparent crystal, is 99.9% through vapor detection thymol content.
Embodiment 32
The reaction crude product for collecting embodiment 8 carries out rectification under vacuum, and control system pressure is 100~150Pa, collect 78~
82 DEG C of fraction, is recrystallized with n-hexane, obtains colourless transparent crystal, is 99.8% through vapor detection thymol content.
Although the present invention has had been described in detail for illustrative purposes in above-mentioned text, those skilled in the art should
Understand, solely for the purpose of illustration, those skilled in the art can be without departing from spirit and scope of the present invention for these detailed descriptions
In the case of, a variety of transformation or improvement can be carried out to technical solution of the present invention and embodiments thereof, these each fall within the present invention
In the range of.Protection scope of the present invention can be defined by the claims.
Claims (10)
1. a kind of synthetic method of thymol, using metacresol and propylene as raw material, with sol-gal process prepare with doping
It is reacted under the catalysis of activated alumina catalyst based on cobalt, the structure of the activated alumina catalyst is：Co&X@Al2O3,
The weight ratio of cobalt is 0.1~15%；The X is group VIII transition metal in addition to cobalt, and content is less than cobalt.
2. synthetic method according to claim 1, which is characterized in that the preparation method of the activated alumina catalyst is such as
Under：It weighs cobalt compound and group VIII transition metal salt compound in addition to cobalt is added in butanediol and/or butanol, then
Aluminum isopropoxide is added at room temperature in the solution continuously stirred, gained mixed liquor is stood, natural aging 24~
96h, is extruded into the bar of diameter 1.5-2.5mm after gained gel is concentrated by evaporation, room temperature is dried after 115-125 DEG C dry 12
~for 24 hours, and 4~8h is then roasted at 400~700 DEG C in air atmosphere, catalyst obtained is finally crushed and screened into 1~
The particle of 2mm.
3. synthetic method according to claim 2, which is characterized in that the cobalt compound is CoCl2、Co(NO3)2、Co
(SO4)2、CoAc2、Co(acac)3In it is one or more.
4. synthetic method according to claim 1, which is characterized in that the material of main part of the catalyst is active oxidation
Aluminium, BET specific surface area are 220~310m2/ g, most probable pore size ranging from 4.9~5.8nm, 0.71~0.73mL/ of Kong Rongwei
g。
5. synthetic method according to claim 1, which is characterized in that the group VIII transition metal in addition to cobalt is
One or more of Fe, Ni, Ru, Rh, Pd, Os, Ir, Pt, weight ratio are 0.1~3%, and the weight ratio of cobalt is 0.5
~10%.
6. synthetic method according to claim 1, which is characterized in that the detailed process for synthesizing thymol is as follows：
1) by constant temperature zone of the catalyst filling among the fixed bed reactors, the upper/lower terminal of catalyst bed is filled with respectively
Point five sections of heating of inert ceramic balls or quartz sand filler, wherein reactor carry out temperature control；There is a thermoelectricity built in one among reactor
Even temperature-measuring casing, to monitor catalyst bed each point actual temperature in real time；
2) metacresol and propylene are respectively with fluid path and gas circuit quantitative feeding, and fluid path squeezes into vaporizer by syringe pump, and propylene passes through
Gas mass flow gauge is delivered to vaporizer, and the two is uniformly mixed in vaporizer, subsequently into fixed bed reactors；
3) completely reacted crude product carries out gas-liquid separation, and liquid mixture passes through rectification under vacuum, is recrystallized to give in target product hundred
Phenol, gas recycling Posterior circle use.
7. synthetic method according to claim 6, which is characterized in that in step 1), the temperature for controlling catalyst bed is
200~240 DEG C, gasification room temperature is 280~350 DEG C, and packing section temperature is 220~250 DEG C, and reaction carries out under normal pressure.
8. synthetic method according to claim 6, which is characterized in that in step 2), the metacresol and isopropylation
The molar ratio of reagent propylene is 1:0.5~1:6.
9. synthetic method according to claim 6, which is characterized in that raw material flow rate has been combined with catalyst bed quality
Consider, i.e., characterized with the mass space velocity of metacresol, value is 0.05~1.75h-1。
10. according to claim 1-6 any one of them synthetic methods, which is characterized in that the continuous use longevity of the catalyst
Life is more than 720h, and the conversion ratio of metacresol is down to 70~80% after this, by this catalyst in 550 under dry air atmosphere
It is reactivated after being roasted 6 hours at DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610473855.5A CN106008169B (en) | 2016-06-22 | 2016-06-22 | A kind of synthetic method of thymol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610473855.5A CN106008169B (en) | 2016-06-22 | 2016-06-22 | A kind of synthetic method of thymol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106008169A CN106008169A (en) | 2016-10-12 |
| CN106008169B true CN106008169B (en) | 2018-07-03 |
Family
ID=57083697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610473855.5A Active CN106008169B (en) | 2016-06-22 | 2016-06-22 | A kind of synthetic method of thymol |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106008169B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107961779B (en) * | 2017-11-24 | 2020-10-23 | 江西省隆南药化有限公司 | Catalyst for synthesizing thymol, preparation method thereof and method for preparing thymol by using catalyst |
| CN108285406A (en) * | 2018-02-07 | 2018-07-17 | 常州大学 | A kind of preparation method of antioxidant BHT |
| CN110668922B (en) * | 2019-04-19 | 2022-06-10 | 江西阿尔法高科药业有限公司 | Refining method of musk camphor |
| CN111943816B (en) * | 2020-07-23 | 2021-04-23 | 安徽海华科技集团有限公司 | Preparation method of 2, 6-di-tert-butyl-p-cresol |
| CN113896617B (en) * | 2021-10-18 | 2022-04-05 | 安徽海华科技集团有限公司 | Chemical synthesis process of carvacrol |
| CN114849769B (en) * | 2022-04-25 | 2023-06-13 | 安徽海华科技集团有限公司 | Catalyst for synthesizing thymol and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4086283A (en) * | 1975-06-25 | 1978-04-25 | Bayer Aktiengesellschaft | Process for preparing thymol |
| CN101402551A (en) * | 2008-11-14 | 2009-04-08 | 广东省石油化工研究院 | Method of preparing thymol |
| CN101538191A (en) * | 2009-05-06 | 2009-09-23 | 西安力邦制药有限公司 | Synthetic method of high-purity propofol |
| EP2524906A1 (en) * | 2011-05-20 | 2012-11-21 | LANXESS Deutschland GmbH | Method for producing para-thymol |
| CN103951546A (en) * | 2014-05-13 | 2014-07-30 | 宿迁科思化学有限公司 | Novel synthetic process of thymol |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2015227289A (en) * | 2014-05-30 | 2015-12-17 | 上野製薬株式会社 | Production method of dialkylphenol |
-
2016
- 2016-06-22 CN CN201610473855.5A patent/CN106008169B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4086283A (en) * | 1975-06-25 | 1978-04-25 | Bayer Aktiengesellschaft | Process for preparing thymol |
| CN101402551A (en) * | 2008-11-14 | 2009-04-08 | 广东省石油化工研究院 | Method of preparing thymol |
| CN101538191A (en) * | 2009-05-06 | 2009-09-23 | 西安力邦制药有限公司 | Synthetic method of high-purity propofol |
| EP2524906A1 (en) * | 2011-05-20 | 2012-11-21 | LANXESS Deutschland GmbH | Method for producing para-thymol |
| CN103951546A (en) * | 2014-05-13 | 2014-07-30 | 宿迁科思化学有限公司 | Novel synthetic process of thymol |
Non-Patent Citations (1)
| Title |
|---|
| 百里香酚的合成研究;仇昆伦等;《食品工业科技》;20091231(第01期);第266-268页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106008169A (en) | 2016-10-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106008169B (en) | A kind of synthetic method of thymol | |
| Wang et al. | CuNi@ C catalysts with high activity derived from metal–organic frameworks precursor for conversion of furfural to cyclopentanone | |
| Lili et al. | Glycerol dehydration to acrolein over activated carbon-supported silicotungstic acids | |
| CN101817713B (en) | Preparation method of 2, 2'-biphenyl diphenol and derivatives thereof | |
| CN104010996A (en) | Method for producing p-xylene and/or p-tolualdehyde | |
| JP6856757B2 (en) | Reaction systems, catalysts and methods for preparing β-phenylethanol | |
| CN107108397A (en) | Method for producing alkadienes | |
| CN105597806A (en) | Hydrodeoxygenation cobalt catalyst and preparation method thereof | |
| CN104031016A (en) | Synthetic method of apigenin | |
| CN109574799A (en) | A method of 3- methyl-3-butene-1-alcohol is prepared using isobutene and methanol | |
| US9656250B2 (en) | Method for preparing iodine-doped TiO2 nano-catalyst and use thereof in heterogeneously catalyzing configuration transformation of trans-carotenoids | |
| CN109503330A (en) | A kind of method that Catalytic lignin phenols selectivity demethoxylation prepares phenol or alkylphenol | |
| CN112387268B (en) | Solid base catalyst for preparing 3-hydroxybutyraldehyde and preparation method thereof | |
| CN104341273B (en) | A kind of catalytic pyrolysis of biomass prepares the method for 4-ethyl-phenol | |
| CN106890669A (en) | A kind of catalyst for producing methyl acetate, its preparation method and application | |
| CN103331160A (en) | Preparation method of high-dispersion copper-based catalyst based on non-precious metal | |
| CN103951546B (en) | Novel synthetic process of thymol | |
| CN111499497B (en) | Preparation method of thymol | |
| KR101805086B1 (en) | Method for preparing catalyst for glycerin dehydration, catalyst for glycerin dehydration, and preparing method of acrolein | |
| JP2012254447A (en) | Catalyst for producing alcohol compound or olefin compound, and method for producing alcohol compound or olefin compound | |
| CN109265421B (en) | Method for preparing terpenoid by catalyzing mevalonic acid with bifunctional catalyst | |
| CN105709728B (en) | A kind of preparation method of catalyst for dehydrogenation of low-carbon paraffin | |
| CN107983334A (en) | A kind of graphene-supported tin tungsten bimetallic catalyst and its preparation method and application | |
| KR101629003B1 (en) | Catalyst for dehydration of glycerin, method of preparing the same, and preparing method of acrolein | |
| CN114890876B (en) | Prenyl isopentenyl ether and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |