CN106008169A - Synthetic method for thymol - Google Patents
Synthetic method for thymol Download PDFInfo
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- CN106008169A CN106008169A CN201610473855.5A CN201610473855A CN106008169A CN 106008169 A CN106008169 A CN 106008169A CN 201610473855 A CN201610473855 A CN 201610473855A CN 106008169 A CN106008169 A CN 106008169A
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- 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
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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
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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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
- B01J23/8913—Cobalt and noble metals
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Abstract
The invention discloses a synthetic method for thymol. In present synthetic methods, some are low in selectivity, and some are high in operation condition control difficulty; in some methods, highly corrosive strong acid or lewis acid generating a large quantity of three wastes serves as a catalyst and can not be recycled, continuous production can not be achieved even by introducing propylene into a reaction kettle, and industrialization is impeded. According to the synthetic method, m-cresol and propylene serve as raw materials, and a reaction is carried out under the catalysis of an activated aluminum oxide catalyst prepared through a sol-gel method with doping cobalt as the main component; the structure of the activated aluminum oxide catalyst is Co&X@Al2O3, the weight ratio of cobalt is 0.1-15%, X is family-VIII transition metal except cobalt, and the content of X is smaller than that of cobalt. When the synthetic method is adopted for synthesizing the target product, conditions are easy to control, the process is environmentally friendly, and the catalyst is high in stability and long in service life; besides, selectivity is very high, continuous production can be achieved, and industrialization is promoted.
Description
Technical field
The invention belongs to the preparation field of fine chemicals, the synthetic method of a kind of thymol.
Background technology
Thymol, also known as thymol, thymol, English entitled thymol, chemical entitled 2-isopropyl-5-methylphenol,
Molecular formula is C10H14O, molecular weight is 150.22, and No. CAS is 89-83-8.The chemical molecular structural formula of thymol is as follows:
Thymol has hundred li of careless or thymy special aromas, and it is mainly used in preparing cough syrup, green pepper as a kind of spice
The essence such as sample mint gum and spice, are the most also one of additives making medicated cigarette.Thymol or important spice
Intermediate, is the important source material of synthesis MENTHOL.Additionally, thymol has bactericidal action, especially to upper respiratory tract sense
Dye and oral cavity bacterium have inhibitory action；Can be used to process wound, store dissec；Preservative can be made, and toxicity is less than benzene
Phenol；Also it is high-efficiency antioxidant agent.
Before the forties in last century, thymol is mainly derived from nature.Along with the development of society, people are to thymol
Demand is increasing.But it is affected by various factors so that the cost of natural extract thymol is the highest.Therefore, nearly more than half
Since century, especially as the development of catalysis technique, synthesis thymol gradually replaces natural thymol.
The preparation of thymol is essentially all employing metacresol and reacts with a kind of alkylating reagent.According to alkylating reagent form
Difference, is broadly divided into isopropyl halide method, propylene method and isopropanol method.United States Patent (USP) US2286953 uses isopropyl chloride to make
Alkylating reagent and metacresol reaction, with methylene chloride as solvent, at AlCl3Under catalysis, the Fu Ke carried out at-10～0 DEG C
Reaction.Although this method also can obtain thymol, but uses AlCl3Catalyst produces a large amount of three wastes, is unfavorable for industry metaplasia
Produce.As far back as 1932, United States Patent (USP) US1886311 just reported the method that alkylating reagent synthesis thymol made by propylene,
Using autoclave to make reactor, temperature is 330～350 DEG C, and pressure is 30～40MPa, metacresol conversion ratio and thymol choosing
Selecting property is respectively 40% and 50～60%, but these process conditions are harsh, and productivity is low.
United States Patent (USP) US4086283 reports the technique of Beyer Co., Ltd, is mainly included at a temperature of 350～365 DEG C, 50bar
Pressure under the metacresol that carries out and the continuous alkylated reaction of liquid phase of propylene.The gas phase collection of illustrative plates of thick product shows and includes 60%
Thymol, 25% unconverted metacresol and 15% other product.Although this productivity is of a relatively high, this technique still comprise with
Lower shortcoming: (1) operating condition is the harshest；(2) product can be polluted by the nitrogenous organic base of the auxiliary agent that adds.After
Coming, the said firm continued to have delivered patent US5030770 in 1991, used channel diameter minimumZeolite molecular sieve
Catalysis metacresol and propylene gas continuous alkylation synthesis thymol mutually, condition is 250 DEG C and normal pressure, wherein mordenite catalyst
Effect is best, and the conversion ratio of metacresol reaches 53%, and in product, the selectivity of thymol reaches 84%.Zeolite catalyst produces
To cross alkylate more, and the Thermodynamically stable isomer 3-isopropyl-5-methylphenol of thymol also produces more,
It is unfavorable for later separation.
Chinese patent CN201410201122.7 uses dense H2SO4And AlCl3Compositions, polyphosphoric acids and AlCl3Group
Compound, dense H2SO4And ZnCl2Composition catalyst, being continually fed into propylene in the reactor containing metacresol can be
Thymol is obtained with the yield of 75～80% at lower temperature 80～150 DEG C.The shortcoming of this technique be catalyst be all great corrosion
Property strong acid and produce the more lewis acid of the three wastes, and can not recycle, being passed through propylene in reactor can not connect
Continuous metaplasia is produced, and is unfavorable for industrialization.
Need badly the most at present one can continuous prodution, it is high that catalyst does not require nothing more than life-span length and activity, especially to hundred li
Phenol selectivity is good, and safe operation process is reliable, the synthesis technique that production cost is low.
Summary of the invention
The technical problem to be solved is to further investigate for above-mentioned prior art, then provides a kind of hundred
In the new synthetic method of phenol, its cation doping using sol-gal process to prepare is main activated alumina catalyst, the most instead
Answering temperature relatively low, catalysis activity is high, and the bright spot of its maximum is to have thymol extra high selectivity, with significantly
Improve production efficiency and simplify later separation step.
To this end, the present invention adopts the following technical scheme that: the synthetic method of a kind of thymol, it is former with metacresol and propylene
Material, reacts, described active oxygen under the catalysis of the activated alumina catalyst based on cation doping prepared with sol-gal process
The structure changing Al catalysts is: Co&X@Al2O3, the weight ratio of cobalt is 0.1～15%；Described X is in addition to cobalt
VIII transition metal, its content is 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 acidic site
And promote catalysis activity, also improve the heat stability of activated alumina.The specific pore passage structure especially formed is special
Favourable to selectively producing thymol.Being different from the alkylation of benzene, the alkylation of metacresol is in unsubstituted four positions of phenyl ring
The upper isomer generated of point (2-, 4-, 5-, 6-position) is the most different, and four isomers of the isopropylation of its correspondence are as follows:
From structure above, only one of which isomer is thymol, so thymol to be selectively produced is great
Challenging.The reaction mechanism of this technique is as shown in Figure 1.The metacresol and the propylene that flow through bed first pass through external diffusion arrival and urge
The surface of catalyst particles, the microchannel of right trailing surface inwardly diffuses in the pore chamber in catalyst, on the hole wall of pore chamber rich in
Abundant Lewis acid andAcid site and abundant electron structure.Metacresol is former with O after losing a proton
Son and Lewis acid activity site combine, and this can cause the C atom on phenyl ring spatially to have different positions, such as Fig. 1 institute
Show.Propylene would generally form isopropyl carbocationic intermediate after entering into pore chamber and be attracted to hole wall surface, when press close to by
It can be initiated electrophilic attack during the metacresol " fixed ".Due to " Gu oxygen " intensity of acidic site and working in coordination with of steric effect
Effect, the most readily accepted attack in 2-position and generate thymol, be allowed to obtain excellent selectivity.The thymol ultimately produced
First pass through internal diffusion to catalyst spheres outer surface, then extend out and be scattered in product stream.
Further, the preparation method of described activated alumina catalyst is as follows: weigh cobalt compound and VIII in addition to cobalt
Group 4 transition metal salt compound is added in butanediol and/or butanol, the most at room temperature aluminum isopropoxide is joined above-mentioned continuously
In the solution of stirring, gained mixed liquor is stood, natural aging 24～96h, straight by being extruded into after gained gel evaporation and concentration
The bar of footpath 1.5-2.5mm, room temperature is dried 12～24h in 115-125 DEG C, then in 400～700 DEG C in air atmosphere after drying
Lower roasting 4～8h, is finally screened into the granule of 1～2mm by prepared break-up of catalyst.
Further, described cobalt compound is CoCl2、Co(NO3)2、Co(SO4)2、CoAc2、Co(acac)3In one
Or multiple, preferably Co (NO3)2、Co(acac)3, more preferably Co (acac)3。
Further, the material of main part of described catalyst is activated alumina, and its BET specific surface area is 220～310m2/ g,
Can several pore diameter ranges be 4.9～5.8nm, pore volume be 0.71～0.73mL/g.
Further, described group VIII transition metal in addition to cobalt is in Fe, Ni, Ru, Rh, Pd, Os, Ir, Pt
One or more, its weight ratio is 0.1～3%, and the weight ratio of cobalt is preferably 0.5～10%, more preferably 1～5%.
The present invention also comprises the following concrete steps synthesizing thymol:
1) by catalyst filling in the constant temperature zone of fixed bed reactors centre, the upper/lower terminal of beds adds respectively
Filling out inert ceramic balls or quartz sand filler, wherein reactor divides five sections of heating to carry out temperature control；A built-in heat is had in the middle of reactor
The temperature-measuring casing of galvanic couple, in order to real-time monitoring catalyst bed each point actual temperature；
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 leads to
Crossing mass-flow gas meter and be delivered to vaporizer, the two is mix homogeneously in vaporizer, subsequently in fixed bed reactors；
3) completely reacted crude product carries out gas-liquid separation, liquid mixture through rectification under vacuum, be recrystallized to give target product hundred
In phenol, gas reclaim Posterior circle use.
Inventor finds that after carefully studying employing fixed bed reactors can be to a great extent than Conventional batch reactor
Reduce by two replacements and polysubstituted product.Therefore, in addition to the characteristic of catalyst itself, the present invention uses serialization fixed bed reaction
Device does reaction unit and also promotes the selective raising of thymol.
Further, step 1) in, the temperature controlling beds is 200～240 DEG C, preferably 210～230 DEG C；Gasification
Room temperature is 280～350 DEG C, and packing section temperature is 220～250 DEG C, and reaction is carried out at ambient pressure.
Further, step 2) in, the mol ratio of described metacresol and isopropylating agent propylene is 1:0.5～1:6, preferably
For 1:1～1:4, more preferably 1:1～1:2.In reaction, metacresol 6-position accepts the 3-isopropyl phenol that attack generates
Boiling point close with thymol, by its rectification separate the most difficult, therefore the control of its amount is the most extremely important.Metacresol
With the reaction of isopropylating agent, in addition to generating single substituted metacresol of isopropyl, generate it also occur that cross alkylated reaction
The most polysubstituted product of dibasic metacresol.The process of the metacresol after separating for rectification is to return to be continuing with, and single
The substituted isomer of isopropyl is mainly 3-isopropyl phenol, and diisopropyl substituent can return again at this
React with metacresol under invention catalyst, carry out turning alkyl or de-alkyl regenerates thymol.
Further, described raw material flow rate is to combine consideration with beds quality, i.e. with the mass space velocity of metacresol
Characterizing, its value is 0.05～1.75h-1, preferably 0.1～1h-1, more preferably 0.3～0.6h-1。
Further, the continuous service life of described catalyst is more than 720h, and the conversion ratio of metacresol is down to after this
70～80%, by this catalyst under dry air atmosphere at 550 DEG C roasting reactivate after 6 hours.
By using technique scheme, compared with prior art, beneficial effects of the present invention is as follows:
(1) activated alumina catalyst and the serialization fixed bed that combine cation doping prepared by the sol-gal process of the present invention are anti-
Answering device, so that the selectivity of thymol brings up to 90～97%, this is not only greatly improved preparation efficiency but also for follow-up
Separating step also creates great convenience, and the content obtaining target product is up to more than 99.9%；Additionally, employing fixed bed device
Can be with serialization synthesis under normal pressure, production efficiency is high.
(2) catalyst of the present invention is substantially reduced the activation energy of metacresol alkylated reaction, and reaction temperature controls at 210～230 DEG C,
Reaction is carried out at ambient pressure, and the conversion ratio of metacresol is 90%, (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 prepares thymol reaction and only need to use metacresol and propylene, is not related to other solvent, used catalyst
For the solid catalyst of stability and high efficiency, can long-time Reusability, not only reduce cost, and make the discharge of the three wastes big
Big minimizing, environmentally friendly.
(4) making mixed solvent natural aging in catalyst preparation process of the present invention, catalytic component is at butanediol/or butanol
Solvent action under can tend to most stable of state and arrange, the catalytic component so prepared is more evenly distributed, closely,
Stable, catalytic performance is more preferable.
Accompanying drawing explanation
Fig. 1 is the reaction mechanism figure of metacresol of the present invention and propylene.
Detailed description of the invention
In order to be more fully understood that the present invention, further describe present disclosure below by way of instantiation.But these examples
It is only explanation of the invention, the most therefore protection scope of the present invention is produced any restriction.
Embodiment 1-20
It is as follows that sol-gal process prepares the method that cobalt doped is main activated alumina catalyst, weighs the cobalt compound of amount of calculation
It is added in butanediol and/or butanol with group VIII transition metal salt compound, the most at room temperature aluminum isopropoxide is added
In the solution of above-mentioned continuous stirring, this mixed liquor is stood, natural aging 24～96h, by gained gel evaporation and concentration
After be extruded into the bar of diameter 2mm, room temperature is dried 12～24h in 120 DEG C after drying, then in air atmosphere in
Roasting 4～8h at 400～700 DEG C, are finally screened into the granule of 1～2mm by prepared break-up of catalyst.
Weigh each 10g of activated alumina catalyst CAT-1～CAT-20 that cobalt doped is master prepared by sol-gal process in batches
Being filled in the centre of fixed bed reactors constant temperature zone, beds upper and lower end is respectively filled with quartz sand filler.Whole reactor
Employing five-part form heats, and has a diameter 3mm sleeve pipe in the middle of reactor, and a built-in thermocouple, in order to monitor bed in real time
Each point actual temperature.Before reaction, under nitrogen flowing vaporizer temperature progressively being risen to 300 DEG C, the temperature of catalytic bed is progressively
Rise to 220 DEG C.After arriving design temperature, continuation nitrogen purges 1h.The mass space velocity controlling metacresol with syringe pump is
0.6h-1, the propylene mass-flow gas meter of corresponding 1.2 molar equivalents enters vaporizer after measuring, and metacresol is at vaporizer gas
Enter together with after being sufficiently mixed with propylene after change uniformly in the beds of reactor and react.Crude reaction flows through pipeline and enters
Carrying out gas-liquid separation in knockout drum, liquid after two hours, takes a period of time from the lower end extraction of knockout drum, successive reaction
The sample of interior generation carries out gas chromatographic analysis, and the conversion ratio of metacresol and the selectivity of thymol are shown in Table 1.
Table 1
Embodiment 21-27
Weigh cobalt doped activated alumina catalyst CAT-8 prepared by 10g sol-gal process and be filled in fixed bed reactors (i.e.
Pipeline) centre of constant temperature zone, beds upper and lower end is respectively filled with quartz sand and fills.Whole reactor uses five-part form to add
Heat, has a diameter 3mm sleeve pipe in the middle of reactor, a built-in thermocouple, in order to monitoring bed each point actual temperature in real time.
Before reaction, under nitrogen flowing vaporizer temperature progressively being risen to 300 DEG C, the temperature of catalytic bed progressively rises to 210～240 DEG C.
After arriving design temperature, continuation nitrogen purges 1h.The mass space velocity controlling metacresol with syringe pump is 0.6～1.2h-1, right
Answer 1～4 molar equivalents propylene mass-flow gas meter measure after enter vaporizer, metacresol vaporizer gasify after with third
Alkene is sufficiently mixed in the beds entering reactor after uniformly together and reacts.Crude reaction flows through pipeline and enters gas-liquid separation
Carrying out gas-liquid separation in tank, liquid is from the lower end extraction of knockout drum, and successive reaction, after two hours, produces in taking a period of time
Sample carries out gas chromatographic analysis, and the conversion ratio of metacresol and the selectivity of thymol are shown in Table 2.
Table 2
Embodiment 28
Use catalyst CAT-8, by above-described embodiment experimental technique into, propylene is changed isopropanol, control isopropanol and a first
The mol ratio of phenol is 4, by fluid path sample introduction after isopropanol and metacresol mix homogeneously, the temperature of beds is controlled
240 DEG C, successive reaction is after two hours, and the sample produced in taking a period of time carries out gas chromatographic analysis, the conversion of metacresol
Rate is 82%, and the selectivity of thymol is 88%.
Embodiment 29
Using catalyst CAT-8, and be ground into powder, propylene changes into isopropanol, control isopropanol rubs with metacresol
Your ratio is 4；Disposably putting in 0.5L autoclave by a certain amount of material and catalyst, nitrogen is protected, and reaction temperature controls
At 220 DEG C, after continuous stirring is reacted six hours, sampling carries out gas chromatographic analysis, and the conversion ratio of metacresol is 47%, hundred
In the selectivity of phenol be 12%.
Embodiment 30
Using catalyst CAT-8, and be ground into powder, propylene changes into isopropanol, control isopropanol rubs with metacresol
Your ratio is 4；Disposably putting in 0.5L autoclave by a certain amount of material and catalyst, nitrogen is protected, and reaction temperature controls
At 280 DEG C, after continuous stirring is reacted six hours, sampling carries out gas chromatographic analysis, and the conversion ratio of metacresol is 67%, hundred
In the selectivity of phenol be 78%.
Embodiment 31
The thick product of reaction collecting embodiment 8 carries out rectification under vacuum, and controlling system pressure is 100～150Pa, collects 78～82 DEG C
Fraction, use petroleum ether recrystallization, obtain colourless transparent crystal, be 99.9% through vapor detection thymol content.
Embodiment 32
The thick product of reaction collecting embodiment 8 carries out rectification under vacuum, and controlling system pressure is 100～150Pa, collects 78～82 DEG C
Fraction, use normal hexane recrystallization, obtain colourless transparent crystal, be 99.8% through vapor detection thymol content.
Although specifically describing the present invention the most for illustrative purposes in above-mentioned literary composition, but those skilled in the art should manage
Solving, solely for the purpose of illustration, those skilled in the art can be without departing from spirit and scope of the present invention in these detailed descriptions
In the case of, technical solution of the present invention and embodiment thereof can be carried out multiple conversion or improvement, these each fall within the present invention's
In the range of.Protection scope of the present invention can be defined by the claims.
Claims (10)
1. a synthetic method for thymol, it is with metacresol and propylene as raw material, prepare with sol-gal process with cation doping
Being to react under the catalysis of main activated alumina catalyst, the structure of described activated alumina catalyst is:
Co&X@Al2O3, the weight ratio of cobalt is 0.1～15%；Described X is group VIII transition metal in addition to cobalt,
Its content is less than cobalt.
Synthetic method the most according to claim 1, it is characterised in that the preparation method of described activated alumina catalyst is such as
Under: weigh cobalt compound and group VIII transition metal salt compound in addition to cobalt is added in butanediol and/or butanol,
The most at room temperature aluminum isopropoxide is joined in the solution of above-mentioned continuous stirring, gained mixed liquor is stood,
Natural aging 24～96h, will be extruded into the bar of diameter 1.5-2.5mm, after room temperature is dried after gained gel evaporation and concentration
In 115-125 DEG C be dried 12～24h, then in air atmosphere at 400～700 DEG C roasting 4～8h, finally prepared is urged
Agent is crushed and screened into the granule of 1～2mm.
Synthetic method the most according to claim 2, it is characterised in that described cobalt compound is CoCl2、Co(NO3)2、
Co(SO4)2、CoAc2、Co(acac)3In one or more.
Synthetic method the most according to claim 1, it is characterised in that the material of main part of described catalyst is activated alumina,
Its BET specific surface area is 220～310m2/ g, most probable pore size scope is 4.9～5.8nm, and pore volume is 0.71～0.73mL/g.
Synthetic method the most according to claim 1, it is characterised in that described group VIII transition metal in addition to cobalt is
One or more in Fe, Ni, Ru, Rh, Pd, Os, Ir, Pt, its weight ratio is 0.1～3%, the weight of cobalt
Amount ratio is 0.5～10%.
Synthetic method the most according to claim 1, it is characterised in that the detailed process of synthesis thymol is as follows:
1) by catalyst filling in the constant temperature zone of fixed bed reactors centre, the upper/lower terminal of beds is filled with respectively
Inert ceramic balls or quartz sand filler, wherein reactor divides five sections of heating to carry out temperature control；One built-in one is had in the middle of reactor
The temperature-measuring casing of thermocouple, in order to real-time monitoring catalyst bed each point actual temperature；
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
Mass-flow gas meter is delivered to vaporizer, and the two is mix homogeneously in vaporizer, subsequently in fixed bed reactors；
3) completely reacted crude product carries out gas-liquid separation, liquid mixture through rectification under vacuum, be recrystallized to give in target product hundred
Phenol, gas reclaims Posterior circle and uses.
Synthetic method the most according to claim 6, it is characterised in that step 1) in, the temperature controlling beds is
200～240 DEG C, vaporizer temperature is 280～350 DEG C, and packing section temperature is 220～250 DEG C, and reaction is carried out at ambient pressure.
Synthetic method the most according to claim 6, it is characterised in that step 2) in, described metacresol and isopropylation
The mol ratio of reagent propylene is 1:0.5～1:6.
Synthetic method the most according to claim 6, it is characterised in that described raw material flow rate is and beds quality
Combining consideration, i.e. characterize with the mass space velocity of metacresol, its value is 0.05～1.75h-1。
10. according to the synthetic method described in any one of claim 1-6, it is characterised in that the continuous service life of described catalyst is big
In 720h, the conversion ratio of metacresol is down to 70～80% after this, by this catalyst under dry air atmosphere in
At 550 DEG C, roasting reactivated after 6 hours.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107961779A (en) * | 2017-11-24 | 2018-04-27 | 江西省隆南药化有限公司 | A kind of catalyst for musk ambrette grass phenol and preparation method thereof, and the method using the catalyst preparation thymol |
| CN108285406A (en) * | 2018-02-07 | 2018-07-17 | 常州大学 | A kind of preparation method of antioxidant BHT |
| CN110668922A (en) * | 2019-04-19 | 2020-01-10 | 江西阿尔法高科药业有限公司 | Refining method of musk medulla |
| CN111943816A (en) * | 2020-07-23 | 2020-11-17 | 安徽海华科技有限公司 | Preparation method of high-purity 2, 6-di-tert-butyl-p-cresol |
| CN113896617A (en) * | 2021-10-18 | 2022-01-07 | 安徽海华科技集团有限公司 | Chemical synthesis process of carvacrol |
| CN114849769A (en) * | 2022-04-25 | 2022-08-05 | 安徽海华科技集团有限公司 | Catalyst for synthesizing thymol and preparation method and application thereof |
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| 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 |
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| CN111943816A (en) * | 2020-07-23 | 2020-11-17 | 安徽海华科技有限公司 | Preparation method of high-purity 2, 6-di-tert-butyl-p-cresol |
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| CN114849769A (en) * | 2022-04-25 | 2022-08-05 | 安徽海华科技集团有限公司 | Catalyst for synthesizing thymol and preparation method and application thereof |
| 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 |
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