CN107235832A - A kind of method for producing guaiacol - Google Patents
A kind of method for producing guaiacol Download PDFInfo
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- CN107235832A CN107235832A CN201610183357.7A CN201610183357A CN107235832A CN 107235832 A CN107235832 A CN 107235832A CN 201610183357 A CN201610183357 A CN 201610183357A CN 107235832 A CN107235832 A CN 107235832A
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- catechol
- methanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
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Abstract
The invention discloses a kind of method for producing guaiacol, methods described includes to be added to gas phase in the mixing gas phase of catechol and methanol as the phosphorus-containing compound of catalyst component, catechol is etherified generation guaiacol under the reaction temperature no more than 275 DEG C.Methods described can avoid the local concentration of phosphorus-containing compound in the reactor too high, prevent catechol from occurring analysis carbon, so that the gas phase catalytic synthesis process of guaiacol can be realized steadily in the long term.
Description
Technical field
The present invention relates to the gas phase catalytic synthesis of the production method of guaiacol, more particularly to guaiacol.
Present invention phosphorus-containing compound makees catalyst component, and inert solid makees catalyst carrier, by specifically urging
Agent Adding Way realizes guaiacol catalytic production steady in a long-term.
Background technology
Guaiacol (guaiacol), i.e. o-methoxyphenol, are in the middle of a kind of important fine chemistry industry
Body, is widely used in the synthesis of medicine, spices and dyestuff, particularly as spices (such as vanillic aldehyde) and
Important source material and intermediate in medicine production.The main production of guaiacol is diazotising-hydrolysis
Technique, i.e., be made guaiacol by raw material o-aminoanisole through diazotising, hydrolysis.CN97118908.0
Diazol hydrolysis process and its improvement are all referred to CN03141536.9, however, these diazonium are hydrolyzed
The shortcomings of there is many high energy consumption, waste water, product band " chlorine " in technique, cause to finished product spices or
The quality of medicine brings adverse effect.The synthetic method of current guaiacol is related to Homogeneous synthesis and out-phase
(gas phase) is synthesized.There is complex technical process, seriously corroded, have severe toxicity and pollution ring in Homogeneous synthesis
The shortcomings of border.Due to the above mentioned problem that Homogeneous synthesis is present, people direct attention to out-phase synthesis work
The research of skill, the particularly vapor solid using alcohol as alkylating reagent catalyze and synthesize research.Out-phase reaction with
Homogeneous reaction is compared has advantage in terms of conversion ratio, accessory substance and energy consumption, particularly by methanol and
Catechol prepares the out-phase reaction technique of guaiacol.For example, Xu Yan etc. proposes to utilize methanol and neighbour
Benzenediol carries out gas phase reaction (the adjacent benzene two of Xu Yan etc., ZnCl2/NaY catalysis in fixed bed reactors
Phenol reacts with methanol etherification, applied chemistry, 2004,21 (7):664-668), obtained under catalyst action
Be higher than 80% to guaiacol yield, but the catalyst preparation process of this method is complicated, sintering temperature compared with
Height, catalyst recycling is inefficient, and in high reaction temperatures, easily occurs more pair
Reaction.
The present inventor has found under study for action, for being produced more by etherification reaction by methanol and catechol
For the out-phase synthesis technique of the wooden phenol of wound, catechol is inclined to " analysis carbon ".Against the reaction time
Extension, analysis carbon phenomenon further substantially, and can be damaged to course of reaction so that gas phase catalytic synthesis
Process is difficult to realize steadily in the long term.Analyse the presence of carbon phenomenon, it has also become hinder the technique further should
With one of with the obstacle of development.
Nobody illustrates the reason for analysis carbon occurs and its influence factor so far in the prior art, therefore existing
The method of technology can not effectively prevent from analysing carbon, even if some techniques have once in a while preferable yield and
Energy consumption, it is also difficult to realize good technology stability, or it cannot be guaranteed that longtime running.
Therefore, a kind of technique of effective production guaiacol is needed in the prior art so that avoid analysis
The generation of carbon phenomenon, and ensure the progress steady in a long-term of technique.
The content of the invention
The purpose of the present invention is that there is provided one for the analysis carbon problem that overcomes in existing guaiacol production technology
Plant more effective, stable guaiacol production technology.
For the out-phase synthesis technique using fixed bed reactors, catalyst is used as with inert solid
Carrier is loaded in the reactor, as catalyst component, is lived with containing phosphate mixture for the stable catalysis of holding
Property, it is necessary to make catalyst activity component arrive at catalyst support surface play catalytic action.This technique
Reaction temperature usually more than 300 DEG C, or even 400 DEG C.The present inventor is in long-term technical study
It was unexpectedly found that：When temperature 300 DEG C even more than 280 DEG C when, analysis carbon phenomenon become it is obvious or
There is generation, and analysis carbon phenomenon is as caused by reactant catechol；On the other hand, when using phosphorous
Compound (for example phosphoric acid, methyl orthophosphoric acid, dimethyl phosphate, trimethyl phosphate, diethyl phosphate,
Triethyl phosphate, pyrophosphoric acid, metaphosphoric acid and polyphosphoric acids etc.) as catalytic active component when, analyse carbon
Tendency is particularly acute, and with the rise of phosphorus-containing compound concentration, facing for analysis carbon occurs for catechol
Boundary's temperature is also accordingly reduced.Without being bound by theory, inventor speculates, it is possible to analyse carbon with reactant
Phosphorus-containing compound local concentration easily occurs at relatively low temperature with respect to rise in system.
The analysis carbon influence factor found for more than, the present inventor studies by many experiments and found：Can
Effectively to prevent from analysing carbon phenomenon by controlling feed postition of the phosphorus-containing compound into reaction system
Occur；On the other hand, when the temperature of control reaction system is no more than certain temperature (such as 275 DEG C),
Also it can effectively prevent analysis carbon phenomenon from occurring.
Therefore, the present inventor proposes a kind of method for producing guaiacol, methods described include using as
The phosphorus-containing compound of catalyst component is added to the mixing gas phase containing catechol and methanol with gas phase
Reactor in, make catechol be etherified under the reaction temperature no more than certain temperature generation guaiaci lignum
Phenol.
If it is important to note that using as the phosphorus-containing compound of catalyst component in advance with liquid or
Solution form is added directly into reactor, and then reheating vaporizes it, can not obtain satisfied effect
Really.
The present inventor proposes that following three kinds of additions can be used for as the mode of the phosphorus-containing compound of catalyst component
The present invention：
I) catalyst component is added in the catechol of liquid phase or catechol/carbinol mixture,
It is set to enter after together gasifying in company with catechol or catechol/carbinol mixture in reactor；Or
Ii) by catalyst component dissolving in methyl alcohol, then using atomization jetting device by gained methanol
Solution is ejected into reactor, is vaporized by catechol-methanol feed gas；Or
Iii methanol) is divided into two-way gas-phase feed, catechol is brought into all the way and while vaporizes it, separately
Bring the catalyst component into all the way and while vaporize it, two-way gas phase is quickly mixed in reactor.
Embodiment
There is provided a kind of method for producing guaiacol, methods described bag in one aspect of the invention
Include the mixing using catechol and methanol is added to gas phase as the phosphorus-containing compound of catalyst component
In gas phase.
Preferably, the present invention the above method in, make catechol in reaction system no more than
Etherificate generation guaiacol under 280 DEG C of reaction temperature.It is highly preferred that the etherification reaction temperature does not surpass
Cross 275 DEG C, no more than 270 DEG C, no more than 265 DEG C, no more than 260 DEG C, no more than 255 DEG C,
No more than 250 DEG C, no more than 245 DEG C, no more than 240 DEG C, no more than 235 DEG C, no more than 230 DEG C,
190 DEG C are even less than no more than 220 DEG C, no more than 210 DEG C, no more than 200 DEG C, no more than 195 DEG C
Reaction temperature under be etherified.
In the method for the invention, added as the phosphorus-containing compound of catalyst component with gas phase.Can
So that phosphorus-containing compound is added in the catechol of liquid phase or catechol/carbinol mixture, make its with
Together gasify with catechol or catechol/carbinol mixture, subsequently into reactor；Can also
By catalyst component dissolving in methyl alcohol, then gained methanol solution is ejected into using atomization jetting device
In reactor, the droplet is vaporized by catechol-methanol feed gas；Or methanol can be divided into two
Road gas-phase feed, brings catechol into and while vaporizing it, the catalysis group is brought on another road into all the way
Divide and vaporize it simultaneously, two-way gas phase is quickly mixed in reactor.
In one aspect of the invention, it can include and consolidate for the inertia of supported catalyst in the reactor
Catalyst carrier body bed, the inert solid catalyst carrier may be selected from activated carbon, Alpha-alumina,
Silica, diatomite, silica gel, h-type zeolite molecular sieve, aluminium phosphate molecular sieve, aluminium silicophosphate point
Sub- sieve, montmorillonite, bentonite, ion exchange resin, iron oxide, zinc oxide and TiO2-ZrO2
Any of or it is a variety of, including its combination.In a preferred embodiment, the inert solid
Catalyst carrier is selected from Alpha-alumina, activated carbon, silica, diatomite, silica gel, h-type zeolite
Molecular sieve, aluminium phosphate molecular sieve, aluminium silicophosphate molecular sieve and montmorillonite.In a preferred implementation
In scheme, the inert solid catalyst carrier is Alpha-alumina.
The phosphorus-containing compound as catalytic active component used in the production method of the present invention includes phosphorus
Acid, methyl orthophosphoric acid, dimethyl phosphate, trimethyl phosphate, diethyl phosphate, triethyl phosphate, Jiao
Phosphoric acid, metaphosphoric acid and polyphosphoric acids or several combinations therein.It is particularly preferred at one
Phosphorus-containing catalyst in aspect, the inventive method is phosphoric acid.
The addition of the phosphorus-containing compound as catalytic active component used in production method of the present invention can
To account for the 0.1-1% of reactant gross mass, preferably 0.1-0.9%, 0.1-0.8%, more preferably 0.1-0.7%,
Particularly preferred 0.2-0.6% and 0.2-0.5%.
In a preferred aspect of the inventive method, reactor may be configured with monitoring reaction system temperature in real time
The device of degree and/or catalyst concn, to monitor the temperature and concentration levels in reaction system in time.
Embodiment
The following is the non-limiting example of the present invention.These embodiments provide the mesh merely to illustrating
, and should not be construed as limitation of the invention.It will be understood by those skilled in the art that can not depart from
On the basis of the spirit and scope of the present invention, many changes and adjustment are carried out to the present invention.In the present invention
Specification and following instance in, unless stated otherwise, all concentration is all percetage by weight.
With reference to specific embodiment, the invention will be further described.
Embodiment 1
1) reaction unit
Stainless steel fixed bed reactors, internal diameter 2000mm, filling 5m3'sAlpha-alumina
Ball.Part charging Liquid Phase Methanol is vaporized by vaporizer, subsequently into catechol saturator.Adjacent benzene
Diphenol is added and gasified in catechol saturator, is mixed with methanol steam, and gas phase compounds pass through mistake
Hot device, which is warming up to after reaction temperature, enters reactor.
2) catalyst component Adding Way
Catalyst component is trimethyl phosphate.Part charging Liquid Phase Methanol is vaporized by vaporizer, Ran Houjin
Enter trimethyl phosphate vaporizer.Trimethyl phosphate is added and gasified in trimethyl phosphate vaporizer, with first
Alcohol steam is mixed, and gas phase compounds are warming up to after reaction temperature by superheater enters reactor.Charging
The weight proportion of feed liquid is：Catechol：Methanol=1：1.
3) etherification reaction
Reaction temperature is 260~263 DEG C, and methanol feed stream amount 1300L/hr is run 720 hours,
Aluminum oxide ball surface remains in that white without carbon distribution, and reaction conversion ratio and selectivity do not change.
Embodiment 2
1) reaction unit
Stainless steel fixed bed reactors, internal diameter 2000mm, filling 5m3'sAlpha-alumina
Ball.Part charging Liquid Phase Methanol is vaporized by vaporizer, subsequently into catechol saturator.Adjacent benzene
Diphenol is added and gasified in catechol saturator, is mixed with methanol steam, and gas phase compounds pass through mistake
Hot device, which is warming up to after reaction temperature, enters reactor.
2) catalyst component Adding Way
Catalyst component is phosphoric acid.Part charging Liquid Phase Methanol is vaporized by vaporizer, subsequently into phosphoric acid
Vaporizer.Phosphoric acid is added and gasified in phosphoric acid vaporizer, is mixed with methanol steam, and gas phase compounds lead to
Cross superheater and be warming up to after reaction temperature and enter reactor.
Charging feed liquid weight proportion be：Catechol：Methanol=1：1.
3) etherification reaction
Reaction temperature is 260~265 DEG C, and methanol feed stream amount 1500L/hr is run 1440 hours,
Aluminum oxide ball surface remains in that white without carbon distribution, and reaction conversion ratio and selectivity do not change.
Embodiment 3
1) reaction unit
Stainless steel single tube reactor, internal diameter 32mm, length 1200mm, reaction tube upper strata are gasification
And preheating section, fillingGlass pellet, height 40cm.Reaction tube middle level is beds,
Load 350cm3'sAlpha-oxidation aluminium ball, height 50cm.Reaction tube lower floor is isolation section,
FillingGlass pellet, height 40cm.
2) catalyst component Adding Way
Catalyst component is phosphoric acid, and phosphoric acid is added directly into charging feed liquid.Feed the weight proportion of feed liquid
For：Catechol：Methanol：Phosphoric acid=1：1.Liquid phase feed liquid is fed by pump to enter at the top of reaction tube.
Phosphoric acid together gasifies in the preheating section of reaction tube in company with charging feed liquid.
3) etherification reaction
Reaction temperature is 275 DEG C, and feed rate 125g/hr is run 2500 hours, alumina balls table
Face remains in that white without carbon distribution, and reaction conversion ratio and selectivity do not change.
Embodiment 4
1) reaction unit
Stainless steel single tube reactor, internal diameter 32mm, length 1200mm, reaction tube upper strata are gasification
And preheating section, fillingGlass pellet, height 40cm.Reaction tube middle level is beds,
Load 350cm3'sAlpha-oxidation aluminium ball, height 50cm.Reaction tube lower floor is isolation section,
FillingGlass pellet, height 40cm.
2) catalyst component Adding Way
Catalyst component is trimethyl phosphate, and trimethyl phosphate is added directly into charging feed liquid.Charging material
The weight proportion of liquid is：Catechol：Methanol=1：1.Feed liquid phase feed liquid and reaction is entered by pump
Tube top portion.
Trimethyl phosphate together gasifies in the preheating section of reaction tube in company with charging feed liquid.
3) etherification reaction
Reaction temperature is 265 DEG C, and feed rate 120g/hr is run 400 hours, aluminum oxide ball surface
Without carbon distribution, white is remained in that, reaction conversion ratio and selectivity do not change.
Comparison example 1
1) reaction unit
Stainless steel fixed bed reactors, internal diameter 2000mm, filling 4.6m3'sAlpha-alumina
Ball.Charging Liquid Phase Methanol is vaporized by vaporizer, subsequently into catechol saturator.Catechol
Add and gasify in catechol saturator, mixed with methanol steam.Gas phase compounds pass through superheater
It is warming up to after reaction temperature and enters reactor.
2) catalyst component Adding Way
Catalyst component is phosphoric acid.Phosphoric acid by the simple distribution apparatus in reactor top be added directly into
Expect in gas phase.
4) etherification reaction
Reaction temperature is 265 DEG C, and methanol feed stream amount 1000L/hr is run 480 hours, reactor
Interior carbon distribution about 250kg.
From result above, compared to the comparative example 1 being directly added into, using adding for the present invention
Entering the embodiment 1-4 of method can be effectively prevented from reacting carbon distribution, with significant technical advantage.
Claims (9)
1. a kind of method for producing guaiacol, methods described includes that phosphatization will be contained as catalyst component
Compound is added to gas phase in the reactor of the mixing gas phase containing catechol and methanol, makes neighbour
Benzenediol is etherified generation guaiacol under the reaction temperature no more than 275 DEG C.
2. according to the method described in claim 1, wherein being included in the reactor is used for supported catalyst
The inert solid catalyst carrier bed of agent, the inert solid catalyst carrier is selected from activated carbon, α
- aluminum oxide, silica, diatomite, silica gel, h-type zeolite molecular sieve, aluminium phosphate molecular sieve, silicon
Aluminium phosphate molecular sieve, montmorillonite, bentonite, ion exchange resin, iron oxide, zinc oxide and
TiO2-ZrO2 and combinations thereof.
3. according to any method of the preceding claims, wherein described as catalyst component
Phosphorus-containing compound be selected from phosphoric acid, methyl orthophosphoric acid, dimethyl phosphate, trimethyl phosphate, diethyl phosphate,
Triethyl phosphate, pyrophosphoric acid, metaphosphoric acid and polyphosphoric acids and combinations thereof.
4. according to any method of the preceding claims, wherein below the phosphorus-containing compound
State method addition：The catechol or catechol/methanol that the catalyst component is added into liquid phase are mixed
In thing, it is set to enter reactor after together gasifying in company with catechol or catechol/carbinol mixture
In.
5. according to any method of the preceding claims, wherein below the phosphorus-containing compound
State method addition：By catalyst component dissolving in methyl alcohol, then using atomization jetting device by institute
Obtain methanol solution to be ejected into reactor, vaporized by catechol-methanol feed gas.
6. according to any method of the preceding claims, wherein below the phosphorus-containing compound
State method addition：Methanol is divided into two-way gas-phase feed, catechol is brought into all the way and while makes its vapour
Change, another road brings the catalyst component into and while vaporize it, make two-way gas phase fast in reactor
Speed mixing.
7. according to any method of the preceding claims, wherein controlling reaction temperature is no more than
265℃。
8. according to any method of the preceding claims, wherein the phosphorus-containing compound
Addition accounts for the 0.1-0.8% of reactant gross mass.
9. according to any method of the preceding claims, wherein the reaction utensil has in real time
Monitor the device of temperature of reaction system and/or catalyst concn.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610183357.7A CN107235832B (en) | 2016-03-28 | 2016-03-28 | Method for producing guaiacol |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610183357.7A CN107235832B (en) | 2016-03-28 | 2016-03-28 | Method for producing guaiacol |
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| CN107235832A true CN107235832A (en) | 2017-10-10 |
| CN107235832B CN107235832B (en) | 2021-03-26 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939747A (en) * | 2021-03-02 | 2021-06-11 | 万华化学集团股份有限公司 | Preparation method of guaiacol |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1270576A (en) * | 1997-08-07 | 2000-10-18 | 阿克西瓦有限公司 | Use of phosphoric acid as homogeneous catalyst during the preparation of ketene |
| CN101081805A (en) * | 2006-06-02 | 2007-12-05 | 中国石油天然气集团公司 | Method for synthesizing guaiacol |
| CN101492353A (en) * | 2009-03-13 | 2009-07-29 | 北京化工大学 | Method for producing guaiacol with methanol method |
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2016
- 2016-03-28 CN CN201610183357.7A patent/CN107235832B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1270576A (en) * | 1997-08-07 | 2000-10-18 | 阿克西瓦有限公司 | Use of phosphoric acid as homogeneous catalyst during the preparation of ketene |
| CN101081805A (en) * | 2006-06-02 | 2007-12-05 | 中国石油天然气集团公司 | Method for synthesizing guaiacol |
| CN101492353A (en) * | 2009-03-13 | 2009-07-29 | 北京化工大学 | Method for producing guaiacol with methanol method |
Non-Patent Citations (2)
| Title |
|---|
| ALI ABEDI JAFARI 等: "Vapor-phase selective o-alkylation of catechol with methanol over lanthanum phosphate and its modified catalysts with Ti and Cs", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 潘春柳: "负载型磷酸催化剂上合成邻羟基苯乙醚", 《石油化工》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112939747A (en) * | 2021-03-02 | 2021-06-11 | 万华化学集团股份有限公司 | Preparation method of guaiacol |
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