CN1583697A - Preparing method for 3,5-dimethyl phenol - Google Patents
Preparing method for 3,5-dimethyl phenol Download PDFInfo
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- CN1583697A CN1583697A CN 200410025166 CN200410025166A CN1583697A CN 1583697 A CN1583697 A CN 1583697A CN 200410025166 CN200410025166 CN 200410025166 CN 200410025166 A CN200410025166 A CN 200410025166A CN 1583697 A CN1583697 A CN 1583697A
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- reaction
- solid catalyst
- catalyst
- xylenol
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Abstract
A process for preparing 3.5-xylenol features that the isophorone, liquid catalyst, and solid catalyst take part in reaction in inertial gas, and conventional collecting 3,5-xylenol.
Description
Technical field
The present invention relates to a kind of 3, the preparation method of 5-xylenol.
Background technology
3, the 5-xylenol is a kind of important Industrial intermediates, is a kind of white powder solid, and its boiling point is 219.5 ℃, can be dissolved in alkaline solution, and can and ethanol dissolve each other.Be the important source material of using during the ironed paper adhesion of oxygenant is produced, also can be used as antibiotic powder, preservative solution, the raw material that shampoo etc. are produced is agricultural chemicals, medicine, the important intermediate of resol.Therefore, 3, the production of 5-xylenol with and the optimization of production process be exactly an important step that improves industrial production efficient.
Traditional 3, the 5-xylenol is mainly derived from coal tar.But its quantity is extremely limited, can't satisfy industrial needs at all.And coal tar will be formed very under the complex state, to isolate purely 3, the technological process of 5-xylenol also is suitable difficulty.
With the method preparation 3 that industry transforms, the 5-xylenol mainly contains two kinds of technologies: a kind of be dimethylbenzene through sulfonation, transform alkalization, acidifying and obtaining.This method preparation cost is relatively expensive, and environmental pollution is very big, is unfavorable for being used for large batch of industrial production.And the method technological process of this preparation is loaded down with trivial details, and is higher to equipment requirements, and the productivity of reaction is also very low.Impurity in the product is more, separates also comparatively difficulty, if it is too high to be used for industrial mass production cost, wastes bigger.
With the isophorone is feedstock production 3, and the 5-xylenol adds catalyzer and at high temperature transforms.This preparation 3, the method for 5-xylenol began to be developed in the last sixties in a century.As United States Patent (USP) 269197 and United States Patent (USP) 4086282 disclosed methods.
Propose among the English Patent GB119783 using activated alumina Al
2O
3As catalyzer, can reach 90% at 550-500 ℃ of following transformation efficiency, but selectivity is not ideal enough, if catalyzer adds ferric oxide.Chromic oxide alkali oxide and alkaline-earth metal, then catalytic effect slightly improves to some extent.
Then mention catalysis C among the GB1451570
0-M
oAppendix again through calcining, adds 10% basic metal of catalyzer complexor again on alumina supporter, carry out heterogeneous catalysis with this catalyzer and transform, and selectivity is lower than 70%, and carbon distribution is more serious.
The method of above-mentioned patent disclosure, solid catalyst is easy to get, and price is cheaper, and catalytic condition also is not difficult to reach.But the productive rate and the selectivity of reaction are all not fully up to expectations; The second, homogeneous catalyst has catalytic effect preferably, can obtain bigger productive rate and selectivity, but this type of catalyzer costs an arm and a leg, and is difficult to obtain, and is also higher to the requirement of catalytic condition.
Summary of the invention
The technical issues that need to address of the present invention are to disclose a kind ofly 3, and the preparation method of 5-xylenol to overcome the defective that prior art exists, satisfies industrial needs.
Technical conceive of the present invention is such:
Whether contriver imagination combines solid catalyst and homogeneous catalyst and is applied to same technological process and can allows this process obtain better optimize.Concrete can selectively guide reaction expensive homogeneous catalyst into required direction as initiator on a small quantity, improves the productive rate and the selectivity of reaction with the solid catalyst synergy then.In addition, can also be in experimentation in requisition for adding some appropriate minor amounts of additives so that catalyzer is brought into play better catalytic effect.
According to above-mentioned design, method of the present invention comprises the steps:
In inert atmosphere, isophorone and liquid catalyst agent composition are fed the reactor that is equipped with solid catalyst from the top, reaction product is derived from reactor bottom, adopts conventional method to collect 3, the 5-xylenol then.
Said inert atmosphere can adopt nitrogen.
The contriver finds, method of the present invention, and operational condition is very crucial as the consumption of temperature, input speed, liquid catalyst.
It is generally acknowledged that high more helping more of temperature decompose, but reaction effect is really not so simple with variation of temperature, its selectivity is along with the rising of temperature has one to increase earlier the Changing Pattern that afterwards reduces.In the time of in temperature is 350～750 ℃ of scopes, along with the continuous rising of temperature, transformation efficiency is dull the rising, and selectivity of catalyst is to be the rising state.Selectivity reaches maximum during to 560～600 ℃.Along with the rising of temperature, the variation of yield also is a process that earlier rises and afterwards descend, and 600 ℃ of later temperature raise then that yield has reduced on the contrary.This just illustrates that selectivity of catalyst has an optimum value in this temperature range.Preferred temperature is 500～600 ℃, and pressure is normal pressure～0.2MPa.
The contriver finds that simultaneously input speed is slow more, and reactant is long more in the conversion zone time length, and then reaction effect should be good more, but the carbon distribution increase, throughput is little.Because the result of reaction combines a lot of aspects factor, air speed ground increases can reduce transformation efficiency, but might improve selectivity, and therefore preferred input speed is counted 20～160ml/h with the 40ml catalyzer;
Said solid catalyst comprises that mass percent is 0.1～20% the active ingredient and the carrier of surplus;
Said activeconstituents is selected from Fe
2O
3, CuO, BaO, Mo
2O
3, CoO, Cr
2O
3, Na
2CO
3, NaHCO
3, one or more mixtures among NaOH or the KOH, said carrier is γ-Al
2O
3
Said solid catalyst can adopt pickling process well known in the art or coprecipitation method preparation, as catalyticing research method, disclosed method in the documents and materials such as Preparation of catalysts.
Said liquid catalyst then is that some contains saturated and unsaturated aliphatics and aromatics that halogen element replaces, preferred bromoalkane, methyl iodide;
The continuous increase of the saturated alkane consumption that replaces along with halogen, the general trend that selectivity changes rises, and certain yield also is like this.When the consumption of liquid catalyst relatively hour, selectivity is bigger with the trend that the consumption of liquid catalyst increases, that is to say, in the scope of this amount, the rising of the reaction preference that the increase of liquid catalyst dosage causes is more obvious, and after the amount of homogeneous catalyst surpasses certain limit, then can not cause bigger influence to reaction result, consider and the reaction effect consideration from the angle of economy, the amount of liquid catalyst preferably the reactant quality 0.1～5%.
Because the charing phenomenon is comparatively serious, sometimes even reactor exit is stopped up.Therefore can in reaction raw materials, add entry, to relax the charing phenomenon.But what of the water yield also have certain influence to experiment.Because water reduces the catalytic effect of catalyzer sometimes as a reductive agent, the adding of less water is favourable to testing, and can prevent the charing of reactant effectively.Too many water is then unfavorable to testing.Flooding quantity has a comparatively suitable value, and in the 40ml solid catalyst, flooding quantity is 10～80ml/h.
Test-results of the present invention can adopt vapor-phase chromatography.
Analyzing and testing result shows, method of the present invention, and the transformation efficiency of reaction can reach 99.5%, and selectivity can reach more than 92.8%.
Because the present invention adopted the liquid-solid catalyzer, reaction is when reacting on reaction by solid-liquid biphase catalyzer one, and no matter reaction still be the selectivity aspect from transformation efficiency, with respect to only want much high with the catalytic effect of solid catalyst.Two-phase catalyst is shared, from the angle of economy, can reduce the consumption of expensive liquid catalyst of price very significantly, for industrializing implementation of the present invention provides condition.
Embodiment
Embodiment 1
In inert atmosphere, isophorone and liquid catalyst agent composition are fed the reactor that is equipped with solid catalyst from the top, reaction product is derived from reactor bottom, is cooled to 0 ℃ then, collects 3, the 5-xylenol.Implementation condition:
Solid catalyst is Cr
2O
3-γ-Al
2O
3, solid catalyst consumption: 40ml, Cr in the solid catalyst
2O
3Mass content is 18%.Liquid catalyst is a bromoalkane, and consumption is 1% of a reactant quality, and rare gas element is a nitrogen, input speed 45ml/h, and flooding quantity 20ml/h, temperature of reaction is 540 ℃, reaction pressure is 0.2Mpa.
Test-results: transformation efficiency is 100%, selectivity 88.2%, yield 88.0%.
Embodiment 2
Adopt the method identical with embodiment, its processing condition are:
Solid catalyst is NaHCO
3-γ-Al
2O
3, solid catalyst consumption: 40ml, NaHCO in the solid catalyst
3Mass content is 10%.Liquid catalyst is a methyl iodide, and consumption is 1.5% of a reactant quality, and rare gas element is a nitrogen, input speed 35ml/h, and flooding quantity 15ml/h, temperature of reaction is 560 ℃, reaction pressure is a normal pressure.
Test-results: transformation efficiency is 98%, selectivity 92.8%, yield 90%.
Embodiment 3
Adopt the method identical with embodiment, its processing condition are:
Solid catalyst is Co-Mo-Na-γ-Al
2O
3, solid catalyst consumption: 40ml, Co-Mo-Na is that mass content is 15% in the solid catalyst.Liquid catalyst is a bromoalkane, and consumption is 2% of a reactant quality, and rare gas element is a nitrogen, input speed 40ml/h, and temperature of reaction is 600 ℃, reaction pressure is 0.2Mpa.
Test-results: transformation efficiency is 98%, selectivity 91%, yield 89%.
Claims (6)
1. one kind 3, the preparation method of 5-xylenol is characterized in that comprising the steps:
In inert atmosphere, isophorone and liquid catalyst agent composition are fed the reactor that is equipped with solid catalyst from the top, reaction product is derived from reactor bottom, adopts conventional method to collect 3, the 5-xylenol then;
Temperature of reaction is 350～750 ℃; Reaction pressure: normal pressure～0.5MPa
Input speed is counted 10～800ml/h with the 40ml solid catalyst;
Said solid catalyst comprises that mass percent is 0.1～20% the active ingredient and the γ-Al of surplus
2O
3
Said activeconstituents is selected from Fe
2O
3, CuO, BaO, Mo
2O
3, CoO, Cr
2O
3, Na
2CO
3, NaHCO
3, one or more mixtures among NaOH or the KOH.
Said liquid catalyst is to contain saturated and unsaturated aliphatics or the aromatics that halogen element replaces.
2. method according to claim 1 is characterized in that said inert atmosphere can adopt nitrogen.
3. method according to claim 1 is characterized in that, 500～600 ℃ of temperature of reaction, reaction pressure are normal pressure～0.2Mpa.
4. method according to claim 1 is characterized in that, said liquid catalyst is bromoalkane, methyl iodide.
5. method according to claim 4 is characterized in that, the amount of the stable hydrocarbon that halogen replaces preferably the reactant quality 0.1～5%.
6. according to each described method of claim 1～5, it is characterized in that add entry in reaction raw materials, flooding quantity is counted 10～80ml/h with the 40ml solid catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410025166 CN1583697A (en) | 2004-06-15 | 2004-06-15 | Preparing method for 3,5-dimethyl phenol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410025166 CN1583697A (en) | 2004-06-15 | 2004-06-15 | Preparing method for 3,5-dimethyl phenol |
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|---|---|
| CN1583697A true CN1583697A (en) | 2005-02-23 |
Family
ID=34601172
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|---|---|---|---|
| CN 200410025166 Pending CN1583697A (en) | 2004-06-15 | 2004-06-15 | Preparing method for 3,5-dimethyl phenol |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671235B (en) * | 2009-10-19 | 2012-07-04 | 杭州华生医药化工有限公司 | Method for preparing 3,5-dimethylphenol by means of isophorone aromatization |
| CN103946346A (en) * | 2011-11-01 | 2014-07-23 | 沙特***石油公司 | Method for contemporaneously dimerizing and hydrating a feed having butene |
| CN106492818A (en) * | 2015-09-07 | 2017-03-15 | 万华化学集团股份有限公司 | A kind of heterogeneous catalysis and preparation method thereof, and the method using the catalyst preparation MX |
| CN108083962A (en) * | 2018-01-16 | 2018-05-29 | 北京化工大学 | Method that is a kind of while preparing 3,5- xylenols and mesitylene |
| CN113941361A (en) * | 2021-10-27 | 2022-01-18 | 山东新和成维生素有限公司 | Aromatization catalyst and preparation method and application thereof |
| RU2786739C1 (en) * | 2021-11-25 | 2022-12-26 | Федеральное государственное бюджетное научное учреждение Уфимский федеральный исследовательский центр Российской академии наук | Method for producing 3,5-xylenol |
-
2004
- 2004-06-15 CN CN 200410025166 patent/CN1583697A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101671235B (en) * | 2009-10-19 | 2012-07-04 | 杭州华生医药化工有限公司 | Method for preparing 3,5-dimethylphenol by means of isophorone aromatization |
| CN103946346A (en) * | 2011-11-01 | 2014-07-23 | 沙特***石油公司 | Method for contemporaneously dimerizing and hydrating a feed having butene |
| US10370612B2 (en) | 2011-11-01 | 2019-08-06 | Saudi Arabian Oil Company | Method and composition for contemporaneously dimerizing and hydrating a feed having butene to produce a gasoline composition |
| CN106492818A (en) * | 2015-09-07 | 2017-03-15 | 万华化学集团股份有限公司 | A kind of heterogeneous catalysis and preparation method thereof, and the method using the catalyst preparation MX |
| CN106492818B (en) * | 2015-09-07 | 2019-04-23 | 万华化学集团股份有限公司 | A kind of heterogeneous catalysis and preparation method thereof, and the method using the catalyst preparation 3,5-dimethylphenol |
| CN108083962A (en) * | 2018-01-16 | 2018-05-29 | 北京化工大学 | Method that is a kind of while preparing 3,5- xylenols and mesitylene |
| CN108083962B (en) * | 2018-01-16 | 2021-12-07 | 北京化工大学 | Method for simultaneously preparing 3, 5-dimethylphenol and mesitylene |
| CN113941361A (en) * | 2021-10-27 | 2022-01-18 | 山东新和成维生素有限公司 | Aromatization catalyst and preparation method and application thereof |
| CN113941361B (en) * | 2021-10-27 | 2023-11-28 | 山东新和成维生素有限公司 | Aromatization catalyst and preparation method and application thereof |
| RU2786739C1 (en) * | 2021-11-25 | 2022-12-26 | Федеральное государственное бюджетное научное учреждение Уфимский федеральный исследовательский центр Российской академии наук | Method for producing 3,5-xylenol |
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