CN103342629A - Fluidization catalytic method for producing m-cresol and p-cresol through isomerization of o-cresol - Google Patents
Fluidization catalytic method for producing m-cresol and p-cresol through isomerization of o-cresol Download PDFInfo
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Abstract
The invention relates to a fluidization catalytic method for producing m-cresol and p-cresol through isomerization of o-cresol. According to the method, o-cresol and a carrier gas are gasified in a preheater, and m-cresol and p-cresol are produced through isomerization by adopting the fluidization catalytic method, so that problems of short service life of a catalyst and low conversion rate in the isomerization process of cresol at present are better solved. The fluidization catalytic method can be applied to industrial production for large-scale production of the m-cresol and the p-cresol.
Description
Technical field
The present invention relates to a kind of ortho-cresol isomerization produce between, the fluidized catalyzing method of p-cresol.
Background technology
Cresols comprises three kinds of isomer, and namely ortho-cresol, p-cresol and meta-cresol all are important fine-chemical intermediates.Especially domestic seriously supply falls short of demand to, meta-cresol, annually needs that import is a great deal of satisfies domestic market demand.
The industrialized route of producing meta-cresol or p-cresol at present has: toluene sulfonation alkali fusion, chlorination toluene hydrolysis method, alkylation of phenol method, isopropyl toluene oxidation style.
The toluene sulfonation alkali fusion: this law technology maturation, technology is simple, but uses a large amount of strong acid and strong bases, and equipment corrosion and environmental pollution are serious.The chlorination toluene hydrolysis method: this method is to the equipment requirements harshness.The alkylation of phenol method: this method selectivity height, technological process is simple, and product cost is low, has become the main method that external major company produces ortho-cresol, and the technology crux of this method is the catalyzer that chooses.But China never has industrialization.The isopropyl toluene oxidation style: the product purity height that this method obtains, suitable for mass production, shortcoming are that technical difficulty is big, the raw material sources difficulty, and technical process is longer, the purification costs height, facility investment is big, wastewater treatment expense height.
In order to solve many technology and environmental problems such as the high pollution that exists in traditional meta-cresol and the p-cresol production process, maximum discharge, new meta-cresol and p-cresol producing and manufacturing technique-cresols isomery is produced the M-and P-cresols method and is just arisen at the historic moment.For example, " Tianjin chemical industry " (the 1st phase in 1994) reported that the development-cresols of cresols isomerization catalyst is at HCl-AlCl
3On isomerization, studied the isomerization reaction of cresols on aluminum trichloride catalyst, obtain meta-cresol content up to 68% cresols.But this method is the liquid phase batch operation, the catalyst recovery complexity, and loss is big, consumes high; Also exist in addition other problem such as equipment corrosion, contaminate environment.US Patent No. 4503269, US5053558 have reported that fixed bed isomerization process and US4283571, US4691063 have reported the isomerized catalyzer of fixed bed, but the transformation efficiency of the ortho-cresol after 36 hours of catalyzer wherein drops to 31.4% from 54.4% of beginning, and such catalyst performance is difficult to satisfy the long playing requirement of fixed bed catalyst far away.
Yet fluidized-bed catalyzed reaction technology can realize the real-time regeneration of decaying catalyst, and it is fast and cause the difficult problem of reaction terminating effectively to solve catalyst deactivation in the fixed bed reaction process.Still there is not at present the ortho-cresol isomerization to adopt the report of fluidized catalytic reaction.
By ortho-cresol fluidisation catalytic isomerization metallization processes can environmental protection ground produce between, p-cresol.This technology is to utilize ortho-cresol, through the fluidisation isoversion, between production, to cresols.With between existing, the p-cresol production technique compares, ortho-cresol fluidisation isoversion has the characteristics of green and environmental protection.
Summary of the invention
The invention provides a kind of utilize the ortho-cresol isomerization produce between, the method for p-cresol.What the present invention mainly solved is the problem that has catalyst activity life time weak point in the cresols isomerization process now, is difficult to regenerate.Therefore, the invention provides between a kind of new ortho-cresol isomerization preparation, the method for the fluidisation catalysis of p-cresol, this method has isomerization reaction continuously and the continuous advantage of catalyst regeneration, has overcome the problem of existing technology existence.
The present invention has adopted following technical scheme:
With ortho-cresol gasification, after mixing and be preheating to temperature of reaction with carrier gas, be passed in the fluidized-bed reactor and contact with the cresols isomerization catalyst, through between obtaining after the isomerization reaction being rich in, the reaction mixture A of p-cresol;
Between above-mentioned reaction mixture A rectifying separation obtained, p-cresol.
In the technique scheme, the ortho-cresol reactor is to adopt fluidized-bed reactor; Carrier gas is 0~10: 1 with ortho-cresol raw materials components mole ratio scope, is preferably 1: 1~5: 1; Temperature of reaction is 280~500 ℃, is preferably 290~440 ℃, more preferably about 290~about 430 ℃; Reaction pressure 0.1~5.0Mpa is preferably 0.1~1.5MPa; Ortho-cresol weight space velocity 0.2~15h
-1, be preferably 1~5.0h
-1
Between above-mentioned ortho-cresol isomerization is produced, in the fluidized catalyzing method of p-cresol, the carrier gas in the isomerization process can be selected nitrogen or hydrogen for use, also can be without carrier gas.Air speed is the key factor of control reaction in isomerization reaction, keeps suitable air speed, controls reaction velocity by regulating carrier gas tolerance.Thereby, by adopting aforesaid method, can solve the short problem of catalyst life in the prior art preferably, also can regulate the yield problem that air speed is controlled isomerization reaction easily.
Between ortho-cresol isomerization of the present invention is produced, in the fluidized catalyzing method of p-cresol, the catalyzer that uses is solid catalyst, solid material with certain acid-basicity all can obtain to use in the method, as solid super-strong acid, solid alkali, heteropolyacid, aluminum oxide and molecular sieve etc., wherein, the most frequently used catalyzer is Si-Al molecular sieve, and suitable material comprises ZSM-5, ZSM-11, ZSM-56, ZSM-48, ZSM-12, MCM-22, USY, mordenite (Mordenite), Beta etc., can also carry out modifying and decorating as the basis with these molecular screen materials, to improve the isomerization performance of catalyzer.Common method of modifying is thermal treatment, and is inorganic modified and metal-modified etc.
In the isomerized reaction mixture of ortho-cresol of the present invention, except, the p-cresol product, also contain a spot of phenol, ortho-cresol, xylenol and many cresols cut.Between ortho-cresol isomerization of the present invention is produced, the fluidized catalyzing method of p-cresol, its product separate part adopts existing ripe rectifying separation technology, the separation system of its head product comprises takes off phenol tower, take off the ortho-cresol tower and, the p-cresol knockout tower.Between after this system separates, obtaining, the p-cresol product.
The ortho-cresol that obtains after separating is fed to again carries out isomerization reaction in the fluidized-bed reactor.
Beneficial effect
The present invention is by gasifying ortho-cresol and carrier gas in preheater, the method of employing fluidisation catalysis is carried out between isomerization production, p-cresol, solved the problem that catalyst life is short, transformation efficiency is low that exists in the present cresols isomerization process preferably, can be applicable between scale operation, in the suitability for industrialized production of p-cresol.With between existing, the p-cresol production technique compares, ortho-cresol fluidisation catalytic isomerization metallization processes of the present invention has the characteristics of green and environmental protection.
Embodiment
The invention will be further described below by embodiment.
Technological process
Ortho-cresol is preheating to liquefaction, the ortho-cresol of preheating liquefaction is sent in the gasifier gasified, and with carrier gas N
2Mix in the gasifier the inside, then, feed fluidized-bed reactor and contact with the isomerization catalyst of silicon-aluminum containing molecular sieve.The isomerization reaction condition is: catalyzer usage quantity 3000 grams, 390 ℃ of temperature of reaction, ortho-cresol air speed are 2h
-1Face nitrogen, reaction pressure is 0.6MPa, used isomerization catalyst contains the aluminum oxide of weight percent 20% and 10% silicon-dioxide, all the other are the Si-Al molecular sieve catalyzer, between reaction obtains being rich in, the mixing phenols gas of p-cresol, rectifying separation after cooling off is isolated phenol, ortho-cresol, meta-cresol, p-cresol and many cresols.Wherein ortho-cresol comes back to gasifier and raw material ortho-cresol and is mixed into fluidized-bed reactor and carries out isomerization.
Embodiment 1~3
Carry out the ortho-cresol isomerization reaction according to the described step of above-mentioned technological process and condition respectively, wherein embodiment 1~3 employed catalyzer is respectively ZSM-5(silica alumina ratio 38), mordenite and Beta.Concrete reaction evaluating the results are shown in Table 1
Table 1
Embodiment | 1 | 2 | 3 |
Catalyzer | ZSM-5 | Mordenite | Beta |
Temperature of reaction (℃) | 390 | 390 | 390 |
Ortho-cresol transformation efficiency (%) | 61 | 57 | 55 |
Between/the p-cresol selectivity | 96 | 95 | 93 |
Table 1 data show, use the isomerization reaction of fluidized-bed catalysis ortho-cresol, can effectively solve short problem of stirring tank fixed bed catalyst life-span.And the transformation efficiency of ortho-cresol keeps higher level.The selectivity of meta-cresol is very high.
Embodiment 4~6
Carry out the ortho-cresol isomerization reaction according to embodiment 1 described step and condition, change the mol ratio of carrier gas nitrogen and ortho-cresol, concrete reaction conditions and evaluation result are listed in table 2.
Table 2
Embodiment | 4 | 5 | 6 |
Phenol nitrogen is than (mol) | 1 | 3 | 6 |
Temperature of reaction (℃) | 390 | 390 | 390 |
Ortho-cresol transformation efficiency (%) | 61 | 60 | 57 |
Between/the p-cresol selectivity | 95 | 96 | 92 |
Table 2 data show that phenol nitrogen mol ratio has individual optimum value, and to optimum value, the ortho-cresol isomerization is increasing to the selectivity of meta-cresol, surpasses optimum value from little, and selectivity is reducing.And the transformation efficiency of ortho-cresol reduces along with the increase of phenol nitrogen ratio.
Embodiment 7~10
Carry out the ortho-cresol isomerization reaction according to embodiment 1 described step and condition, change temperature of reaction, concrete reaction conditions and evaluation result are listed in table 3
Table 3
Embodiment | 7 | 8 | 9 | 10 |
Catalyzer | ZSM-5 | ZSM-5 | ZSM-5 | ZSM-5 |
Temperature of reaction (℃) | 290 | 350 | 390 | 430 |
Ortho-cresol transformation efficiency (%) | 53 | 56 | 61 | 65 |
Between/the p-cresol selectivity | 94 | 95 | 96 | 92 |
Table 3 data show that the temperature of reaction of ortho-cresol isomerization reaction is bigger to isomerization result influence.Show that by above-mentioned experimental result the more excellent temperature of reaction of isomerization is about 290~about 430 ℃, the best is about 390 ℃.
Claims (6)
1. between an ortho-cresol isomerization is produced, the fluidized catalyzing method of p-cresol, may further comprise the steps:
With ortho-cresol gasification, after mixing and be preheating to temperature of reaction with carrier gas, be passed in the fluidized-bed reactor and contact with the cresols isomerization catalyst, through between obtaining after the isomerization reaction being rich in, the reaction mixture of p-cresol;
Between above-mentioned reaction mixture rectifying separation obtained, p-cresol.
2. between ortho-cresol isomerization according to claim 1 is produced, the fluidized catalyzing method of p-cresol, it is characterized in that described carrier gas is nitrogen or hydrogen.
3. between ortho-cresol isomerization according to claim 1 is produced, the fluidized catalyzing method of p-cresol, it is characterized in that described catalyzer is solid super-strong acid, solid alkali, heteropolyacid, aluminum oxide or molecular sieve.
4. between ortho-cresol isomerization according to claim 3 is produced, the fluidized catalyzing method of p-cresol, it is characterized in that described molecular sieve catalyst is ZSM-5, ZSM-11, ZSM-56, ZSM-48, ZSM-12, MCM-22, USY molecular sieve, mordenite or Beta molecular sieve.
5. between ortho-cresol isomerization according to claim 1 is produced, the fluidized catalyzing method of p-cresol, it is characterized in that described carrier gas is 0~10: 1 with the raw materials components mole ratio of ortho-cresol.
6. between ortho-cresol isomerization according to claim 1 is produced, the fluidized catalyzing method of p-cresol, it is characterized in that, the isomerized reaction conditions of described ortho-cresol is as follows: 280~500 ℃ of temperature of reaction, reaction pressure 0.1~5.0MPa, ortho-cresol weight space velocity 0.2~15h
-1
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104923293A (en) * | 2015-06-17 | 2015-09-23 | 湖南长岭石化科技开发有限公司 | O-cresol isomerization catalyst, preparing method of o-cresol isomerization catalyst and method for catalyzed synthesis of mixture of m-cresol and p-cresol through o-cresol isomerization catalyst |
CN109078656A (en) * | 2018-09-30 | 2018-12-25 | 西安元创化工科技股份有限公司 | A kind of preparation method for the sylvan isomerization catalyst loading aluminium chloride |
CN113731476A (en) * | 2021-06-23 | 2021-12-03 | 浙江环化科技有限公司 | Solid acid catalyst and method for producing m-cresol |
CN115445653A (en) * | 2022-09-01 | 2022-12-09 | 宁夏派可威生物科技有限公司 | Preparation process of cresol isomerization catalyst |
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US4283571A (en) * | 1978-02-03 | 1981-08-11 | Union Rheinische Braunkohlen Kraftstoff Aktiengesellschaft | Process for the catalytic isomerization of o-cresol |
US4503269A (en) * | 1983-09-21 | 1985-03-05 | Uop Inc. | Isomerization of cresols |
US5015785A (en) * | 1989-08-09 | 1991-05-14 | Basf Aktiengesellschaft | Preparation of mixtures of isomeric cresols with a molar ratio of para- to meta-cresol of at least 0.6:1 to 10:1 |
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2013
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Patent Citations (3)
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US4283571A (en) * | 1978-02-03 | 1981-08-11 | Union Rheinische Braunkohlen Kraftstoff Aktiengesellschaft | Process for the catalytic isomerization of o-cresol |
US4503269A (en) * | 1983-09-21 | 1985-03-05 | Uop Inc. | Isomerization of cresols |
US5015785A (en) * | 1989-08-09 | 1991-05-14 | Basf Aktiengesellschaft | Preparation of mixtures of isomeric cresols with a molar ratio of para- to meta-cresol of at least 0.6:1 to 10:1 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104923293A (en) * | 2015-06-17 | 2015-09-23 | 湖南长岭石化科技开发有限公司 | O-cresol isomerization catalyst, preparing method of o-cresol isomerization catalyst and method for catalyzed synthesis of mixture of m-cresol and p-cresol through o-cresol isomerization catalyst |
CN104923293B (en) * | 2015-06-17 | 2017-08-22 | 湖南长岭石化科技开发有限公司 | Orthoresol isomerization catalyst, its preparation method and the method that M-and P-cresols is catalyzed and synthesized using it |
CN109078656A (en) * | 2018-09-30 | 2018-12-25 | 西安元创化工科技股份有限公司 | A kind of preparation method for the sylvan isomerization catalyst loading aluminium chloride |
CN113731476A (en) * | 2021-06-23 | 2021-12-03 | 浙江环化科技有限公司 | Solid acid catalyst and method for producing m-cresol |
CN113731476B (en) * | 2021-06-23 | 2023-10-03 | 浙江环化科技有限公司 | Method for producing m-cresol |
CN115445653A (en) * | 2022-09-01 | 2022-12-09 | 宁夏派可威生物科技有限公司 | Preparation process of cresol isomerization catalyst |
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