CN103896740A - Method for producing methyl phenol - Google Patents
Method for producing methyl phenol Download PDFInfo
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- CN103896740A CN103896740A CN201310240660.2A CN201310240660A CN103896740A CN 103896740 A CN103896740 A CN 103896740A CN 201310240660 A CN201310240660 A CN 201310240660A CN 103896740 A CN103896740 A CN 103896740A
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- 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
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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
- C07C37/16—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 condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7007—Zeolite Beta
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/36—Steaming
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- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/37—Acid treatment
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a method for producing methyl phenol. The method comprises the following steps of: under the reaction conditions that the reaction temperature is 250-450 DEG C, the feeding weight airspeed is 0.3-5h<-1> and the pressure is normal, preheating materials containing ether, phenol and methanol, then mixing the materials with water steam, continuously passing through a plurality of sections of solid catalyst bed layer, carrying out gas-phase reaction to generate the methyl phenol, wherein the solid catalyst is selected from one or more in aluminium oxide, kaoline and a molecular sieve catalyst, and the phenol is selected from benzene phenol, dimethyl phenol and a mixture of the benzene phenol and the dimethyl phenol; the ether is selected from anisole, dimethyl ether, methyl anisole or a mixture of any two or more of the anisole, the dimethyl ether and the methyl anisole. When once-through yield of the methyl phenol is 0.2g/g (catalyst), the para-position selectivity for the methyl phenol can reach 45%; the stability of the catalyst is good, and no equipment corrosion occurs in the production process, so that the methyl phenol is an environmental-friendly catalyst and has good industrial application prospect.
Description
Technical field
The present invention relates to a kind of method of producing cresols.
Background technology
Cresols has three kinds of isomerss, p-cresol, ortho-cresol and meta-cresol.P-cresol is colourless liquid or the crystal with special odor, is corrosive and toxicity, is widely used in the industries such as oxidation inhibitor, dyestuff, medicine, agricultural chemicals, spices.Ortho-cresol, has another name called: 2-cresols is the important fine-chemical intermediates such as synthetic pesticide, medicine, dyestuff, synthetic resins, spices, oxidation inhibitor.Meta-cresol, has another name called 3-cresols, m-cresol, m-methyl phenol mainly as pesticide intermediate, produces sterilant Sumithion, Tiguvon, meta-tolyl-N-methylcarbamate (MTMC), Permanone, is also the intermediate of color film, resin, softening agent and spices.In coal tar phenol, approximately contain phenol 30%, ortho-cresol 10%-13%, meta-cresol 14%-18%, p-cresol 9%-12%, xylenol 13%-15%, traditional cresols preparation method is natural partition method, adopts separation method can reclaim 3 kinds of isomer of cresols.Due to resource-constrained, complex technical process in addition, the numerous deficiencies that wait of tripping device, through effort and exploration for many years, develop many kinds of cresols chemical synthesis process, after chemosynthesis succeeds, natural partition method is prepared cresols production equipment and is constantly closed.
Toluene sulfonation alkali fusion is traditional synthetic production technology of cresols, this law technology maturation, technique be simple, be suitable for producing p-cresol, but this method is used a large amount of strong acid and strong bases, equipment corrosion and environmental pollution are serious, and be batch production, be applicable to small-scale production, this method of domestic main employing is at present produced p-cresol.Chlorination toluene hydrolysis method, the chlorination of toluene benzene substitution in ring, hydrolysis obtains cresols mixture.Cresols neighbour that this method obtains,, to ratio be 1: 2: 1.This method environmental pollution is more serious, and by product is many, and therefore quality product is not high.Alkylation of phenol method, take phenol as raw material, methyl alcohol is alkylating agent, under liquid-phase condition, phenol, methyl alcohol are, under the condition of 300-400 ℃ and pressure 1～3MPa, to adopt Al in temperature
2o
3for catalyzer, phenol carries out methylation reaction and prepares ortho-cresol.This method obtains product and consists of ortho-cresol 43%～51%, meta-cresol 17%～36%, p-cresol 17%～36%, but severe reaction conditions does not possess competitive power compared with other cresols synthetic routes.Isopropyl toluene method, isopropyl toluene, under the initiation of the peroxide radical of hydrogen, changes into cymene hydroperoxide, be oxidized with the oxygen of air again, produce be rich between, paracresol, simultaneously by-product acetone, but react complexity synthetic higher than phenol far away.This method obtains product does not almost have ortho position product,, contraposition ratio is about 7: 3, is main synthetic meta-cresol operational path both at home and abroad at present.This method obtains that product purity is high, suitable for mass production, and shortcoming is that technical difficulty is large, and technical process is long, distilation expense is high.
In recent years, the research of toluene hydroxylation cresols processed also obtains certain progress, CN101786943 discloses a kind of method of preparing cresol by toluene one-step hydroxylation reaction, with the composite catalyst of HTS and acid treatment diatomite high-temperature roasting composition, take hydrogen peroxide as oxygenant, acetone is solvent, adopts the fixed bed catalyst system of continous way.The peak rate of conversion of toluene is 14%.Because toluene conversion is low, make this technology only rest on laboratory stage.CN101811938 discloses the method for dimethyl carbonate as methylating reagent p-methyl phenol processed.For the larger alkylating reagent of molecule, the HMCM-22 of lanthanum modification and MCM-41 mixed molecular sieve have good p-methyl phenol selectivity.Dimethyl carbonate, under acidic site effect, easily decomposes, and therefore in this reaction system, the utilization ratio of dimethyl carbonate is low, causes the production process Raw cost of cresols to increase.
At present, a large amount of document patents is all the reaction of phenol methanol alkylation based on metal oxide catalyst, take ortho-cresol as primary product, in product without the p-cresol of high added value, a certain amount of xylenol of by-product simultaneously.Take molecular sieve as the report of catalyzer phenol methanol alkylation cresols processed less.Catalysis journal, 1998,19 (5): 423-427, the reactivity worth of report phenol methyl alcohol on beta molecular sieve, adopts magnesium, manganese, lanthanum modification, the poor stability of catalyzer.Catalysis journal, 2001,22 (6): 545-549, report adopts P
2o
5, MgO and Sb
2o
3can improve the selectivity of aromatic oxide to HZSM-5 modification, reduce the selectivity of cresols and xylenol. along with the increase of oxide carried amount, ortho-cresol selectivity raises. and the oxide modifying of appropriateness can improve the selectivity of p-cresol, after phosphorus modification, para-selectivity increases to 35.87%, but the selectivity of cresols drops to 44.10%.Document Appl.Catal.A:Gen, 342 (2008) 40-48; Document J.Mol.Catal.A:Chem., in 327 (2010) 63-72 and document Catalysis Today133-135 (2008) 720-728, phenol methanol alkylation on hydrogen type molecular sieve catalyzer is reported, but experiment is used a large amount of nitrogen to do carrier gas, severe reaction conditions, but catalyzer is stable poor, there is no industrial application value.
CN101514144 discloses a kind of method of preparing Ortho Cresol.A certain proportion of phenol, 2,6-xylenol, first alcohol and water evenly mix and squeeze into through pump the reaction tubes that alkaline metal oxide catalyzer is housed, and pass into inert carrier gas in reaction tubes, and reaction product reclaims and obtains Ortho Cresol through condensation.This technique has realized the transalkylation reaction of xylenol and phenol on metal oxide catalyst, obtains more ortho-cresol.
Produce at present the full scale plant of cresols both at home and abroad without the alkylation of molecular sieve catalytic phenol methanol vapor phase, traditional cresols industrial product route, uses in strong acid and strong base, production process and produces a large amount of trade effluents, and environmental pollution is serious, and equipment corrosion is serious.Develop a kind of industrial technology with solid catalyst phenol vapor-phase alkylation production cresols extremely urgent.The technique of the production cresols of document patent report is one-stage process, take molecular sieve as catalyzer, the method for polycomponent charging, multi-stage fixed-bed production cresols rarely has report.The object of the present invention is to provide a kind of method of producing cresols, take polycomponent as raw material, adopt solid catalyst, react at multi-stage fixed-bed beds, cresols once through yield 0.2g cresols/g catalyzer. time, the para-selectivity of p-cresol can reach 45%.Use cheap kaolin and the catalyzer of alumina preparation, reduced catalyzer cost.In production process, without equipment corrosion, be a kind of eco-friendly processing method, there is good prospects for commercial application.
Summary of the invention
Be that to produce in cresols technology equipment corrosion serious according to the technical problem that solves in the past, in production process, produce the problem of a large amount of waste water, the invention provides a kind of method of producing cresols.Take phenols, ethers and methyl alcohol polycomponent as raw material, in fixed-bed reactor, produce cresols at multistage solid catalyst bed, production process is etching apparatus not, does not produce a large amount of trade effluents, is a kind of environmental friendliness friendly process.
For addressing the above problem, the technical solution used in the present invention is as follows: a kind of method of producing cresols, it is characterized in that, and 250 ℃-450 ℃ of temperature of reaction, 300 ℃-400 ℃ of preferable reaction temperature, feed weight air speed 0.3-5h
-1, preferred weight air speed 0.5-1.5h
-1, under synthesis under normal pressure condition, the raw material that comprises ether, phenol and methyl alcohol is mixed with water vapour after preheating continuously by multistage solid catalyst bed, carry out gas-phase reaction and generate cresols, wherein said solid catalyst is selected from aluminum oxide, kaolin and molecular sieve catalyst one or more, mol ratio ether: phenol: methyl alcohol=0-30: 50-70: 10-50 preferred molar ratio ether: phenol: methyl alcohol=5-15: 50-65: 15-30, described phenol is selected from phenol, xylenol and their mixture; Described ether is selected from methyl-phenoxide, dme, methylanisole or they two or more mixture arbitrarily.The mol ratio of water vapour and incoming mixture is 0.1-3.0, preferably 0.5-1.5, more especially 1.0.
In the present invention, molecular sieve catalyst, take molecular sieve as active ingredient, with binding agent mixing moulding, through being selected from one or more processing in acid treatment, oxide modifying and steam treatment, carries out acidic site modulation and is prepared from.
Particularly, molecular sieve catalyst preparation comprises: (1) molecular sieve and binding agent silicon oxide or silicon sol mixing moulding, be dried, 600 ℃ of roastings 10 hours.(2) through 10% nitric acid treatment, dry, 600 ℃ of roastings 10 hours.(3) in extrusion process, directly add modified compound to carry out oxide modifying, dry, 600 ℃ of roastings 10 hours.(4) 350-500 ℃ of steam treatment 2-10 hour.
In the method for the invention, solid catalyst aluminum oxide is made by industrial boehmite moulding; Solid catalyst kaolin is made by industrial kaolin moulding.
In the method for the invention, described molecular screening is from ZSM-5, BETA, and MCM-22, and MCM-49, a molecular sieve mole sial atomic ratio is 20-80, a preferred molecular sieve mole sial atomic ratio is 30-50.
In the method for the invention, molecular sieve molded middle employing Hydrogen or ammonium type molecular sieve, its weight content is 60-85%, all the other are binding agent.
In the method for the invention, multistage beds can be more than two sections and two sections beds, preferably the beds of two sections to four sections.
In the method for the invention, 250 ℃-450 ℃ of multistage reaction bed temperatures, preferably bed temperature 300-400 ℃.
In the method for the invention, raw material can be from the whole chargings of first paragraph, or sectional feeding.
In the method for the invention, raw material can be polycomponent charging, can be also two kinds of component chargings.
In the method for the invention, in multistage beds, the final stage beds of reaction mass contact is MCM-22 or MCM-49 molecular sieve catalyst.
In the method for the invention, the different catalysts bed that described multi-layer catalyst bed can be same reactor, or can be also the series connection between different reactor
In the method for the invention, it is composite modified that oxide modifying uses a kind of modification or the many oxide that are selected from rare-earth oxide and alkaline earth metal oxide.
In the method for the invention, steam treatment is 100% water vapour, and treatment temp is 350 ℃-500 ℃, and the time is 2-10 hour.
In general, establishing multi-stage fixed-bed object is in order to remove reaction heat, or cold feed reduces temperature of reaction, maintenance beds axial temperature homogeneous.What need to further illustrate at this is, multistage beds decapacitation of the present invention guarantees outside beds axial temperature homogeneous, it is mainly the feature for this reaction system, the different component chargings of multistage catalyzer, realize the suitable reaction in different catalysts of different components, improve cresols productive rate.Raw material can be all by products of phenol methanol alkylation except cresols, methyl-phenoxide, methylanisole, xylenol.Raw material can be also dme and phenol.Adopt the present invention, realize that all by products of phenol methanol alkylation are capable of circulation to react to reactive system.In addition, for by product methyl-phenoxide, the methylanisole of other devices, xylenol and dme, select different feed zones according to different inlet amounies, also can realize effective conversion.
Easily there is isomerization reaction, disproportionation reaction, molecular transposition in methyl-phenoxide, have under the condition of water participation on strongly-acid position on an acidic catalyst, hydrolysis reaction easily occurs and generate phenol and methyl alcohol.Phenol and methanol alkylation generate cresols.Under the condition that methylanisole has water to participate on acidic site, easily there is hydrolysis reaction, generate cresols and methyl alcohol.Xylenol carries out transalkylation reaction with phenol and generates cresols on an acidic catalyst.
Water vapor is except acting on methyl-phenoxide hydrolysis, and interpolation water vapour also plays increases the air speed of reaction mass to shift out reaction heat, avoids bed temperature local superheating; Reduce the effects such as material viscosity.
For the acidic site intensity difference of different catalysts, adopt different component co-feeding, for example methyl-phenoxide and methylanisole feed zone require acidity of catalyst position strong, should adopt ZSM-5 and beta as catalyzer.
The sequencing of the various modification programs of molecular sieve catalyst is not the key factor that affects catalytic performance.It should be noted that, the various method of modifying of catalyzer, are different and different according to the density of the strength of acid of parent molecule sieve and different acidic sites, and the various method of modifying that use in patent are composite modified obtains required catalyzer.For the less molecular sieve parent of the acidic site density of catalyzer, adopt one or more method of modifying of the present invention just can obtain desirable acidic site density.Therefore, the single method of modifying of various elements, also belongs to the field of containing of the present invention.For example, metal oxide modified, the single modification such as steam treatment all belongs to the scope of this patent.
A little less than the acidity of aluminum oxide and kaolin catalyst, under temperature of reaction, the reaction of phenol methanol alkylation can occur, but in product, the content of p-cresol is low, normal conditions can be used as first paragraph catalyzer.Obtain higher p-cresol selectivity, need to there is the enterprising single step reaction of catalyzer of selecting shape function.Methyl-phenoxide, methylanisole, xylenol charging are second segment charging, catalyzer is molecular sieve catalyst.
Methyl alcohol or dme, according to different products distribution, are selected suitable feed zone, and in general methyl alcohol and dme, as alkylating reagent, determine feed zone and inlet amount according to the content of phenol in reactant flow.
It should be noted that, the catalyst fixed bed reactor of polycomponent multistage in the present invention, the catalyzer of the final stage beds of reactant flow warp is MCM-22 molecular sieve catalyst or MCM-49 molecular sieve catalyst preferably.The solid catalyst function of other conversion zones is to transform different reactants.
The reacted reaction product of multistage, in the end one section of bed cresols carries out isomerization reaction, and in product, para-selectivity further improves.And simple metal oxide is applied this reaction as catalyzer, para-selectivity is very low, even in product without p-cresol.
Although adopted two sections, the three sections explanation summary of the invention that beds is detailed in embodiment, in fact between first paragraph and final stage beds, multistage beds can be set, also can realize the conversion of different products.Therefore four sections and more the bed of the catalyzer of multistage also belong to this scope of invention.Multi-layer catalyst bed, can be the different catalysts bed of same reactor, can be also the series connection between different reactor.That is to say, the series connection between different reactor, reaction stream, through the beds of each reactor, is also multi-catalyst bed, also belongs to the field that the present invention is contained.
For fixed-bed reactor, bed temperature homogeneous, reduces and imports and exports the temperature difference, and avoiding beds local superheating is the key of commercial catalysts stability.And the research of studying at present phenol methanol alkylation cresols processed is relatively less, and the industrial technology of phenol methanol alkylation cresols processed take molecular sieve as catalyzer has no report, and multistage bed sectional shifts out reaction heat, according to keeping overall bed temperature homogeneous.Avoid the more by product of high temperature production.Guarantee the safe and reliable of the stabilization of industry of catalyzer and technique.
MCM-49 molecular sieve in embodiment is synthetic according to the method in patent US5236575.MCM-22 molecular sieve in embodiment is synthetic according to the method in patent US4954325.ZSM-5 molecular sieve, Catalyst Factory, Nankai Univ is produced, name of product NKF-5.Beta molecular sieve, Catalyst Factory, Nankai Univ is produced, name of product NKF-6.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated.
Embodiment 1
The preparation process of molecular sieve catalyst is as follows: 170 grams, the Hydrogen MCM-22 molecular sieve that mole silica alumina ratio is 30, mix with 100 grams of silica weight 30% silicon sol, add a certain amount of lime acetate to mix, add 10% appropriate rare nitric acid as extrusion aid, extruded moulding.120 ℃ of oven dry, 550 ℃ of roastings 4 hours.Above-mentioned catalyzer is cut into 1～3mm and makes cylindrical catalyst parent A0.The precursor catalyst A0 of 20 grams adds 50ml, the salpeter solution of weight content 10%, soaking at room temperature 12 hours.120 ℃ of oven dry, 500 ℃ of roastings make A1 for 2 hours.20 grams of A1 are carried out to steam treatment 10 hours in 100% steam atmosphere, and treatment temp is 350 ℃, and roasting makes molecular sieve catalyst A for 3 hours at 550 ℃.The weight content that makes molecular sieve in catalyzer is 85%, the weight content 1% of calcium oxide.
Embodiment 2
The preparation process of molecular sieve catalyst is as follows: 170 grams, the Hydrogen MCM-49 molecular sieve that mole silica alumina ratio is 28, mix with 100 grams of silica weight 30% silicon sol, add a certain amount of nitrate of baryta calcium to mix, add 10% appropriate rare nitric acid as extrusion aid, extruded moulding.120 ℃ of oven dry, 550 ℃ of roastings 4 hours.Above-mentioned catalyzer is cut into 1～3mm and makes cylindrical catalyst parent B0.The precursor catalyst B0 of 20 grams adds 50ml, the salpeter solution of weight content 10%, soaking at room temperature 12 hours.120 ℃ of oven dry, 500 ℃ of roastings make B1 for 2 hours.20 grams of B1 are carried out to steam treatment 4 hours in 100% steam atmosphere, and treatment temp is 400 ℃, and roasting makes molecular sieve catalyst B for 3 hours at 550 ℃.The weight content that makes molecular sieve in catalyzer is 85%, barytic weight content 3%.
Embodiment 3
The preparation process of molecular sieve catalyst is as follows: 170 grams of the ammonia type ZSM-5 molecular sieves that mole silica alumina ratio is 80, mix with 100 grams of silica weight 30% silicon sol, add a certain amount of lanthanum nitrate to mix, add 10% appropriate rare nitric acid as extrusion aid, extruded moulding.120 ℃ of oven dry, 550 ℃ of roastings 4 hours.Above-mentioned catalyzer is cut into 1～3mm and makes cylindrical catalyst parent C0.The precursor catalyst C0 of 20 grams adds 50ml, the salpeter solution of weight content 10%, soaking at room temperature 12 hours.120 ℃ of oven dry, 500 ℃ of roastings make C1 for 2 hours.20 grams of C1 are carried out to steam treatment 2 hours in 100% steam atmosphere, and treatment temp is 500 ℃, and roasting makes molecular sieve catalyst C for 3 hours at 550 ℃.The weight content that makes molecular sieve in catalyzer is 85%, the weight content 3% of lanthanum trioxide.
Embodiment 4
The preparation process of molecular sieve catalyst is as follows: 120 grams, 50 grams silicon-dioxide of Hydrogen beta molecular sieve that mole silica alumina ratio is 20 mix with 100 grams of silica weight 30% silicon sol, add a certain amount of lanthanum nitrate to mix, add 10% appropriate rare nitric acid as extrusion aid, extruded moulding.120 ℃ of oven dry, 550 ℃ of roastings 4 hours.Above-mentioned catalyzer is cut into 1～3mm and makes cylindrical catalyst mother body D 0.The precursor catalyst D0 of 20 grams adds 50ml, the salpeter solution of weight content 10%, soaking at room temperature 12 hours.120 ℃ of oven dry, 500 ℃ of roastings make D1 for 2 hours.20 grams of D1 are carried out to steam treatment 2 hours in 100% steam atmosphere, and treatment temp is 350 ℃, and roasting makes molecular sieve catalyst D for 3 hours at 550 ℃.The content that makes molecular sieve in catalyzer is 60%, the weight content 3% of cerium oxide.
Embodiment 5
200 grams of industrial boehmites, add rare nitric acid extruded moulding of appropriate 10%, and room temperature is placed 10 hours, 120 ℃ dry 10 hours.650 ℃ of roastings 4 hours, make aluminium oxide catalyst.
200 grams of industrial kaolin, add rare nitric acid extruded moulding of appropriate 10%, and room temperature is placed 10 hours, 120 ℃ dry 10 hours.600 ℃ of roastings 4 hours, make kaolin catalyst.
Embodiment 6
The catalyzer that embodiment 1-5 is made reacts on multi-stage fixed-bed reaction unit.Raw material and water vapour enter beds through preheating and react, and reaction product on-line chromatograph is analyzed.Gas-chromatography is Agilent 7890A, and chromatographic column is cyclodextrin post 30m X0.25mm X0.25 μ m.Chromatographiccondition: column temperature: 100 ℃ of initial temperature, stop 5 minutes, 10 ℃/min of temperature rise rates rise to 150 ℃, constant temperature 10 minutes, 10 ℃/min of temperature rise rates rise to 180 ℃, constant temperature 7 minutes. and carrier gas is high pure nitrogen, before post, press: 6.5pisa, column flow rate 12.6cm/sec.Carrier gas is water vapour, and the mol ratio of water vapour and incoming mixture is 1.0.Cresols once through yield is with g cresols/g catalyzer. and in time, represents.
Comparative example
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.Use the molecular sieve catalyst A of embodiment 1,45ml.Adopt one section of beds, reaction raw materials enters from reactor head, 300 ℃ of temperature of reaction, weight space velocity 0.5h
-1.Reaction raw materials mol ratio methyl-phenoxide: methyl alcohol: phenol: xylenol=10: 20: 60: 10.React after 120 hours para-selectivity 35% in product, cresols once through yield 0.12g cresols/g catalyzer. time.
Embodiment 7
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.First paragraph uses the aluminium oxide catalyst 15ml in embodiment 5; Second segment uses the molecular sieve catalyst A of embodiment 1,30ml.Reaction raw materials enters from reactor head, 300 ℃ of temperature of reaction, weight space velocity 0.5h
-1.Reaction raw materials mol ratio methyl-phenoxide: methyl alcohol: phenol: xylenol=10: 20: 60: 10.React after 1000 hours para-selectivity 38% in product, cresols once through yield 0.15g cresols/g catalyzer. time.
Embodiment 8
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.First paragraph uses the aluminium oxide catalyst 15ml in embodiment 5; Second segment uses the molecular sieve catalyst A of embodiment 1,30ml.Reaction raw materials enters from reactor head, 300 ℃ of temperature of reaction, weight space velocity 0.8h
-1.Reaction raw materials mol ratio methyl-phenoxide: methylanisole: methyl alcohol: phenol: xylenol=10: 5: 20: 60: 5.React after 720 hours para-selectivity 40% in product, cresols once through yield 0.14g cresols/g catalyzer. time.
Embodiment 9
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.First paragraph uses the kaolin catalyst 15ml in embodiment 5, and second segment uses the molecular sieve catalyst B of embodiment 2,30ml.Reaction raw materials enters from reactor head, 350 ℃ of temperature of reaction, weight space velocity 1.0h
-1.Reaction raw materials mol ratio methyl-phenoxide: methyl alcohol: phenol: xylenol=5: 30: 60: 5.React after 120 hours para-selectivity 35% in product, cresols once through yield 0.14g cresols/g catalyzer. time.
Embodiment 10
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.First paragraph uses the aluminium oxide catalyst 15ml in embodiment 5; Second segment uses the molecular sieve catalyst C of embodiment 3,15ml; The 3rd section uses the molecular sieve catalyst A of embodiment 1,15ml.Reaction raw materials enters from reactor head, 400 ℃ of temperature of reaction, weight space velocity 0.5h
-1reaction raw materials mol ratio methyl-phenoxide: methyl alcohol: phenol: xylenol=15: 10: 65: 10.React after 120 hours para-selectivity 37% in product, cresols once through yield 0.16g cresols/g catalyzer. time.
Embodiment 11
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.First paragraph uses the aluminium oxide catalyst 15ml in embodiment 5; Second segment uses the molecular sieve catalyst D of embodiment 3,15ml; The 3rd section adopts the molecular sieve catalyst A of embodiment 1,15ml.Reaction raw materials enters from reactor head, 450 ℃ of temperature of reaction, weight space velocity 1.5h
-1.Reaction raw materials mol ratio methyl-phenoxide: methyl alcohol: phenol=5: 30: 65.React after 120 hours para-selectivity 35% in product, cresols once through yield 0.16g cresols/g catalyzer. time.
Embodiment 12
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.First paragraph uses the aluminium oxide catalyst 15ml in embodiment 5; Second segment uses the molecular sieve catalyst C of embodiment 3,10ml; The 3rd section adopts the molecular sieve catalyst A of embodiment 1,20ml.Reaction raw materials enters from reactor head, 350 ℃ of temperature of reaction, weight space velocity 1.0h
-1.Reaction raw materials mol ratio is dme: methyl alcohol: phenol: xylenol=5: 30: 60: 5.React after 120 hours para-selectivity 37% in product, cresols once through yield 0.16g cresols/g catalyzer. time.
Embodiment 13
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.First paragraph uses the aluminium oxide catalyst 15ml in embodiment 5, and first paragraph reaction feed mol ratio is methyl-phenoxide: dme: methyl alcohol: phenol: xylenol=5: 5: 20: 65: 5; Second segment adopts the molecular sieve catalyst A of embodiment 1,15ml; The 3rd section adopts the molecular sieve catalyst A of embodiment 1, and 15ml the 3rd section feeding methyl alcohol 1.2g/h enters from the 3rd section of beds top.350 ℃ of temperature of reaction, weight space velocity 1.0h
-1.React after 720 hours para-selectivity 37% in product, cresols once through yield 0.2g cresols/g catalyzer. time.
Embodiment 14
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.First paragraph adopts the kaolin catalyst 15ml in embodiment 5; Second segment adopts the molecular sieve catalyst C of embodiment 3,20ml; The 3rd section adopts the molecular sieve catalyst A of embodiment 1,10ml.Reaction raw materials enters from reactor head, 450 ℃ of temperature of reaction, weight space velocity 5h
-1.Reaction raw materials mol ratio is dme: methyl alcohol: phenol: xylenol=5: 30: 60: 5.React after 120 hours para-selectivity 35% in product, cresols once through yield 0.14g cresols/g catalyzer. time.
Embodiment 15
Adopt device and analytical procedure in embodiment 6, catalytic performance is evaluated.First paragraph adopts the aluminium oxide catalyst 15ml in embodiment 5; Second segment adopts the molecular sieve catalyst C of embodiment 3,10ml; The 3rd section adopts the molecular sieve catalyst A of embodiment 1,20ml.Reaction raw materials enters from reactor head, 250 ℃ of temperature of reaction, weight space velocity 0.3h
-1reaction raw materials mol ratio is dme: methyl alcohol: phenol: methyl-phenoxide=10: 20: 60: 5.React after 120 hours para-selectivity 45% in product, cresols once through yield 0.16g cresols/g catalyzer. time.
Embodiment 16
Adopt device and analytical procedure in embodiment 6, catalyst reaction performance is evaluated.First paragraph adopts the aluminium oxide catalyst 15ml in embodiment 5, phenol, and xylenol and methyl alcohol is from reactor head charging, phenol: xylenol: methyl alcohol mol ratio=30: 20: 50; Second segment adopts the molecular sieve catalyst C of embodiment 3,15ml; The 3rd section adopts the molecular sieve catalyst A of embodiment 1,20ml.320 ℃ of temperature of reaction, weight space velocity 0.5h
-1.React after 120 hours para-selectivity 35% in product, cresols once through yield 0.14g cresols/g catalyzer. time.
Embodiment 17
Adopt device and analytical procedure in embodiment 6, catalyst reaction performance is evaluated.First paragraph adopts the molecular sieve catalyst C in embodiment 3,15ml, and reaction mass is from reactor head charging, phenol: methyl alcohol mol ratio=60: 40.400 ℃ of first paragraph temperature of reaction; Second segment adopts the aluminium oxide catalyst of embodiment 5,15ml, 350 ℃ of temperature of reaction; The 3rd section adopts the molecular sieve catalyst A of embodiment 1,15ml, and the 3rd section feeding methyl alcohol 1.2g/h, enters from the 3rd section of beds top.300 ℃ of temperature of reaction, weight space velocity 0.5h
-1.React after 120 hours para-selectivity 36% in product, cresols once through yield 0.15g cresols/g catalyzer. time.
Embodiment 18
Adopt analytical procedure in embodiment 6, device adopts two reactors in series, and catalytic performance is evaluated.The first reactor adopts the aluminium oxide catalyst 20ml in embodiment 5; The second reactor adopts the molecular sieve catalyst C of embodiment 3,30ml; Reaction raw materials enters from the first reactor head, and reacted liquid enters the second reactor and proceeds reaction.The first 300 ℃ of reactor reaction temperature, the second 300 ℃ of reactor reaction temperature. weight space velocity 0.3h
-1reaction raw materials mol ratio is methyl alcohol: phenol: methyl-phenoxide=30: 60: 10.React after 120 hours para-selectivity 38% in product, cresols once through yield 0.17g cresols/g catalyzer. time.
Claims (10)
1. a method of producing cresols, is characterized in that, at 250 ℃-450 ℃ of temperature of reaction, feed weight air speed 0.3-5h
-1, under synthesis under normal pressure condition, the raw material that comprises ether, phenol and methyl alcohol is mixed with water vapour after preheating continuously by multistage solid catalyst bed, carry out gas-phase reaction and generate cresols, wherein said solid catalyst is selected from aluminum oxide, kaolin and molecular sieve catalyst one or more, mol ratio ether: phenol: methyl alcohol=0-30: 50-70: 10-50, described phenol is selected from phenol, xylenol and their mixture; Described ether is selected from methyl-phenoxide, dme, methylanisole or they two or more mixture arbitrarily.
2. method according to claim 1, it is characterized in that, described molecular sieve catalyst is take molecular sieve as active ingredient, with binding agent mixing moulding, through being selected from one or more processing in acid treatment, oxide modifying and steam treatment, carry out acidic site modulation and be prepared from.
3. method according to claim 1, is characterized in that, described molecular sieve is for being selected from ZSM-5, BETA, and MCM-22, and MCM-49, a molecular sieve mole sial atomic ratio is 20-80.
4. method according to claim 2, is characterized in that, molecular sieve molded middle employing Hydrogen or ammonium type molecular sieve, and its weight content is 60-85%, all the other are binding agent.
5. method according to claim 1, is characterized in that, multistage beds is more than two sections and two sections beds, preferably the beds of two sections to four sections.
6. method according to claim 1, is characterized in that raw material is from the whole chargings of first paragraph, or sectional feeding.
7. method according to claim 1, is characterized in that, the different catalysts bed that described multi-layer catalyst bed is same reactor, or the series connection between different reactor.
8. method according to claim 1, is characterized in that, in described multistage beds, the final stage beds of reaction mass contact is MCM-22, or MCM-49 molecular sieve catalyst.
9. according to the method described in claim 2, it is characterized in that, oxide modifying uses a kind of modification or the many oxide that are selected from rare-earth oxide and alkaline earth metal oxide composite modified.
10. method according to claim 2, is characterized in that, steam treatment is 100% water vapour, and treatment temp is 350 ℃-500 ℃, and the time is 2-10 hour.
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| CN104725196A (en) * | 2015-04-13 | 2015-06-24 | 江苏三吉利化工股份有限公司 | Method for synthesizing 2,6-xylenol and o-cresol by means of co-production |
| CN106378176A (en) * | 2016-08-29 | 2017-02-08 | 中国科学院过程工程研究所 | Metal salt- and/or metallic oxide-loaded catalyst, preparation method and application thereof |
| CN109277114A (en) * | 2017-07-19 | 2019-01-29 | 中国科学院大连化学物理研究所 | The preparation method of catalyst for etherification and the method for producing methyl phenyl ethers anisole |
| CN109277113A (en) * | 2017-07-19 | 2019-01-29 | 中国科学院大连化学物理研究所 | The preparation method of catalyst for etherification and the method for producing methylanisole |
| CN109970514A (en) * | 2019-03-04 | 2019-07-05 | 宝鸡文理学院 | A kind of method that catalytic refining methanol method synthesizes phenol in methyl phenyl ethers anisole technique |
| CN109970513A (en) * | 2019-03-04 | 2019-07-05 | 宝鸡文理学院 | A method of phenol in catalysis recycling methanol method synthesis methyl phenyl ethers anisole technique |
| CN110790637A (en) * | 2018-08-01 | 2020-02-14 | 中国科学院大连化学物理研究所 | Method for producing 2, 6-xylenol by phenol alkylation |
| CN111068769A (en) * | 2019-12-24 | 2020-04-28 | 河北工业大学 | Catalyst for dimethyl phenol catalytic hydrogenation demethylation reaction and preparation method and application thereof |
| CN113351243A (en) * | 2021-06-21 | 2021-09-07 | 山西大学 | Catalyst for producing m-cresol from o-cresol by isomerization and preparation method thereof |
| CN115109608A (en) * | 2022-05-19 | 2022-09-27 | 中国科学院大连化学物理研究所 | Method for preparing liquid fuel with low aromatic hydrocarbon content |
| CN115745751A (en) * | 2022-11-29 | 2023-03-07 | 大连理工大学 | Liquid-solid phase reaction method for continuously producing anisole by using phenol and methanol raw materials on fixed bed reactor |
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| CN116496146A (en) * | 2023-04-14 | 2023-07-28 | 大连理工大学 | Preparation method of methylphenol and homologs |
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| WO2014101374A1 (en) | 2014-07-03 |
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