WO2014101374A1 - 一种生产甲酚的方法 - Google Patents

一种生产甲酚的方法 Download PDF

Info

Publication number
WO2014101374A1
WO2014101374A1 PCT/CN2013/077235 CN2013077235W WO2014101374A1 WO 2014101374 A1 WO2014101374 A1 WO 2014101374A1 CN 2013077235 W CN2013077235 W CN 2013077235W WO 2014101374 A1 WO2014101374 A1 WO 2014101374A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
cresol
molecular sieve
stage
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/CN2013/077235
Other languages
English (en)
French (fr)
Inventor
王坤院
徐云鹏
刘中民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Dalian Institute of Chemical Physics of CAS
Original Assignee
Dalian Institute of Chemical Physics of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dalian Institute of Chemical Physics of CAS filed Critical Dalian Institute of Chemical Physics of CAS
Publication of WO2014101374A1 publication Critical patent/WO2014101374A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • 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
    • B01J29/40—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
    • 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
    • B01J29/7007—Zeolite Beta
    • 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
    • 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
    • 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
    • B01J2229/37—Acid treatment
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • 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

Definitions

  • the present invention relates to a process for producing cresol. Background technique
  • P-cresol is a colorless liquid or crystal with a special odor, which is corrosive and toxic, and is widely used in industries such as antioxidants, dyes, medicines, pesticides, and fragrances.
  • O-cresol also known as 2-methyl phenol
  • M-cresol also known as 3-cresol, m-cresol, m-methylphenol, is mainly used as a pesticide intermediate to produce insecticides such as chlorpyrifos, fenthion, carbaryl, and permethrin.
  • Coal tar contains about 30% phenol, 10%-13% o-cresol, 14%-18% m-cresol, 9%-12% p-cresol, 13%-15% xylenol, traditional cresol
  • the preparation method is a natural separation method, and the separation method can recover the three isomers of cresol. Due to limited resources, complicated process, and numerous separation devices, after many years of hard work and exploration, many kinds of cresol chemical synthesis processes have been developed. After successful chemical synthesis, the cresol production equipment produced by natural separation method is continuously shut down.
  • the toluene sulfonation alkali fusion method is a traditional cresol synthesis production technology.
  • the method is mature, simple in process and suitable for the production of p-cresol, but the method uses a large amount of strong acid and alkali, equipment corrosion and environmental pollution are serious, and is intermittent Production, suitable for small-scale production, currently mainly used in this country to produce p-cresol.
  • the toluene chlorination method the chlorobenzene is substituted for chlorination, and the mixture is hydrolyzed to obtain a cresol mixture.
  • the ratio of cresol to o, m, and p, obtained by this method is 1:2:1.
  • Phenol thiolation method using phenol as raw material and methanol as alkylating agent, under liquid phase conditions, phenol and methanol are used at a temperature of 300-400 ° C and a pressure of l ⁇ 3 MPa, using A1 2 0 3 as Catalyst, phenol is methylated to prepare o-cresol.
  • the product obtained by this method is 43% ⁇ 51% of o-cresol, 17% ⁇ 36% of m-cresol and 17% ⁇ 36% of p-cresol, but the reaction conditions are harsh, and there is no competition compared with other mixed cresol synthetic routes. force.
  • Isopropyltoluene method isopropyl toluene is converted to methyl cumene hydroperoxide by the peroxide free radical of hydrogen, and then oxidized with oxygen of air to produce a rich, inter-parallel Cresol, at the same time Acetone is produced, but the reaction complexity is much higher than the synthesis of phenol.
  • the method has almost no ortho-products, and the ratio of meta- and para-position is about 7:3. It is the main synthetic m-cresol process route at home and abroad.
  • the method has high purity and is suitable for large-scale production, and has the disadvantages of high technical difficulty, long process flow and high purification and purification cost.
  • CN101786943 discloses a method for preparing cresol by one-step hydroxylation reaction of toluene, a composite catalyst composed of titanium silicon molecular sieve and acid-treated diatomaceous earth at high temperature roasting. Using hydrogen peroxide as the oxidant and acetone as the solvent, a continuous fixed bed catalytic reaction system was used. The highest conversion of toluene was 14%. Due to the low conversion of toluene, this technology is only in the laboratory stage. CN101811938 discloses a process for preparing methylphenol by using dimethyl carbonate as a methylating agent.
  • the hydrazine-modified HMCM-22 and MCM-41 hybrid molecular sieves have better p-methylphenol selectivity.
  • Dimethyl carbonate is easily decomposed under the action of acid sites, so the utilization rate of dimethyl carbonate in the reaction system is low, resulting in an increase in the cost of raw materials in the production process of cresol.
  • CN 101514144 discloses a process for the preparation of o-cresol.
  • a certain proportion of phenol, 2,6-xylenol, methanol and water are uniformly mixed and pumped into a reaction tube containing a basic metal oxide catalyst, and an inert carrier gas is introduced into the reaction tube, and the reaction product is recovered by condensation.
  • O-cresol was obtained. This process achieves the thiol transfer reaction of xylenol with phenol on a metal oxide catalyst. More o-cresol.
  • the object of the present invention is to provide a method for producing cresol, which uses a multi-component as a raw material and uses a solid catalyst to carry out a reaction in a multi-stage fixed bed catalyst bed with a cresol yield of 0.2 g cresol/g catalyst per pass.
  • the para-selectivity of p-cresol is up to 45%.
  • Catalysts prepared using inexpensive kaolin and alumina reduce the cost of the catalyst. There is no equipment corrosion during the production process, which is an environmentally friendly process with good industrial application prospects. Summary of the invention
  • the present invention provides a method for producing cresol. Using phenols, ethers and methanol as raw materials, in the fixed bed reactor, cresol is produced in a multi-stage solid catalyst bed, the production process does not corrode equipment, does not produce a large amount of industrial wastewater, is an environmentally friendly green Process.
  • the technical scheme adopted by the present invention is as follows: a method for producing cresol, characterized in that the reaction temperature is from 250 ° C to 450 ° C, preferably the reaction temperature is from 300 ° C to 400 ° C, and the feed weight is Airspeed ( ⁇ preferred weight space velocity O - h ⁇ Under normal pressure reaction conditions, the raw materials containing ether, phenol and methanol are preheated and mixed with steam to continuously pass through the multistage solid catalyst bed to carry out gas phase reaction to form cresol
  • the molecular sieve catalyst is prepared by mixing a molecular sieve as an active component with a binder, and performing acid treatment by one or more selected from the group consisting of acid treatment, oxide modification and steam treatment. Prepared by sexual modulation.
  • the preparation of the molecular sieve catalyst comprises: (1) molecular sieve mixed with a binder silica or a silicon sol, dried, and calcined at 600 ° C for 10 hours. (2) Treated with 10% nitric acid, dried and calcined at 600 ° C for 10 hours. (3) The modified compound is directly added to the oxide strip during the extrusion process, and dried, and calcined at 600 ° C for 10 hours. (4) 350-500 ° C steam treatment 2-10 hours.
  • the solid catalyst alumina is obtained by molding an industrial boehmite; the solid catalyst kaolin is obtained by molding an industrial kaolin.
  • the molecules are selected from ZSM-5, BETA, MCM-22, and MCM-49, and the molecular sieve molar silicon to aluminum atomic ratio is 20-80, and preferably the molecular sieve molar silicon-aluminum atomic ratio is 30-50.
  • a molecular sieve of hydrogen or ammonium type is used in the molecular sieve molding, and the weight thereof is 60-85%, and the balance is a binder.
  • the multistage catalyst bed may be a two or more stage catalyst bed, preferably a two to four stage catalyst bed.
  • the multistage catalyst bed has a temperature of from 250 ° C to 450 ° C, preferably a bed temperature of from 300 to 400 ° C.
  • the feedstock can be fed entirely from the first stage, or fed in stages.
  • the feedstock may be a multi-component feed or a two-component feed.
  • the last stage of the catalyst bed contacted by the reaction mass in the multi-stage catalyst bed is MCM-22 or MCM-49 molecular sieve catalyst.
  • the multilayer catalyst bed may be a different catalyst bed of the same reactor, or may be a series connection between different reactors.
  • the oxide modification uses a modification or a plurality of oxide composite modification selected from the group consisting of rare earth metal oxides and alkaline earth metal oxides.
  • the steam treatment is 100% steam
  • the treatment temperature is from 350 ° C to 500 ° C
  • the time is from 2 to 10 hours.
  • the purpose of the multi-stage fixed bed is to remove the heat of reaction, or the cold feed to lower the reaction temperature and to maintain a uniform axial temperature of the catalyst bed.
  • the multi-stage catalyst bed of the present invention mainly aims at the characteristics of the reaction system, and the different components of the multi-stage catalyst are fed, and different components are realized.
  • the starting material may be all by-products other than cresol, benzyl ether, methyl anisole, xylenol.
  • the starting materials can also be dimethyl ether and phenol.
  • all by-products of phenol methanol hydration can be recycled to the reaction system for reaction.
  • by-products anisole, methyl anisole, xylenol, and dimethyl ether depending on the amount of feed, different feed sections can be selected to achieve efficient conversion.
  • the anisole is prone to isomerization, disproportionation, and molecular rearrangement on the acidic catalyst. Under the condition that water is present at the strong acid sites, hydrolysis reaction is likely to occur to form phenol and methanol. The phenol and methanol are thiolated to form cresol. Methylanisole is susceptible to hydrolysis under conditions in which water is present at the acidic site to form cresol and methanol. The xylenol is transalkylated with phenol on an acidic catalyst to form cresol.
  • the addition of water vapor also increases the space velocity of the reaction material in order to remove the heat of reaction, avoid local overheating of the bed temperature, and reduce the viscosity of the material.
  • the anisole and methyl anisole feed sections require a strong acidity of the catalyst, and ZSM-5 and beta should be used as catalysts.
  • the acidity of the alumina and kaolin catalysts is weak. At the reaction temperature, phenol methanol thiolation can occur, but the content of p-cresol in the product is low, and it is usually used as the first stage catalyst. In order to obtain higher p-cresol selectivity, it is necessary to further react on a catalyst having a shape-selective function.
  • the anisole, methylanisole, and xylenol feeds are the second stage feed, and the catalyst is a molecular sieve catalyst.
  • Methanol or dimethyl ether according to different product distribution, select the appropriate feed section, generally methanol and dimethyl ether as alkylation reagent, according to the content of phenol in the reaction stream to determine the feed section and
  • the catalyst of the last stage of the catalyst bed through the reactant stream is preferably MCM-22 molecular sieve catalyst or MCM-49 molecular sieve catalyst.
  • the solid catalyst function of the other reaction stages is to convert different reactants.
  • the reaction product after the multistage reaction is subjected to isomerization reaction in the last stage of the layer of cresol, and the para-selectivity in the product is further improved.
  • the simple metal oxide is used as a catalyst to apply this reaction, the para-selectivity is very low, and even the product has no p-cresol.
  • the multi-layer catalyst bed may be a different catalyst bed of the same reactor or a series connection between different reactors. That is to say, the series connection between the different reactors, the reaction flowing through the catalyst bed of each reactor, and also the multi-catalyst bed, also belong to the field covered by the present invention.
  • the bed temperature is uniform, reducing the temperature difference between the inlet and outlet, and avoiding local overheating of the catalyst bed is the key to the stability of the industrial catalyst.
  • the multi-stage bed can be removed from the reaction heat in stages. The overall bed temperature is uniform. Avoiding the production of more by-products at high temperatures. The industrial stability of the catalyst and the safety and reliability of the process are guaranteed.
  • the MCM-49 molecular sieve in the examples was synthesized according to the method of Patent No. 5,236,575.
  • the MCM-22 molecular sieve in the examples was synthesized according to the method of Patent US 4,954,325.
  • Example 1 The invention is further illustrated by the following examples in connection with the examples.
  • Example 1 The invention is further illustrated by the following examples in connection with the examples.
  • the preparation process of the molecular sieve catalyst is as follows: 170 g of a hydrogen type MCM-22 molecular sieve having a molar ratio of silicon to aluminum of 30, mixed with 100 g of silica weight 30% silica sol, and adding a certain amount of acetic acid. The calcium is evenly mixed, and an appropriate amount of 10% dilute nitric acid is added as a squeezing agent to form a squeezing strip. Dry at 120 Torr and calcine at 550 ° C for 4 hours. The above catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor A0.
  • Example 2 20 g of the parent catalyst AO was added to 50 ml of a 10% by weight nitric acid solution and immersed for 12 hours at room temperature. It is dried at 120 ° C and calcined at 500 ° C for 2 hours to obtain Al. 20 g of A1 was subjected to steam treatment in a 100% steam atmosphere for 10 hours, a treatment temperature of 350 ° C, and calcination at 550 ° C for 3 hours to obtain a molecular sieve catalyst A. The weight content of the molecular sieve in the catalyst was 85%, and the weight content of calcium oxide was 1%.
  • Example 2 20 g of the parent catalyst AO was added to 50 ml of a 10% by weight nitric acid solution and immersed for 12 hours at room temperature. It is dried at 120 ° C and calcined at 500 ° C for 2 hours to obtain Al. 20 g of A1 was subjected to steam treatment in a 100% steam atmosphere for 10 hours, a treatment temperature of 350 ° C, and
  • the preparation process of the molecular sieve catalyst is as follows: 170 g of a hydrogen type MCM-49 molecular sieve having a molar ratio of silicon to aluminum of 28, mixed with 100 g of silica weight 30% silica sol, and a certain amount of strontium nitrate is uniformly mixed, and an appropriate amount of 10 is added. % dilute nitric acid is used as a squeezing agent to form a strip. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The above catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor B0.
  • the preparation process of the molecular sieve catalyst is as follows: 170 g of ammonia type ZSM-5 molecular sieve with a molar ratio of silicon to aluminum of 80, mixed with 100 g of silica weight 30% silica sol, and a certain amount of cerium nitrate is uniformly mixed, and an appropriate amount of 10% is added. Dilute nitric acid is used as a squeezing agent to form a strip. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The above catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor C0.
  • the preparation process of the molecular sieve catalyst is as follows: 120 g of a hydrogen type beta molecular sieve having a molar ratio of silica to alumina of 120, 50 g of silica and 100 g of a silica sol having a weight of 30 g of silica, and a certain amount of cerium nitrate is uniformly mixed, and an appropriate amount is added.
  • the 10% dilute nitric acid is used as a squeezing agent to form a strip. It is dried at 120 ° C and calcined at 550 ° C for 4 hours.
  • the above catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor D0.
  • Example 5 20 g of the parent catalyst DO was added to 50 ml of a 10% by weight nitric acid solution and immersed for 12 hours at room temperature. Dry at 120 °C and calcine at 500 °C for 2 hours to obtain Dl. 20 g of D1 was subjected to steam treatment in a 100% steam atmosphere for 2 hours, and the treatment temperature was 350 ° C, and calcination was carried out at 550 ° C for 3 hours to obtain a molecular sieve catalyst D. The content of the molecular sieve in the catalyst was 60%, and the weight of cerium oxide was 3%.
  • Example 5 20 g of the parent catalyst DO was added to 50 ml of a 10% by weight nitric acid solution and immersed for 12 hours at room temperature. Dry at 120 °C and calcine at 500 °C for 2 hours to obtain Dl. 20 g of D1 was subjected to steam treatment in a 100% steam atmosphere for 2 hours, and the treatment temperature was 350 ° C, and calcination was carried
  • the catalysts obtained in Examples 1-5 were reacted on a multistage fixed bed reactor.
  • the raw material and water vapor are preheated into the catalyst bed for reaction, and the reaction product is analyzed by on-line chromatography.
  • the gas chromatograph is the Agilent 7890A, and the column is a cyclodextrin column 30m X 0.25mm X 0.25 ⁇ .
  • Chromatographic conditions Column temperature: initial temperature 100 °C, stay for 5 minutes, 10 °C / minute heating rate increased to 150 ⁇ , constant temperature 10 minutes, 10 °C / minute heating rate increased to 180 °C, constant temperature 7 minutes.
  • the carrier gas was high purity nitrogen, precolumn pressure: 6.5 pisa, column flow rate 12.6 cm/sec.
  • the diluent gas is water vapor and the molar ratio of water vapor to feed mixture is 1.0.
  • the cresol single pass yield is expressed as g cresol / g catalyst.
  • the catalytic performance was evaluated by using the apparatus and analysis method of Example 6.
  • the molecular sieve catalyst A of Example 1 was used, 45 ml.
  • the product had a para-selectivity of 35% and a cresol single-pass yield of 0.12 g of cresol/g of catalyst.
  • the catalytic performance was evaluated by using the apparatus and analysis method of Example 6.
  • the first stage used 15 ml of the alumina catalyst of Example 5; the second stage used the molecular sieve catalyst A of Example 1, 30 ml.
  • the product had a para-selectivity of 38% and a one-way yield of cresol of 0.15 g of cresol / g of catalyst.
  • the catalytic performance was evaluated by using the apparatus and analysis method of Example 6.
  • the first stage used 15 ml of the alumina catalyst of Example 5; the second stage used the molecular sieve catalyst A of Example 1, 30 ml.
  • the reaction starting material enters from the top of the reactor at a reaction temperature of 300 ° C and a weight space velocity of 0.811 - 1 .
  • Reaction material molar ratio anisole: methyl anisole: methanol: phenol: xylenol 10: 5: 20: 60: 5.
  • the product had a para-selectivity of 40% and a cresol single-pass yield of 0.14 g of cresol/g of catalyst.
  • the catalytic performance was evaluated by using the apparatus and analysis method of Example 6.
  • the first stage used 15 ml of the kaolin catalyst of Example 5, and the second stage used the molecular sieve catalyst B of Example 2, 30 ml.
  • the reaction raw material enters from the top of the reactor, the reaction temperature is 350 ° C, the weight space velocity l.
  • Oh - the reaction raw material molar ratio anisole: methanol: phenol: xylenol 5: 30: 60: 5.
  • the product has a para-selectivity of 35% and a cresol yield of 0.14 g of cresol/g catalyst.
  • the catalytic performance was evaluated by using the apparatus and analysis method of Example 6.
  • the first stage used 15 ml of the alumina catalyst of Example 5; the second stage used the molecular sieve catalyst C of Example 3, 15 ml; and the third stage used the molecular sieve catalyst A of Example 1, 15 ml.
  • the para-selectivity in the product was 37%, and the cresol single-pass yield was 0.16 g cresol/g catalyst.
  • the catalytic performance was evaluated by using the apparatus and analysis method of Example 6.
  • the first stage used 15 ml of the alumina catalyst of Example 5; the second stage used the molecular sieve catalyst D of Example 3, 15 ml; and the third stage used the molecular sieve catalyst A of Example 1, 15 ml.
  • the reaction starting material enters from the top of the reactor at a reaction temperature of 450 ° C and a space velocity of 1.511.
  • the product had a p-selectivity of 35% and a cresol yield of 0.16 g of cresol / g of catalyst per pass.
  • the catalytic performance was evaluated by using the apparatus and analysis method of Example 6.
  • the first stage used 15 ml of the alumina catalyst of Example 5; the second stage used the molecular sieve catalyst C of Example 3, 10 ml; and the third stage used the molecular sieve catalyst A of Example 1, 20 ml.
  • the reaction raw material enters from the top of the reactor, the reaction temperature is 350 ° C, the weight space velocity l.
  • the product had a para-selectivity of 37% and a one-way yield of cresol of 0.16 g of cresol / g of catalyst.
  • the catalytic performance was evaluated by using the apparatus and analysis method of Example 6.
  • the second stage uses the molecular sieve catalyst A of Example 1, 15 ml;
  • the third stage uses the molecular sieve catalyst A of Example 1, 15 ml.
  • the catalytic performance was evaluated by using the apparatus and analysis method of Example 6.
  • the first stage used 15 ml of the kaolin catalyst of Example 5; the second stage used the molecular sieve catalyst C of Example 3, 20 ml; and the third stage used the molecular sieve catalyst A of Example 1, 10 ml.
  • the reaction raw material enters from the top of the reactor at a reaction temperature of 450 ° C, and the space velocity is 511.
  • the product had a selectivity of 35% and a cresol yield of 0.14 g of cresol / g of catalyst per pass.
  • the catalytic performance was evaluated using the apparatus and analytical method of Example 6.
  • the first stage used 15 ml of the alumina catalyst of Example 5; the second stage used the molecular sieve catalyst C of Example 3, 10 ml; and the third stage used the molecular sieve catalyst A of Example 1, 20 ml.
  • the catalyst reaction performance was evaluated by the apparatus and analysis method of Example 6.
  • the reaction temperature was 320 ° C
  • the weight space velocity was 0.5 h - after the reaction for 120 hours
  • the product had a para-selectivity of 35% and a cresol single-pass yield of 0.14 g of cresol / g of catalyst.
  • the catalyst reaction performance was evaluated by using the apparatus and analysis method of Example 6.
  • First A portion of the molecular sieve catalyst C of Example 3, 15 ml, was used, and the reaction mass was fed from the top of the reactor, and the phenol: methanol molar ratio 60:40.
  • the first reaction temperature is 400 ⁇ ;
  • the second stage uses the alumina catalyst of Example 5, 15 ml, and the reaction temperature is 350 ° C;
  • the third stage uses the molecular sieve catalyst A of Example 1, 15 ml, and the third stage feeds methanol 1.2 g / h, entering from the top of the third stage catalyst bed.
  • the reaction temperature was 300 ° C, the weight space velocity was 0.5 h - after the reaction for 120 hours, the product was 36% para-selective, and the cresol yield was 0.15 g cresol / g catalyst.
  • Example 6 Using the analytical method of Example 6, the apparatus was used in series with two reactors to evaluate the catalytic performance.
  • the first reactor used 20 ml of the alumina catalyst of Example 5; the second reactor used the molecular sieve catalyst C of Example 3, 30 ml; the reaction raw material entered from the top of the first reactor, and the reacted liquid entered the second reactor to continue. Carry out the reaction.
  • the first reactor has a reaction temperature of 300 ° C
  • the second reactor has a reaction temperature of 300 ° C.
  • the product had a para-selectivity of 38% and a cresol yield of 0.17 g of cresol/g of catalyst per pass.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Dispersion Chemistry (AREA)

Abstract

本发明提供了一种生产甲酚的方法，在反应温度250-450℃、进料重量空速0.3-5h-1、常压反应条件下，将包含醚、酚和甲醇的原料经预热后与水蒸气混合连续通过多段固体催化剂床层，进行气相反应生成甲酚，其中所述固体催化剂选自氧化铝、高岭土和分子筛催化剂中一种或多种，所述酚选自苯酚、二甲酚和它们的混合物；所述醚选自苯甲醚、二甲醚、甲基苯甲醚或它们任意两种或多种的混合物。甲酚单程收率0.2g甲酚/g催化剂时，对甲酚的对位选择性可达45%。催化剂稳定性好，生产过程中无设备腐蚀，是一种环境友好的催化剂，具有良好的工业应用前景。

Description

一种生产甲酚的方法
技术领域
本发明涉及一种生产甲酚的方法。 背景技术
甲酚有三种同分异构体， 对甲酚、邻甲酚和间甲酚。对甲酚是具有特 殊气味的无色液体或晶体， 有腐蚀性和毒性， 广泛应用于抗氧剂、 染料、 医药、 农药、 香料等行业。 邻甲酚， 又名: 2-甲酚， 是合成农药、 医药、 染 料、 合成树脂、 香料、 抗氧剂等重要的精细化工中间体。 间甲酚， 又名 3-甲酚、 间甲苯酚、间甲基苯酚主要用作农药中间体， 生产杀虫剂杀螟松、 倍硫磷、 速灭威、 二氯苯醚菊酯， 也是彩色胶片、 树脂、 增塑剂和香料的 中间体。煤焦油酚中约含有苯酚 30%，邻甲酚 10%-13%，间甲酚 14%-18%， 对甲酚 9%-12%， 二甲酚 13%-15%， 传统的甲酚制备方法是天然分离法， 采用分离方法可以回收甲酚 3种异构体。 由于资源有限， 加之工艺过程复 杂， 分离装置众多等不足， 经过多年的努力与探索， 开发出许多种甲酚化 学合成工艺， 自化学合成获得成功之后， 天然分离法制备甲酚生产装置不 断地被关闭。
甲苯磺化碱熔法是传统的甲酚合成生产技术， 该法技术成熟、工艺简 单、 适于生产对甲酚， 但是该法使用大量强酸强碱， 设备腐蚀和环境污染 严重， 而且是间歇式生产， 适用于小规模生产， 目前国内主要采用该法生 产对甲酚。甲苯氯化水解法， 甲苯苯环上取代氯化，水解得到甲酚混合物。 该法得到的甲酚邻、 间、 对之比为 1 :2: 1。 该法环境污染比较严重， 副产 物多， 因此产品质量不高。 苯酚垸基化法， 以苯酚为原料， 甲醇为烷基化 剂， 在液相条件下， 苯酚、 甲醇在温度为 300-400°C和压力 l~3MPa的条 件下， 采用 A1203为催化剂， 苯酚进行甲基化反应制备邻甲酚。 该法获得 产品组成为邻甲酚 43%~51%、 间甲酚 17%〜36%、 对甲酚 17%〜36%， 但 是反应条件苛刻， 与其他混合甲酚合成路线相比不具备竞争力。异丙基甲 苯法， 异丙基甲苯在氢的过氧化物游离基的引发下， 转化成甲基异丙苯氢 过氧化物， 再用空气的氧气进行氧化， 生产出富含间、 对位甲酚， 同时副 产丙酮， 但是反应复杂程度远远高于苯酚的合成。该法得到产品几乎没有 邻位产品， 间、 对位比例约为 7:3， 是目前国内外主要合成间甲酚工艺路 线。 此法得到产品纯度高、 适宜大规模生产， 缺点是技术难度大， 工艺流 程长、 蒸馏提纯费用高。
近年来， 甲苯羟基化制甲酚的研究也取得一定进展， CN101786943 公开了一种甲苯一步羟基化反应制备甲酚的方法，以钛硅分子筛和酸处理 硅藻土高温焙烧组成的复合型催化剂，以过氧化氢为氧化剂，丙酮为溶剂， 采用连续式的固定床催化反应体系。 甲苯的最高转化率为 14%。 由于甲苯 转化率低， 使得该项技术仅停留在实验室阶段。 CN101811938公开了碳酸 二甲脂作为甲基化试剂制对甲基苯酚的方法。 对于分子较大的烷基化试 剂， 镧改性的 HMCM-22和 MCM-41混合分子筛具有较好的对甲基苯酚 选择性。 碳酸二甲脂在酸性位作用下， 易分解， 因此该反应体系中碳酸二 甲脂的利用率低， 导致甲酚的生产过程中原料成本增加。
目前，大量的文献专利都是基于金属氧化物催化剂上的苯酚甲醇烷基 化反应， 以邻甲酚为主要产物， 产物中无高附加值的对甲酚， 同时副产一 定量的二甲酚。 以分子筛为催化剂苯酚甲醇烷基化制甲酚的报道较少。催 化学报， 1998,19 (5) :423-427，报道苯酚甲醇在 beta分子筛上的反应性能， 采用镁、锰、镧改性，催化剂的稳定性差。催化学报， 2001,22 (6):545-549, 报道采用P205 ,MgO 和 Sb203 对 HZSM-5 改性都可以提高芳香醚的选择 性,降低甲酚和二甲酚的选择性. 随着氧化物负载量的增加,邻甲酚选择性 升高. 适度的氧化物改性可以提高对甲酚的选择性， 磷改性后对位选择性 增加为 35.87%，但甲酚的选择性下降为 44.10%。文献入 1. &1&1.八:0611, 342 (2008) 40- 48;文献 J. Mol. Catal. A:Chem., 327 (2010) 63-72及文献 Catalysis Today 133-135 (2008) 720-728中对氢型分子筛催化剂上苯酚甲醇烷基化 进行报道， 但实验使用大量的氮气做稀释气， 反应条件苛刻， 但催化剂的 稳定差， 没有工业应用价值。
CN 101514144公开了一种制备邻甲苯酚的方法。 一定比例的苯酚、 2, 6-二甲酚、 甲醇和水均匀混合经泵打入装有碱性金属氧化物催化剂的反 应管， 并往反应管中通入惰性载气， 反应产物经冷凝回收得到邻甲苯酚。 此工艺在金属氧化物催化剂上实现了二甲酚与苯酚的垸基转移反应，得到 更多的邻甲酚。
目前国内外无分子筛催化苯酚甲醇气相垸基化生产甲酚的工业装置， 传统的甲酚工业生产路线， 使用强酸强碱、生产过程中产生大量的工业废 水， 环境污染严重， 设备腐蚀严重。 开发一种以固体催化剂苯酚气相烷基 化生产甲酚的工业技术迫在眉睫。文献专利报道的生产甲酚的工艺均为一 段法， 以分子筛为催化剂、 多组分进料、 多段固定床生产甲酚的方法鲜有 报道。 本发明的目的在于提供一种生产甲酚的方法， 以多组分为原料， 采 用固体催化剂， 在多段固定床催化剂床层进行反应， 甲酚单程收率 0.2g甲 酚 /g催化剂.时， 对甲酚的对位选择性可达 45%。 使用廉价的高岭土及氧化 铝制备的催化剂， 降低了催化剂成本。 生产过程中无设备腐蚀， 是一种环 境友好的工艺方法， 具有良好的工业应用前景。 发明内容
依据所解决的技术问题是以往生产甲酚技术中设备腐蚀严重，生产过 程中产生大量废水的问题， 本发明提供一种生产甲酚的方法。 以酚类、 醚 类及甲醇多组分为原料， 在固定床反应器中， 在多段固体催化剂床层生产 甲酚， 生产过程不腐蚀设备， 不产生大量的工业废水， 是一种环境友好绿 色工艺。
为解决上述问题，本发明采用的技术方案如下：一种生产甲酚的方法， 其特征在于， 在反应温度 250°C-450°C， 优选反应温度 300°C-400°C、 进 料重量空速（ ^ΙιΛ 优选重量空速 O - h^ 常压反应条件下， 将包含 醚、 酚和甲醇的原料经预热后与水蒸气混合连续通过多段固体催化剂床 层， 进行气相反应生成甲酚， 其中所述固体催化剂选自氧化铝、 高岭土和 分子筛催化剂中一种或多种， 摩尔比醚： 酚： 甲醇 =0-30 : 50-70： 10-50 优选摩尔比醚： 酚： 甲醇 =5-15 : 50-65： 15-30， 所述酚选自苯酚、 二甲酚 和它们的混合物； 所述醚选自苯甲醚、 二甲醚、 甲基苯甲醚或它们任意两 种或多种的混合物。水蒸气与进料混合物的摩尔比为 0.1-3.0，优选 0.5-1.5， 更特别是 1.0。
在本发明中，分子筛催化剂以分子筛为活性组分，与粘结剂混合成型， 经过选自酸处理、氧化物改性和水蒸气处理中的一种或多种处理， 进行酸 性位调变制备而成。
具体地， 分子筛催化剂制备包括： （1 )分子筛与粘结剂氧化硅或硅溶 胶混合成型，干燥、 600°C焙烧 10小时。（2)经 10%硝酸处理，干燥、 600°C 焙烧 10小时。 （3 ) 挤条过程中直接加入改性化合物进行氧化物改性， 干 燥、 600°C焙烧 10小时。 (4) 350-500°C水蒸气处理 2-10小时。
在本发明的方法中， 固体催化剂氧化铝由工业薄水铝石成型制得； 固 体催化剂高岭土由工业高岭土成型制得。
在本发明的方法中， 所述分子筛选自 ZSM-5,BETA,MCM-22,和 MCM-49,分子筛摩尔硅铝原子比为 20-80， 优选分子筛摩尔硅铝原子比为 30-50。
在本发明的方法中， 分子筛成型中采用氢型或铵型分子筛， 其重量含 量为 60-85%， 其余为粘结剂。
在本发明的方法中，多段催化剂床层可以是两段及两段以上催化剂床 层， 优选两段至四段的催化剂床层。
在本发明的方法中， 多段催化剂床层温度 250°C-450°C， 优选床层温 度 300-400 °C。
在本发明的方法中， 原料可以从第一段全部进料， 或者分段进料。 在本发明的方法中，原料可以是多组分进料，也可以是两种组份进料。 在本发明的方法中，多段催化剂床层中反应物料接触的最后一段催化 剂床层为 MCM-22或 MCM-49分子筛催化剂。
在本发明的方法中，所述多层催化剂床层可以是同一个反应器的不同 催化剂床层， 或也可以是不同反应器之间的串联
在本发明的方法中，氧化物改性使用选自稀土金属氧化物和碱土金属 氧化物中的一种改性或多种氧化物复合改性。
在本发明的方法中， 水蒸气处理为 100%水蒸气， 处理温度为 350°C-500°C , 时间为 2-10小时。
一般来说， 设多段固定床的目的是为了移除反应热， 或冷进料降低反 应温度， 保持催化剂床层轴向温度均一。 在此需要进一步说明的是， 本发 明的多段催化剂床层除能保证催化剂床层轴向温度均一外，主要是针对该 反应体系的特点， 多段催化剂不同组份进料、实现不同组份在不同催化剂 上适当的反应， 提高甲酚产率。原料可以是苯酚甲醇垸基化除甲酚外的所 有副产物， 苯甲醚， 甲基苯甲醚， 二甲酚。 原料也可以是二甲醚和苯酚。 采用本发明， 实现苯酚甲醇垸基化所有副产物可循环至反应系统进行反 应。 除此之外， 对于其他装置的副产物苯甲醚、 甲基苯甲醚， 二甲酚、 及 二甲醚， 根据不同的进料量选择不同的进料段， 也可实现有效转化。
苯甲醚在酸性催化剂上易发生异构化反应、 歧化反应、 分子重排， 在 强酸性位上有水参与的条件下， 易发生水解反应生成苯酚和甲醇。苯酚和 甲醇垸基化生成甲酚。甲基苯甲醚在酸性位上有水参与的条件下易发生水 解反应， 生成甲酚和甲醇。 二甲酚在酸性催化剂上与苯酚进行烷基转移反 应生成甲酚。
水蒸汽除作用于苯甲醚水解外，添加水蒸气还起到增加反应物料的空 速以便移出反应热， 避免床层温度局部过热； 减少物料粘度等作用。
针对不同催化剂的酸性位强度不同， 采用不同的组份联合进料， 例如 苯甲醚和甲基苯甲醚进料段的要求催化剂酸性位强，宜采用 ZSM-5及 beta 作为催化剂。
分子筛催化剂的各种改性程序的先后顺序，并不是影响催化性能的关 键因素。 需要说明的是， 催化剂的各种改性方法， 是根据母体分子筛的酸 强度和不同酸性位的密度不同而不同，专利中使用的各种改性方法复合改 性得到所需的催化剂。对于催化剂的酸性位密度较小的分子筛母体， 采用 本发明的一种或多种改性方法就可得到理想的酸性位密度。 因此， 各种元 素的单一改性方法， 也属于本发明的涵盖领域。 例如， 金属氧化物改性， 水蒸气处理等单一改性均属于该专利的范围。
氧化铝及高岭土催化剂的酸性弱， 在反应温度下， 可发生苯酚甲醇垸 基化反应， 但是产物中对甲酚的含量低， 通常情况可作为第一段催化剂。 要获得较高的对甲酚选择性， 需要在具有择形功能的催化剂上进一步反 应。 苯甲醚， 甲基苯甲醚、 二甲酚进料为第二段进料， 催化剂为分子筛催 化剂。
甲醇或二甲醚根据不同的产物分布， 选择适宜的进料段， 一般来说甲 醇和二甲醚作为烷基化试剂，根据反应物流中苯酚的含量决定进料段及进 需要特别说明的是， 本发明中多组分多段催化剂固定床反应器， 反应 物流经的最后一段催化剂床层的催化剂优选是 MCM-22 分子筛催化剂或 MCM-49分子筛催化剂。其他反应段的固体催化剂功能是转化不同的反应 物。
多段反应后的反应产物， 在最后一段床层甲酚进行异构化反应， 产物 中对位选择性进一步提高。 而单纯的金属氧化物作为催化剂应用本反应， 对位选择性是很低的， 甚至产物中无对甲酚。
尽管实施例中采用了两段、三段催化剂床层详细的说明发明内容， 实 际上在第一段和最后一段催化剂床层之间可以设置多段催化剂床层，也可 以实现不同产物的转化。因此四段及更多段的催化剂的床层也属于该发明 的范围。 多层催化剂床层， 可以是同一个反应器的不同催化剂床层， 也可 以是不同反应器之间的串联。 也就是说， 不同反应器之间的串联， 反应流 经各反应器的催化剂床层，也是多催化剂床层，也属于本发明涵盖的领域。
对于固定床反应器来说， 床层温度均一， 减少进出口温差， 避免催化 剂床层局部过热是工业催化剂稳定性的关键。而目前研究苯酚甲醇垸基化 制甲酚的研究相对较少，而以分子筛为催化剂的苯酚甲醇烷基化制甲酚的 工业技术未见报道， 多段床层可分段移出反应热， 根据保持整体床层温度 均一。避免了高温生产更多的副产物。保证了催化剂的工业稳定性及工艺 的安全可靠。
实施例中的 MCM-49分子筛是按照专利 US5236575中的方法合成。 实施例中的 MCM-22分子筛是按照专利 US4954325中的方法合成。 ZSM-5 分子筛， 南开大学催化剂厂生产， 产品名称 KF-5。 beta分子筛， 南开大 学催化剂厂生产， 产品名称 NKF-6。
具体实施方式
以下结合实施例对本发明进行作进一步阐述。 实施例 1
分子筛催化剂的制备过程如下： 摩尔硅铝比为 30的氢型 MCM-22分 子筛 170克， 与 100克二氧化硅重量 30%硅溶胶混合， 加入一定量的乙酸 钙混合均匀， 加入适量的 10%稀硝酸作为助挤剂， 挤条成型。 120Ό烘干， 550°C焙烧 4小时。 上述催化剂切成 l~3mm制得柱状催化剂母体 A0。 20 克的母体催化剂 AO加入 50ml， 重量含量 10%的硝酸溶液， 室温浸泡 12 小时。 120°C烘干， 500°C焙烧 2小时制得 Al。 将 20克 A1在 100%水蒸 气气氛中进行水蒸气处理 10小时， 处理温度为 350°C， 550°C下焙烧 3小 时制得分子筛催化剂 A。 制得催化剂中分子筛的重量含量为 85%,氧化钙 的重量含量 1%。 实施例 2
分子筛催化剂的制备过程如下： 摩尔硅铝比为 28的氢型 MCM-49分 子筛 170克，与 100克二氧化硅重量 30%硅溶胶混合，加入一定量的硝酸 钡钙混合均匀， 加入适量的 10%稀硝酸作为助挤剂， 挤条成型。 120°C烘 干， 550°C焙烧 4小时。上述催化剂切成 l~3mm制得柱状催化剂母体 B0。 20克的母体催化剂 B0加入 50ml， 重量含量 10%的硝酸溶液， 室温浸泡 12小时。 120°C烘干， 500°C焙烧 2小时制得 Bl。 将 20克 B1在 100%水 蒸气气氛中进行水蒸气处理 4小时， 处理温度为 400°C， 550°C下焙烧 3 小时制得分子筛催化剂6。制得催化剂中分子筛的重量含量为 85%，氧化 钡的重量含量 3%。 实施例 3
分子筛催化剂的制备过程如下：摩尔硅铝比为 80的氨型 ZSM-5分子 筛 170克，与 100克二氧化硅重量 30%硅溶胶混合，加入一定量的硝酸镧 混合均匀， 加入适量的 10%稀硝酸作为助挤剂， 挤条成型。 120°C烘干， 550°C焙烧 4小时。 上述催化剂切成 l~3mm制得柱状催化剂母体 C0。 20 克的母体催化剂 CO加入 50ml， 重量含量 10%的硝酸溶液， 室温浸泡 12 小时。 120°C烘干， 500°C焙烧 2小时制得 Cl。 将 20克 C1在 100%水蒸 气气氛中进行水蒸气处理 2小时， 处理温度为 500°C， 550°C下焙烧 3小 时制得分子筛催化剂 C。制得催化剂中分子筛的重量含量为 85%，氧化镧 的重量含量 3%。 实施例 4
分子筛催化剂的制备过程如下： 摩尔硅铝比为 20的氢型 beta分子筛 120克、 50克二氧化硅与 100克二氧化硅重量 30%硅溶胶混合，加入一定 量的硝酸镧混合均匀， 加入适量的 10%稀硝酸作为助挤剂， 挤条成型。 120°C烘干， 550 °C焙烧 4小时。 上述催化剂切成 l〜3mm制得柱状催化剂 母体 D0。 20克的母体催化剂 DO加入 50ml， 重量含量 10%的硝酸溶液， 室温浸泡 12小时。 120 °C烘干， 500 °C焙烧 2小时制得 Dl。 将 20克 D1 在 100%水蒸气气氛中进行水蒸气处理 2小时， 处理温度为 350 °C， 550 °C 下焙烧 3小时制得分子筛催化剂 D。 制得催化剂中分子筛的含量为 60%， 氧化铈的重量含量 3%。 实施例 5
200克工业薄水铝石， 加入适量的 10%的稀硝酸挤条成型， 室温放置 10小时， 120 °C干燥 10小时。 650 °C焙烧 4小时， 制得氧化铝催化剂。
200克工业高岭土，加入适量的 10%的稀硝酸挤条成型，室温放置 10 小时， 120 °C干燥 10小时。 600 °C焙烧 4小时， 制得高岭土催化剂。 实施例 6
将实施例 1-5制得的催化剂，在多段固定床反应装置上进行反应。 原 料及水蒸气经预热进入催化剂床层进行反应， 反应产物在线色谱分析。 气相色谱为安捷伦 7890A, 色谱柱为环糊精柱 30m X 0.25mm X 0.25μπι。 色谱分析条件： 柱温： 初温 100 °C， 停留 5分钟， 10 °C/分钟升温速率升 至 150 Ό , 恒温 10分钟， 10 °C/分钟升温速率升至 180 °C， 恒温 7分钟. 载气为高纯氮气，柱前压： 6.5pisa,柱流速 12.6cm/sec。稀释气为水蒸气， 水蒸气与进料混合物的摩尔比为 1.0。 甲酚单程收率以 g甲酚 /g催化剂. 时表示。
反应器出口对甲基苯酚的重量百分比
对位选择性 = X 100% 对比实施例
采用实施例 6中装置及分析方法， 对催化性能进行评价。 使用实施 例 1的分子筛催化剂 A, 45ml。采用一段催化剂床层， 反应原料从反应器 顶部进入， 反应温度 300°C， 重量空速 (^！！ 反应原料摩尔比苯甲醚： 甲醇： 苯酚： 二甲酚 =10: 20： 60： 10。 反应 120小时后， 产物中对位选 择性 35%， 甲酚单程收率 0.12g甲酚 /g催化剂.时。 实施例 Ί
采用实施例 6中装置及分析方法， 对催化性能进行评价。 第一段使 用实施例 5中的氧化铝催化剂 15ml; 第二段使用实施例 1的分子筛催化 剂 A, 30ml。 反应原料从反应器顶部进入， 反应温度 300 °C， 重量空速 0.5h— 反应原料摩尔比苯甲醚： 甲醇： 苯酚： 二甲酚 =10: 20： 60： 10。 反应 1000小时后， 产物中对位选择性 38%， 甲酚单程收率 0.15g甲酚 /g 催化剂.时 。 实施例 8
采用实施例 6中装置及分析方法， 对催化性能进行评价。 第一段使 用实施例 5中的氧化铝催化剂 15ml; 第二段使用实施例 1的分子筛催化 剂 A, 30ml。 反应原料从反应器顶部进入， 反应温度 300 °C， 重量空速 0.811-1。 反应原料摩尔比苯甲醚： 甲基苯甲醚： 甲醇： 苯酚： 二甲酚 =10: 5： 20： 60： 5。 反应 720小时后， 产物中对位选择性 40%， 甲酚单程收 率 0.14g甲酚 /g催化剂.时。 实施例 9
采用实施例 6中装置及分析方法， 对催化性能进行评价。 第一段使 用实施例 5中的高岭土催化剂 15ml， 第二段使用实施例 2的分子筛催化 剂 B, 30ml。 反应原料从反应器顶部进入， 反应温度 350 °C， 重量空速 l .Oh— 反应原料摩尔比苯甲醚： 甲醇： 苯酚： 二甲酚 =5: 30： 60： 5。 反应 120小时后， 产物中对位选择性 35%， 甲酚单程收率 0.14g甲酚 /g 催化剂.时. 采用实施例 6中装置及分析方法， 对催化性能进行评价。 第一段使 用实施例 5中的氧化铝催化剂 15ml; 第二段使用实施例 3的分子筛催化 剂 C， 15ml; 第三段使用实施例 1的分子筛催化剂 A, 15ml。 反应原料从 反应器顶部进入， 反应温度 400°C， 重量空速 ( h—1反应原料摩尔比苯甲 醚： 甲醇： 苯酚： 二甲酚 =15 : 10： 65： 10。 反应 120小时后， 产物中对 位选择性 37%， 甲酚单程收率 0.16g甲酚 /g催化剂.时。 实施例 11
采用实施例 6中装置及分析方法， 对催化性能进行评价。 第一段使 用实施例 5中的氧化铝催化剂 15ml; 第二段使用实施例 3的分子筛催化 剂 D， 15ml; 第三段采用实施例 1的分子筛催化剂 A, 15ml。 反应原料从 反应器顶部进入， 反应温度 450°C， 重量空速 1.511 反应原料摩尔比苯 甲醚： 甲醇：苯酚 =5: 30： 65。反应 120小时后，产物中对位选择性 35%， 甲酚单程收率 0.16g甲酚 /g催化剂.时。 实施例 12
采用实施例 6中装置及分析方法， 对催化性能进行评价。 第一段使 用实施例 5中的氧化铝催化剂 15ml; 第二段使用实施例 3的分子筛催化 剂 C， 10ml; 第三段采用实施例 1的分子筛催化剂 A, 20ml。 反应原料从 反应器顶部进入， 反应温度 350°C， 重量空速 l .Oh— 反应原料摩尔比为 二甲醚： 甲醇： 苯酚： 二甲酚 =5: 30： 60： 5。 反应 120小时后， 产物中 对位选择性 37%， 甲酚单程收率 0.16g甲酚 /g催化剂.时。 实施例 13
采用实施例 6中装置及分析方法， 对催化性能进行评价。 第一段使 用实施例 5中的氧化铝催化剂 15ml， 第一段反应进料摩尔比为苯甲醚： 二甲醚： 甲醇： 苯酚： 二甲酚 =5 : 5： 20： 65： 5； 第二段采用实施例 1 的分子筛催化剂 A， 15ml; 第三段釆用实施例 1的分子筛催化剂 A, 15ml 第三段进料甲醇 1.2g/h从第三段催化剂床层顶部进入。反应温度 350°C， 重量空速 l.Oh- 反应 720小时后， 产物中对位选择性 37%， 甲酚单程收 率 0.2g甲酚 /g催化剂.时。 实施例 14
采用实施例 6中装置及分析方法， 对催化性能进行评价。 第一段采 用实施例 5中的高岭土催化剂 15ml; 第二段采用实施例 3的分子筛催化 剂 C， 20ml; 第三段采用实施例 1的分子筛催化剂 A, 10ml。反应原料从 反应器顶部进入， 反应温度 450°C， 重量空速 511人反应原料摩尔比为二 甲醚： 甲醇： 苯酚： 二甲酚 =5: 30： 60： 5。 反应 120小时后， 产物中对 位选择性 35%， 甲酚单程收率 0.14g甲酚 /g催化剂.时。 实施例 15
采用实施例 6中装置及分析方法，对催化性能进行评价。第一段采 用实施例 5中的氧化铝催化剂 15ml; 第二段采用实施例 3的分子筛催化 剂 C， 10ml; 第三段采用实施例 1的分子筛催化剂 A, 20ml。反应原料从 反应器顶部进入， 反应温度 250Ό , 重量空速 0.3h— 1反应原料摩尔比为二 甲醚： 甲醇： 苯酚： 苯甲醚 =10: 20： 60： 5。 反应 120小时后， 产物中 对位选择性 45%， 甲酚单程收率 0.16g甲酚 /g催化剂.时。 实施例 16
采用实施例 6中装置及分析方法，对催化剂反应性能进行评价。第 一段采用实施例 5中的氧化铝催化剂 15ml， 苯酚， 二甲酚及甲醇从反应 器顶部进料， 苯酚： 二甲酚： 甲醇摩尔比 =30: 20： 50； 第二段采用实施 例 3的分子筛催化剂 C， 15ml; 第三段采用实施例 1的分子筛催化剂 A, 20ml。 反应温度 320°C， 重量空速 0.5h— 反应 120小时后， 产物中对位 选择性 35%， 甲酚单程收率 0.14g甲酚 /g催化剂.时。 实施例 17
采用实施例 6中装置及分析方法，对催化剂反应性能进行评价。第 一段采用实施例 3中的分子筛催化剂 C, 15ml,反应物料从反应器顶部进 料， 苯酚： 甲醇摩尔比 =60: 40。 第一段反应温度 400Ό ; 第二段采用实 施例 5 的氧化铝催化剂， 15ml， 反应温度 350°C ; 第三段采用实施例 1 的分子筛催化剂 A, 15ml， 第三段进料甲醇 1.2g/h， 从第三段催化剂床层 顶部进入。 反应温度 300°C， 重量空速 0.5h— 反应 120小时后， 产物中 对位选择性 36%， 甲酚单程收率 0.15g甲酚 /g催化剂.时。 实施例 18
采用实施例 6中分析方法， 装置采用两个反应器串联， 对催化性能 进行评价。 第一反应器采用实施例 5中的氧化铝催化剂 20ml; 第二反应 器采用实施例 3的分子筛催化剂 C， 30ml; 反应原料从第一反应器顶部 进入， 反应后的液体进入第二反应器继续进行反应。 第一反应器反应温 度 300°C，第二反应器反应温度 300 °C .重量空速 OJh 反应原料摩尔比为 甲醇： 苯酚： 苯甲醚 =30: 60： 10。 反应 120小时后， 产物中对位选择性 38%， 甲酚单程收率 0.17g甲酚 /g催化剂.时。

Claims

权 利 要 求
1、 一种生产甲酚的方法， 其特征在于， 在反应温度 250°C-450°C、进 料重量空速 0.3-511-1、 常压反应条件下， 将包含醚、 酚和甲醇的原料经预 热后与水蒸气混合连续通过多段固体催化剂床层， 进行气相反应生成甲 酚，其中所述固体催化剂选自氧化铝、高岭土和分子筛催化剂中一种或多 种， 摩尔比醚： 酚： 甲醇 =0-30: 50-70： 10-50, 所述酚选自苯酚、 二甲酚 和它们的混合物； 所述醚选自苯甲醚、 二甲醚、 甲基苯甲醚或它们任意两 种或多种的混合物。
2、 根据权利要求 1所述的方法， 其特征在于， 所述分子筛催化剂以 分子筛为活性组分， 与粘结剂混合成型， 经过选自酸处理、氧化物改性和 水蒸气处理中的一种或多种处理， 进行酸性位调变制备而成。
3、 根据权利要求 1 所述的方法， 其特征在于， 所述分子筛为选自 ZSM-5,BETA,MCM-22,和 MCM-49,分子筛摩尔硅铝原子比为 20-80。
4、 根据权利要求 2所述的方法， 其特征在于， 分子筛成型中采用氢 型或铵型分子筛， 其重量含量为 60-85%， 其余为粘结剂。
5、 根据权利要求 1所述的方法， 其特征在于， 多段催化剂床层是两 段及两段以上催化剂床层， 优选两段至四段的催化剂床层。
6、根据权利要求 1所述的方法， 其特征在于原料从第一段全部进料， 或者分段进料。
7、 根据权利要求 1所述的方法， 其特征在于， 所述多层催化剂床层 是同一个反应器的不同催化剂床层， 或是不同反应器之间的串联。
8、 根据权利要求 1所述的方法， 其特征在于， 所述多段催化剂床层 中反应物料接触的最后一段催化剂床层为 MCM-22,或 MCM-49分子筛催 化剂。
9、 根据权利要求 2中所述的方法， 其特征在于， 氧化物改性使用选 自稀土金属氧化物和碱土金属氧化物中的一种改性或多种氧化物复合改 性。
10、 根据权利要求 2所述的方法， 其特征在于， 水蒸气处理为 100% 水蒸气， 处理温度为 350°C-500°C， 时间为 2-10小时。
PCT/CN2013/077235 2012-12-25 2013-06-14 一种生产甲酚的方法 Ceased WO2014101374A1 (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201210571475 2012-12-25
CN201210571475.7 2012-12-25

Publications (1)

Publication Number Publication Date
WO2014101374A1 true WO2014101374A1 (zh) 2014-07-03

Family

ID=50988370

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2013/077235 Ceased WO2014101374A1 (zh) 2012-12-25 2013-06-14 一种生产甲酚的方法

Country Status (2)

Country Link
CN (1) CN103896740B (zh)
WO (1) WO2014101374A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311337A (zh) * 2015-06-23 2017-01-11 中国石油化工股份有限公司 一种甲苯羟基化制甲酚的催化剂及制备方法

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104725196B (zh) * 2015-04-13 2016-08-17 江苏三吉利化工股份有限公司 一种邻甲酚联产2，6-二甲酚的合成方法
CN106378176A (zh) * 2016-08-29 2017-02-08 中国科学院过程工程研究所 金属盐和/或金属氧化物负载催化剂、其制备方法及应用
CN109277114A (zh) * 2017-07-19 2019-01-29 中国科学院大连化学物理研究所 醚化催化剂的制备方法以及生产苯甲醚的方法
CN109277113A (zh) * 2017-07-19 2019-01-29 中国科学院大连化学物理研究所 醚化催化剂的制备方法以及生产甲基苯甲醚的方法
CN110790637B (zh) * 2018-08-01 2021-03-30 中国科学院大连化学物理研究所 一种苯酚烷基化生产2,6-二甲酚的方法
CN109970514B (zh) * 2019-03-04 2021-10-19 宝鸡文理学院 一种催化精制甲醇法合成苯甲醚工艺中苯酚的方法
CN109970513B (zh) * 2019-03-04 2021-12-28 宝鸡文理学院 一种催化回收甲醇法合成苯甲醚工艺中苯酚的方法
CN111068769B (zh) * 2019-12-24 2022-07-19 河北工业大学 一种二甲酚催化加氢脱甲基反应用催化剂及其制备方法和应用
CN113351243B (zh) * 2021-06-21 2022-12-30 山西大学 一种用于邻甲酚异构生产间甲酚的催化剂及其制备方法
EP4134361A1 (de) * 2021-08-13 2023-02-15 LANXESS Deutschland GmbH Verfahren zur herstellung von kresol aus ditolylether
CN115109608B (zh) * 2022-05-19 2023-10-24 中国科学院大连化学物理研究所 一种制备低芳烃含量液体燃料的方法
CN115745751B (zh) * 2022-11-29 2023-12-29 大连理工大学 在固定床反应器上用苯酚和甲醇原料连续生产苯甲醚的液固相反应方法
CN116969814B (zh) * 2023-02-03 2025-08-29 山西沸石科技有限公司 一种固定床绝热反应器苯酚甲醇气相烷基化生产甲基苯酚的方法
CN116496146B (zh) * 2023-04-14 2024-08-30 大连理工大学 一种甲基苯酚及同系物的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446856A (en) * 1964-05-29 1969-05-27 Gen Electric Methylation of phenols
CN101514144A (zh) * 2009-04-05 2009-08-26 湖南长岭石化科技开发有限公司 一种制备邻甲苯酚的方法

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4060560A (en) * 1976-03-26 1977-11-29 Continental Oil Company Disproportionation of xylenols with phenol to form cresols
NO20042200L (no) * 2003-05-30 2004-11-30 Ube Industries Novel proton type B zeolite, preparation method thereof and process for preparing phenol compound using the same

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3446856A (en) * 1964-05-29 1969-05-27 Gen Electric Methylation of phenols
CN101514144A (zh) * 2009-04-05 2009-08-26 湖南长岭石化科技开发有限公司 一种制备邻甲苯酚的方法

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DURGAKUMAR, V. ET AL.: "Alkylation of Phenol with Methanol over AIPO and SAPO Molecular SIEVES.", CATALYSIS LETTERS., vol. 5, 1990, pages 377 - 384 *
IHAN, SEN ET AL.: "Phenol Methylation with Methanol and Modified HZSM-5.", CHEMICAL INDUSTRY AND ENGINEERING., vol. 20, no. 5, October 2003 (2003-10-01), pages 282 - 285 , 302 *
KRISHNA, G. B. ET AL.: "Al-MCM-41 catalysed alkylation of phenol with methanol.", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL., vol. 197, 2003, pages 255 - 262 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106311337A (zh) * 2015-06-23 2017-01-11 中国石油化工股份有限公司 一种甲苯羟基化制甲酚的催化剂及制备方法

Also Published As

Publication number Publication date
CN103896740B (zh) 2016-08-10
CN103896740A (zh) 2014-07-02

Similar Documents

Publication Publication Date Title
WO2014101374A1 (zh) 一种生产甲酚的方法
US8653314B2 (en) Method for providing a co-feed in the coupling of toluene with a carbon source
JP6021905B2 (ja) Ｃ１〜ｃ８アルコールを用いた芳香族炭化水素のアルキル化のための方法
DK2328852T3 (en) PROCESS OF ALKYLING THE BENZEN WITH ISOPROPANOL OR MIXTURES OF ISOPROPANOL AND PROPYLENE
CN103570504B (zh) 一种苯酚甲醇气相烷基化生产甲酚的方法
TW201132623A (en) Hydrogenation process
CN102126916A (zh) 1,1-二芳基烷烃及其衍生物的制造方法
CN103570505B (zh) 一种以分子筛为催化剂生产甲酚的方法
KR101512860B1 (ko) 프로필렌의 제조 방법
KR20120139677A (ko) 스티렌 제조 방법과 상기 제조 방법에 사용하기 위한 촉매
TW201311613A (zh) 芳香族碳氫化合物以烯烴進行烷基化的方法
WO2014015476A1 (zh) 一种苯酚甲醇气相烷基化生产甲酚的方法
CN102781885B (zh) 用于制备乙苯的方法
CN112441866A (zh) 一种由异丁烯生产正丁烯的方法
CN113501747A (zh) 一种用于苯酚选择性生产甲酚的反应与分离复合工艺
Sad et al. Synthesis of cresols by alkylation of phenol with methanol on solid acids
CN103288602B (zh) 一种由苯甲醚制对甲基苯酚的方法及所使用的催化剂的制备方法
US20120296130A1 (en) Method for alkylation of toluene to form styrene utilizing an oxy-dehydrogenation reactor
US20120296132A1 (en) Use of an oxidant in the coupling of toluene with a carbon source
CN120827905A (zh) 催化剂及其制备方法、甲基化反应
JP2004505099A (ja) ヒドロキシ芳香族化合物の製造方法
CN108623428B (zh) 一种苯和甲醇烷基化的反应方法
CN109879726B (zh) 一种萘液相氧化制备萘酚的方法
US20120296131A1 (en) Method for alkylation of toluene in a pre-existing dehydrogenation plant
Das et al. Fe-MFI zeolite catalyzed C3 alkylation of benzene

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13869263

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13869263

Country of ref document: EP

Kind code of ref document: A1