WO2019119363A1 - Procédé de production d'éther mixte à partir de phénol mixte et de méthol par éthérification en phase gazeuse - Google Patents

Procédé de production d'éther mixte à partir de phénol mixte et de méthol par éthérification en phase gazeuse Download PDF

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WO2019119363A1
WO2019119363A1 PCT/CN2017/117811 CN2017117811W WO2019119363A1 WO 2019119363 A1 WO2019119363 A1 WO 2019119363A1 CN 2017117811 W CN2017117811 W CN 2017117811W WO 2019119363 A1 WO2019119363 A1 WO 2019119363A1
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catalyst
molecular sieve
hours
oxide
etherification
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PCT/CN2017/117811
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English (en)
Chinese (zh)
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王坤院
刘中民
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中国科学院大连化学物理研究所
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Priority to PCT/CN2017/117811 priority Critical patent/WO2019119363A1/fr
Publication of WO2019119363A1 publication Critical patent/WO2019119363A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
    • C07C39/02—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with no unsaturation outside the aromatic ring
    • C07C39/06—Alkylated phenols
    • C07C39/07—Alkylated phenols containing only methyl groups, e.g. cresols, xylenols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/09—Preparation of ethers by dehydration of compounds containing hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C43/00—Ethers; Compounds having groups, groups or groups
    • C07C43/02—Ethers
    • C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
    • C07C43/205—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring the aromatic ring being a non-condensed ring

Definitions

  • the invention relates to a method for producing mixed ether by gas phase etherification of mixed phenol methanol, belonging to the field of catalysis.
  • the medium-low temperature coal tar contains a large amount of phenolic compounds, especially phenol and methylphenol, which are deoxidized and converted during the hydrogenation and upgrading process, with reduced added value, increased hydrogen consumption and reduced economic efficiency.
  • the traditional solution is to cut out the phenolic oil fraction with the most abundant phenol from coal tar, and then separate the phenolic compound from phenol oil to obtain high value-added fine chemicals.
  • this method produces a large amount of acid-base waste liquid in the phenol extraction process, which not only has hidden dangers of environmental pollution, but also increases the treatment cost of acid-base waste liquid.
  • the phenol impurity obtained from coal tar is more limited to its industrial application.
  • the phenolic fraction containing less than 220 °C is directly reacted with methanol to prepare a high-octane gasoline component.
  • methanol a high-octane gasoline component.
  • the traditional coal tar processing technology is hydrogenation of coal tar to aromatics, which consumes a large amount of hydrogen and is economically inferior.
  • Mixed phenol methanol etherification reaction to produce mixed ether, as a gasoline high-octane gasoline component additive has good economic benefits and has broad market prospects.
  • a method for producing a mixed ether by gas phase etherification of mixed phenol methanol comprises mixing phenol methanol as a raw material, and performing gas phase etherification on a molecular sieve catalyst to produce a mixed ether, and the product selectivity is up to 98%.
  • the catalyst has good stability. The production process does not corrode equipment and does not produce a large amount of industrial wastewater. It is an environmentally friendly green process.
  • the method for producing a mixed ether by gas phase etherification of mixed phenol with methanol comprises at least the following steps:
  • the mixture containing the mixed phenol and methanol is passed through a reaction zone containing an etherification catalyst to obtain an ether;
  • a molecular sieve is included in the etherification catalyst; the molecular sieve is an active component;
  • the weight percentage of the molecular sieve in the etherification catalyst is 20%-85%.
  • the weight ratio of the molecular sieve to the binder is from 20:80 to 85:15.
  • the mixture containing mixed phenol and methanol is a gas phase mixture containing mixed phenol and methanol.
  • the raw material mixed phenol includes phenol, cresol and xylenol.
  • the mixed phenol is at least two of phenol, cresol and xylenol.
  • the mixed phenol comprises from 5% by weight to 80% by weight of phenol, from 10% by weight to 80% by weight of cresol, and from 5% by weight to 60% by weight of xylenol, based on the total weight of the mixed phenol.
  • the method at least includes the following steps:
  • the multi-stage solid catalyst bed is two or more catalyst beds, and the catalyst on each of the catalyst beds is independently selected from at least one of the etherification catalysts;
  • the diluent gas is N 2 or water vapor, and the molar ratio of the diluent gas to the mixed phenol is 0.5-20:1.
  • the diluent gas is used to disperse and dilute the mixed phenol and methanol.
  • the upper limit of the molar ratio of the diluent gas to the mixed phenol is selected from the group consisting of 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8 : 1, 9: 1, 10: 1, 12: 1, 15: 1, 18: 1 or 20: 1; the lower limit is selected from 0.5: 1, 1:1, 2: 1, 0.5: 1, 3: 1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 12:1, 15:1 or 18:1.
  • the forming is spray forming or extrusion molding.
  • the etherification catalyst can be used as a fluidized bed catalyst or a fixed bed catalyst.
  • the above-mentioned preparation steps are carried out to obtain a fluidized bed catalyst.
  • the extruded bed is formed into a matrix by the above steps to obtain a fixed bed catalyst.
  • the multi-stage catalyst bed may be two or more catalyst beds, and the multi-stage catalyst bed is the same catalyst or different catalysts.
  • the reaction conditions are: normal pressure, the reaction temperature is 250-450 ° C, and the feed weight space velocity is 0.5-20 h -1 .
  • the upper limit of the reaction temperature is selected from the group consisting of 280 ° C, 300 ° C, 320 ° C, 350 ° C, 360 ° C, 380 ° C, 400 ° C or 450 ° C; the lower limit is selected from 250 ° C, 280 ° C, 300 ° C, 320 ° C, 350 ° C, 360 ° C, 380 ° C, 400 ° C or 450 ° C.
  • the upper limit of the feed weight airspeed range is selected from the group consisting of 0.5h -1 , 1h -1 , 2h -1 , 3h -1 , 4h -1 , 5h -1 , 6h -1 , 7h -1 , 8h - 1 , 9h -1 , 10h -1 , 12h -1 , 15h -1 , 18h -1 or 20h -1 ; lower limit is selected from 0.5h -1 , 1h -1 , 2h -1 , 0.5h -1 , 3h -1 4h -1 , 5h -1 , 6h -1 , 7h -1 , 8h -1 , 9h -1 , 10h -1 , 12h -1 , 15h -1 or 18h -1 .
  • the molar ratio of the mixed phenol to methanol is 1:5.
  • the method for producing mixed ether by gas phase etherification of mixed phenol methanol comprises at least the following steps: at a reaction temperature of 250-450 ° C, a feed weight space velocity of 0.5-20 h -1 , and a normal pressure reaction condition.
  • the raw material mixed phenol and methanol are preheated, mixed with the diluent gas, continuously passed through the multistage solid catalyst bed, and subjected to gas phase reaction to form an ether.
  • the mixed phenol methanol etherification catalyst is prepared according to the preparation method as described above.
  • the mixed phenol contains phenol, cresol, and xylenol.
  • the molecular sieve has a molar silicon to aluminum ratio of from 20:1 to 80:1.
  • the molecular sieve has a molar silicon to aluminum ratio of from 20:1 to 60:1.
  • the molar ratio of the molar ratio of silicon to aluminum of the molecular sieve is selected from 25:1, 30:1, 40:1, 50:1, 60:1, 70:1 or 80:1; the lower limit is selected from 20:1. 25:1, 30:1, 40:1, 50:1, 60:1 or 70:1.
  • the molecular sieve has a molar silicon to aluminum ratio of from 20:1 to 40:1.
  • the molecular sieve has a molar silicon to aluminum ratio of from 30:1 to 60:1.
  • the molecular sieve has a molar silicon to aluminum ratio of from 30:1 to 40:1.
  • the molecule is selected from MCM-22 molecular sieve, ZSM-5 molecular sieve, beta molecular sieve, ammonium MCM-22 molecular sieve, ammonium ZSM-5 molecular sieve, ammonium beta molecular sieve, hydrogen type MCM-22 molecular sieve, hydrogen type At least one of ZSM-5 molecular sieve and hydrogen type beta molecular sieve.
  • the hydrogen type molecular sieve or the ammonium type molecular sieve is prepared by subjecting a molecular sieve to a hydrogenation reaction or an ammonium reaction by a conventional production method in the art.
  • a modifier is further included in the etherification catalyst
  • the modifier is selected from at least one of an oxide and a binder
  • the oxide is at least one selected from the group consisting of cerium oxide, calcium oxide, and cerium oxide;
  • the binder is at least one selected from the group consisting of silica sol, diatomaceous earth, silica, alumina, and aluminum sol.
  • the weight percentage of oxide in the etherification catalyst is from 0.1 to 10%.
  • the molecular weight of the molecular sieve in the etherification catalyst is 20%-85%; the weight percentage of the oxide is 3-10%; the weight ratio of the molecular sieve to the binder is 20:80-85:15 .
  • the molecular weight of the molecular sieve in the etherification catalyst is 70%-85%; the weight percentage of the oxide is 0.1-10%; the weight ratio of the molecular sieve to the binder is 17:10-17:15 ;or
  • the molecular weight of the molecular sieve in the etherification catalyst is 20%-85%; the weight percentage of the oxide is 3-10%; and the weight ratio of the molecular sieve to the binder is 4:15-4:1.
  • the molecular sieve in the etherification catalyst is an active ingredient, and the oxide and the binder are modifiers.
  • the upper limit of the weight percentage of the molecular sieve in the etherification catalyst is selected from the group consisting of 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80% or 85%; the lower limit is selected from 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75% or 80%.
  • the upper limit of the weight percentage of the oxide in the etherification catalyst is selected from the group consisting of 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%.
  • the lower limit is selected from 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%.
  • the weight percentage of the oxide in the etherification catalyst is from 0.1 to 10% by weight. It is preferably from 1 to 8% by weight, and more preferably from 3 to 5% by weight.
  • the upper limit of the weight ratio of the molecular sieve and the binder in the etherification catalyst is selected from the group consisting of 20:80, 4:15, 7:20, 3:4, 30:70, 40:60, 50:50, 17 : 15, 7:6, 60:40, 8:5, 5:3, 17:10, 70:30, 16:5, 4:1; the lower limit is selected from 4:15, 7:20, 3:4, 30:70, 40:60, 50:50, 17:15, 7:6, 60:40, 8:5, 5:3, 17:10, 70:30, 16:5, 4:1 or 17: 3.
  • the weight ratio of the molecular sieve to the binder is from 40:60 to 85:15, preferably from 50:50 to 80:20, and more preferably from 65:35 to 70:30.
  • the molar ratio of the mixed phenol to methanol is from 1:5 to 1:6.
  • the etherification catalyst is used to produce ethers from phenols and methanol.
  • the etherification catalyst is used to mix phenol with methanol to produce a mixed ether.
  • the mixed phenol methanol etherification catalyst is prepared by using molecular sieve as an active component, steam treatment, oxide modification and acid treatment for acid position modulation.
  • the preparation method of the etherification catalyst comprises at least the following steps:
  • the oxide modification comprises immersing the object to be treated in a salt solution of the metal in the oxide, drying, and calcining; or molding a mixture containing the object to be treated and the oxide, drying, and baking.
  • the modifying the oxide comprises molding a mixture containing the molecular sieve and the binder, drying, calcining, and then immersing in a salt solution of the metal in the oxide, drying, roasting; or containing molecular sieve,
  • the mixture of binder and oxide is shaped, dried, and calcined.
  • the etherification catalyst preparation comprises:
  • the catalyst prepared in the step (2) is further subjected to oxide modification, dried, and calcined at 550 ° C - 700 ° C for 3-10 hours;
  • the catalyst in the step (3) is further subjected to an acid treatment, dried, and calcined at 500 ° C to 600 ° C for 2 to 10 hours.
  • the shaped molecular sieve adopts a hydrogen type or ammonium type molecular sieve, and the content thereof is 20-85%, and the rest is a binder.
  • the method for preparing the etherification catalyst comprises at least the following steps:
  • step (b1) subjecting the product in step (a1) to oxide modification, followed by steam treatment, followed by acid treatment, and calcination to obtain the etherification catalyst;
  • the method for preparing the etherification catalyst comprises at least the following steps:
  • step (b2) The product in the step (a2) is subjected to steam treatment, followed by acid treatment, and calcination to obtain the etherification catalyst.
  • the calcination conditions in the step (a1) and the step (a2) are calcined at 550 ° C - 700 ° C for 4-10 hours;
  • the calcination conditions in the step (b1) and the step (b2) are calcined at 500 ° C to 600 ° C for 2 to 10 hours.
  • the molding method in the step (a1) and the step (a2) may be spray drying or extrusion molding.
  • the molecular sieve may be a hydrogen or ammonium type ZSM-5 and MCM-22, beta molecular sieve.
  • the calcination conditions in the step (a1) and the step (a2) are calcination at 550 ° C; the calcination conditions in the step (b1) and the step (b2) are calcined at 500 ° C for 2 hours.
  • the calcination conditions in the step (b1) and the step (b2) are calcined at 600 ° C for 2 hours.
  • the calcination conditions in the step (a1) and the step (a2) are calcined at 550 ° C for 4 hours; and the calcination conditions in the step (b1) and the step (b2) are calcined at 500 ° C to 600 ° C for 2-3 hours. .
  • the calcination conditions are calcined at 600-700 ° C for 3 hours.
  • the modifying the oxide in the step (b1) comprises: immersing the product in the step (a1) in a salt solution of the metal in the oxide, drying, and roasting at a temperature of 550 ° C to 700 ° C 3-10 hour.
  • the oxide modification in the step (b1) comprises: immersing the product in the step (a1) in a salt solution of the metal in the oxide, drying, and calcining at 700 ° C for 3 hours.
  • the oxide modification in the step (b1) comprises: immersing the product in the step (a1) in a salt solution of the metal in the oxide, drying, and baking at 600 ° C for 3 hours.
  • the immersion time is from 20 to 36 hours.
  • the salt solution of the metal in the oxide is at least one selected from the group consisting of a nitrate, a sulfate, and a chloride corresponding to the metal.
  • the salt solution of the metal in the oxide is the nitrate corresponding to the metal.
  • the steam treatment in the step (b1) and the step (b2) comprises: treating the object to be treated in a 100% steam atmosphere at 300-800 ° C for 0.5-10 hours; then at 500-700 ° C. Roast for 3-5 hours.
  • the water vapor is saturated water vapor.
  • the steam treatment in the step (b1) and the step (b2) comprises: treating the object to be treated in a 100% steam atmosphere at 350-550 ° C for 4-10 hours; then baking at 550 ° C. 3 hour.
  • the steam treatment in the step (b1) and the step (b2) comprises: treating the object to be treated in a 100% steam atmosphere at 350-600 ° C for 2-10 hours; then baking at 550 ° C. 3 hour.
  • the acid treatment in the step (b1) and the step (b2) comprises: adding the object to be treated to the acidic solution, and immersing at room temperature -80 ° C for 4-24 hours.
  • the acid treatment in step (b1) and step (b2) comprises: adding the object to be treated It is immersed in a mineral acid at room temperature for 4-24 hours or at 30-80 ° C in an organic acid for 4-12 hours.
  • the acid treatment in the step (b1) and the step (b2) comprises: adding the object to be treated to the acidic solution, and immersing at room temperature -80 ° C for 10-24 hours.
  • the acidic solution is selected from at least one of dilute nitric acid, sulfuric acid, phosphoric acid, oxalic acid, and citric acid.
  • the concentration of the acidic solution is from 0.1 to 0.5 mol/L.
  • the acidic solution has a mass concentration of 10%-20%.
  • the drying is performed before the acid treatment in the step (b1) and the step (b2), and the drying temperature is 100-150 °C.
  • the drying temperature is 120 °C.
  • the preparation method of the etherification catalyst comprises the following steps:
  • step (1) The product obtained in the step (1) is further subjected to oxide modification, dried, and calcined at 550 ° C - 700 ° C for 3-10 hours;
  • step (3) The product obtained in the step (3) is further subjected to an acid treatment, dried, and calcined at 500 ° C to 600 ° C for 2 to 10 hours.
  • the preparation method of the etherification catalyst comprises the following steps:
  • the product catalyst obtained in the step (1) is steam-treated at 300-700 ° C for 0.5-10 hours;
  • step (3) The product catalyst obtained in the step (2) is further subjected to oxide modification, dried, and calcined at 550 ° C - 700 ° C for 3-10 hours;
  • the product catalyst obtained in the step (3) is further subjected to an acid treatment, dried, and calcined at 500 ° C to 600 ° C for 2 to 10 hours.
  • the method for producing a mixed ether by gas phase etherification of mixed phenol methanol comprises: a feed weight space velocity of 0.5 to 20 h -1 at a reaction temperature of 250 to 450 ° C, and Under normal pressure reaction conditions, the raw material is mixed with the phenol raw material, the methanol is preheated, mixed with the diluent gas, and passed through a multistage solid etherification catalyst bed to carry out gas phase reaction to form an ether, which is obtained according to the above.
  • the mixed phenol comprises phenol, cresol, xylenol.
  • the mixed phenol methanol etherification catalyst is prepared by using molecular sieve as an active component, steam treatment, oxide modification and acid treatment for acid position modulation.
  • the method for producing mixed ether by mixing phenol methanol etherification in the present application the mixed phenol and methanol are preheated, mixed with the diluent gas and continuously passed through the catalyst bed, at a reaction temperature of 250-450 ° C, and the feed weight space velocity is 0.5-20 h. -1 .
  • the mixed phenol methanol etherification catalyst was prepared by using MCM-22, ZSM-5, beta molecular sieve as the active component.
  • the mixed phenol methanol is used as raw material, and the selectivity of the etherified product can reach above 98%, and the catalyst stability is good. There is no equipment corrosion during the production process, it is an environmentally friendly catalyst with good industrial application prospects.
  • the conversion rate of the mixed phenol in the method for producing mixed ether by the gas phase etherification of mixed phenol methanol in the present application can reach 30% or more.
  • the conversion ratio of the mixed phenol in the method for producing mixed ether by the gas phase etherification of mixed phenol methanol in the present application is 35% to 45%.
  • the conversion ratio of the mixed phenol in the method for producing mixed ether by the gas phase etherification of mixed phenol methanol in the present application is 30% to 48%.
  • the method for producing a mixed ether by vapor phase etherification of mixed phenol methanol as described in the present application has an ether selectivity of 98% or more.
  • Molecules selected for use in accordance with the teachings of the present application are screened from one or more of ZSM-5 molecular sieves, MCM-22 molecular sieves, and beta molecular sieve molecular sieves.
  • the MCM-22 molecular sieve used in the present application is synthesized according to the method in US Pat. No. 4,954,325; the ZSM-5 molecular sieve is produced by the Nankai University Catalyst Factory and its product name is NKF-5; the beta molecular sieve is produced by the Nankai University Catalyst Factory, and its product name For NKF-6.
  • the invention solves the technical problem that the conventional coal tar hydrogenation production aromatic hydrocarbon technology has the disadvantages of large hydrogen consumption and poor economy, and the invention provides a method for producing mixed ether by mixing phenol methanol etherification.
  • the present invention provides a method for producing mixed ether by etherification of mixed phenol methanol, which has excellent catalyst performance and good stability; and the catalyst preparation process is simple and the production cost is low.
  • the method relates to a method for producing a high octane component of gasoline from a phenol mixture in coal tar, and the production process is non-polluting, and is a green environmental protection new technology.
  • the production of mixed ether by the method of the present application has a simple production process, and can greatly reduce the production cost compared with the conventional production process, and has good economic benefits.
  • the method in the present application uses a mixed phenol methanol as a raw material to produce a mixed ether by gas phase etherification on a molecular sieve catalyst, and the product selectivity is up to 98% or more, and the catalyst has good stability.
  • the production process does not corrode equipment and does not produce a large amount of industrial wastewater. It is an environmentally friendly green process.
  • the preparation process of the catalyst is as follows: 120 g of ZSM-5 molecular sieve having a molar ratio of silica to alumina of 20 is mixed with 60 g of diatomaceous earth, 100 g of silica sol containing 20% by weight of silica, and an appropriate amount of 10% is added. Nitric acid is extruded as a squeezing agent. It was dried at 120 ° C and calcined at 500 ° C for 10 hours. The above catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor A0. 20 g of A0 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 A1.
  • the catalyst A was obtained by drying at 120 ° C and calcination at 550 ° C for 10 hours, wherein the molecular sieve content was 60%.
  • the preparation process of the catalyst was as follows: 170 g of a ZSM-5 molecular sieve having a molar ratio of silicon to aluminum of 30, mixed with 30 g of alumina, and an appropriate amount of 10% dilute nitric acid was added as a squeezing agent to form a squeezing strip. It was dried at 120 ° C and calcined at 700 ° C for 4 hours. The catalyst is cut into 1 to 3 mm to obtain a columnar catalyst precursor B0. 20 g of the mother catalyst B0 is subjected to steam treatment in a 100% steam atmosphere for 1 hour, the treatment temperature is 700 ° C, and calcination at 550 ° C for 3 hours to obtain B1.
  • the preparation process of the catalyst is as follows: 200 g of ZSM-5 molecular sieve with a molar ratio of silicon to aluminum of 40, mixed with 20 g of diatomaceous earth, 100 g of silica weight 30% silica sol, and an appropriate amount of 10% dilute nitric acid as a squeezing agent. Extrusion molding. 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 D0.
  • the preparation process of the catalyst was as follows: 170 g of an ammonium type ZSM-5 molecular sieve having a molar ratio of silicon to aluminum of 30, 150 g of a silica weight of 20% silica sol, and an appropriate amount of 10% dilute nitric acid as a squeezing agent for extrusion molding. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst is cut into 1 to 3 mm to prepare a columnar catalyst precursor F0.
  • 20 g of the precursor catalyst F0 sample is immersed in an aqueous solution of lanthanum nitrate for 24 hours, dried at 120 ° C, calcined at 700 ° C for 3 hours to obtain F1, and 20 g of F1 at 100%.
  • the steam was treated in a steam atmosphere for 10 hours, the treatment temperature was 350 ° C, and calcination was carried out at 550 ° C for 3 hours to obtain F 2 .
  • 20 g of F 2 was added to 150 ml of an oxalic acid solution having a weight content of 0.5 mol/L, and soaked at 80 ° C for 4 hours.
  • the catalyst F was obtained by drying at 120 ° C and calcination at 500 ° C for 2 hours.
  • the cerium oxide content is 10% by weight, and the molecular sieve content of the catalyst is 85%.
  • the preparation process of the catalyst was as follows: 160 g of an ammonium type ZSM-5 molecular sieve having a molar ratio of silicon to aluminum of 40, mixed with 100 g of silica weight 40% silica sol, and an appropriate amount of 10% dilute nitric acid was added as a squeezing agent to form a squeezing strip. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor G0.
  • 20 g of the precursor catalyst G0 sample was immersed in an aqueous solution of lanthanum nitrate for 36 hours, dried at 120 ° C, calcined at 700 ° C for 3 hours to obtain G1, and 20 g of G1 at 100%.
  • the steam was treated in a steam atmosphere for 10 hours, the treatment temperature was 450 ° C, and calcination was carried out at 550 ° C for 3 hours to obtain G 2 .
  • 20 g of G 2 was added to 50 ml of a 0.5 mol/L oxalic acid solution, and soaked at 80 ° C for 12 hours.
  • the catalyst G was obtained by drying at 120 ° C and calcination at 500 ° C for 2 hours.
  • the cerium oxide content is 10% by weight, and the molecular sieve content in the catalyst is 80%.
  • the preparation process of the catalyst is as follows: 140 g of an ammonium type ZSM-5 molecular sieve having a molar ratio of silicon to aluminum of 30, mixed with 20 g of silica, 100 g of silica by weight of 40% silica sol, and an appropriate amount of 10% dilute nitric acid as a co-extrusion.
  • the agent is extruded into a strip. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. Above reminder The catalyst was cut into 1 to 3 mm to obtain a columnar catalyst precursor H0.
  • the preparation process of the catalyst was as follows: 170 g of a ZSM-5 molecular sieve having a molar ratio of silicon to aluminum of 30, mixed with 100 g of a silica weight of 30% silica sol, and an appropriate amount of 10% dilute nitric acid was added as a squeezing agent to form a squeezing strip. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor I0.
  • 20 g of the mother catalyst I0 was immersed in an aqueous solution of cerium nitrate for 20 hours, dried at 120 ° C, calcined at 700 ° C for 3 hours to obtain I1, and 20 g of I1 at 100%.
  • the steam was treated in a steam atmosphere for 10 hours, the treatment temperature was 350 ° C, and calcination was carried out at 550 ° C for 3 hours to obtain I 2 , and 20 g of the I 2 sample was added to a citric acid solution having a weight content of 0.5 mol/L, and soaked at 30 ° C for 8 hours.
  • the catalyst I was obtained by drying at 120 ° C and calcination at 600 ° C for 2 hours.
  • the cerium oxide has a weight content of 3%, and the content of the molecular sieve in the catalyst is 85%.
  • the preparation process of the catalyst was as follows: 160 g of ZSM-5 molecular sieve having a molar ratio of silica to alumina of 20, mixed with 100 g of silica weight 40% silica sol, and an appropriate amount of 10% dilute nitric acid was added as a squeezing agent to form a squeezing strip. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst is cut into 1-3 mm to obtain a columnar catalyst precursor J0.
  • 20 g of the mother catalyst J0 is immersed in an aqueous solution of cerium nitrate for 24 hours, dried at 120 ° C, and calcined at 700 ° C for 3 hours to obtain J1, and 20 g of J1 at 100%.
  • the steam was treated in a steam atmosphere for 4 hours, the treatment temperature was 350 ° C, and calcination was carried out at 550 ° C for 3 hours to obtain J2.
  • 20 g of the J2 sample was added to 50 ml of a 8% by weight nitric acid solution and soaked at 30 ° C for 10 hours. It was dried at 120 ° C and calcined at 500 ° C for 2 hours.
  • Catalyst J was prepared in an amount of 10% by weight of cerium oxide.
  • the molecular sieve content of the catalyst was 80%.
  • the preparation process of the catalyst is as follows: 160 g of ZSM-5 molecular sieve with a molar ratio of silicon to aluminum of 30, mixed with 50 g of silica weight 40% silica sol, 20 g of antimony trioxide, and an appropriate amount of 10% dilute nitric acid as a sintering aid. Extrusion molding. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor K0. 20 g of the mother catalyst K0 was subjected to steam treatment in a 100% steam atmosphere for 4 hours, a treatment temperature of 350 ° C, and calcination at 550 ° C for 3 hours to obtain K1.
  • K1 20 g was added to 50 ml of a 10% by weight nitric acid solution and soaked at 30 ° C for 10 hours. It is dried at 120 ° C and calcined at 500 ° C for 2 hours to obtain K.
  • Catalyst K was prepared with a cerium oxide weight content of 10. The molecular sieve content of the catalyst was 80%.
  • the preparation process of the catalyst was as follows: 160 g of a ZSM-5 molecular sieve having a molar ratio of silicon to aluminum of 30, and 10 g of dilute nitric acid of 30 g of diatomaceous earth and 10 g of cerium oxide as a squeezing agent. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor L0. 20 g of the mother catalyst L0 was subjected to steam treatment in a 100% steam atmosphere for 2 hours, a treatment temperature of 600 ° C, and calcination at 550 ° C for 3 hours to obtain L1.
  • the preparation process of the catalyst was as follows: 170 g of MCM-22 molecular sieve having a molar ratio of silica to alumina of 20, mixed with 150 g of alumina sol having a weight of 20%, and an appropriate amount of 10% dilute nitric acid was added as a squeezing agent to form a squeezing strip. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor M0. 20 g of the mother catalyst M0 was subjected to steam treatment in a 100% steam atmosphere for 10 hours, a treatment temperature of 450 ° C, and calcination at 550 ° C for 3 hours to obtain M1.
  • the preparation process of the catalyst is as follows: 170 g of MCM-22 molecular sieve with a molar ratio of silicon to aluminum of 60, mixed with 100 g of silica weight 30% silica sol, 6 g of cerium oxide, and an appropriate amount of 10% dilute nitric acid as a squeezing agent. Strip molding. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor N0. 20 g of the mother catalyst N0 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 N1.
  • the preparation process of the catalyst was as follows: 40 g of MCM-22 molecular sieve having a molar ratio of silicon to aluminum of 50, mixed with 150 g of alumina, 10 g of cerium oxide, and an appropriate amount of 10% dilute nitric acid was added as a squeezing agent to form a squeezing strip. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor P0. 20 g of the precursor catalyst P0 was subjected to steam treatment in a 100% steam atmosphere for 10 hours, at a treatment temperature of 350 ° C, and calcined at 550 ° C for 3 hours to obtain P1.
  • the preparation process of the catalyst is as follows: 70 g of MCM-22 molecular sieve with a molar ratio of silicon to aluminum of 40, mixed with 100 g of diatomaceous earth, 100 g of silica weight 20% silica sol, 10 g of calcium oxide, and an appropriate amount of 10% diluted. Nitric acid is extruded as a squeezing agent. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor R0.
  • 20 g of the parent catalyst R0 was subjected to steam treatment in a 100% steam atmosphere for 6 hours, a treatment temperature of 350 ° C, and calcination at 550 ° C for 3 hours to obtain R1.
  • 20 g of R1 was added to 50 ml of a 5% by weight nitric acid solution and immersed for 10 hours at room temperature.
  • the catalyst R was obtained by drying at 120 ° C and calcination at 500 ° C for 2 hours.
  • the content of the molecular sieve in the catalyst was 35%, and the calcium oxide content was 5%.
  • the preparation process of the catalyst was as follows: 170 g of a beta molecular sieve having a molar ratio of silica to alumina of 20, mixed with 100 ml of silica weight 30% silica sol, and an appropriate amount of 10% dilute nitric acid was added as a squeezing agent to form a squeezing strip. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1 to 3 mm to prepare a columnar catalyst precursor S0. 20 g of the mother catalyst S0 was subjected to steam treatment in a 100% steam atmosphere for 4 hours, at a treatment temperature of 650 ° C, and calcined at 550 ° C for 3 hours to obtain S1.
  • the preparation process of the catalyst was as follows: 160 g of MCM-22 molecular sieve having a molar ratio of silicon to aluminum of 30, mixed with 100 g of silica weight 40% silica sol, and an appropriate amount of 10% dilute nitric acid was added as a squeezing agent for extrusion molding. It was dried at 120 ° C and calcined at 550 ° C for 4 hours. The catalyst was cut into 1-3 mm to prepare a columnar catalyst precursor T0. 20 g of the mother catalyst T0 was subjected to steam treatment in a 100% steam atmosphere for 6 hours, a treatment temperature of 550 ° C, and calcination at 550 ° C for 3 hours to obtain T1.
  • T1 20 g of T1 was added to 50 ml of a 1% by weight aqueous solution of sulfuric acid, and immersed for 24 hours at room temperature. It is dried at 120 ° C and calcined at 600 ° C for 2 hours to obtain T.
  • the content of the molecular sieve in the catalyst was 80%.
  • the catalysts prepared in Examples 1-16 were subjected to a mixed phenol methanol etherification reaction on a fixed bed reactor.
  • the raw materials are mixed with phenol, methanol and water vapor to be preheated into the reactor for reaction, and the reaction products are analyzed by on-line chromatography.
  • the gas chromatograph is Agilent 7890A, and the column is a cyclodextrin column of 30 m X 0.25 mm X 0.25 ⁇ m. Chromatographic conditions: column temperature: initial temperature 150 ° C, stay for 15 minutes, 10 ° C / min heating rate increased to 180 ° C, constant temperature 5.3 minutes; carrier gas for high purity nitrogen, column pressure: 6.5 pisa, column flow rate 12.6 cm / Sec.
  • the reaction catalyst loading is 6.0 g
  • the weight space velocity is 0.5-20 hr-1
  • the reaction temperature is 250-500 ° C
  • the mixed phenol to methanol molar ratio is 1:5
  • the dilution gas is water vapor
  • the molar ratio of diluent gas to mixed phenol is shown in Table 1.
  • the catalyst evaluation device and the test method were the same as in Example 17.
  • the reaction catalyst loading is 20.0 g
  • the molar ratio of mixed phenol to methanol is 1:6, the weight space velocity is 3 hours -1 , the dilution gas is steam or nitrogen, and the molar ratio of diluent gas to mixed phenol is 6, phenol: cresol : xylenol (molar ratio) is 30:60:10.
  • Table 2 The results of the reaction of the catalysts in the various examples are shown in Table 2.
  • the catalyst prepared according to the technical scheme of the present invention has good stability and is an environmentally friendly catalyst. Further, a higher mixed phenol conversion ratio and ether selectivity can be achieved by using the catalyst to produce a mixed ether by etherification reaction using mixed phenol and methanol as raw materials.

Abstract

L'invention concerne un procédé de production d'un éther mixte à partir d'un mélange de phénol et de méthol par éthérification en phase gazeuse, comprenant au moins les étapes suivantes consistant à : faire passer un mélange contenant le phénol mélangé et le méthol à travers une zone de réaction contenant un catalyseur d'éthérification pour la réaction, de manière à obtenir l'éther. Le procédé de production d'un éther mixte à partir d'un mélange de phénol et de méthol utilise le phénol et le méthol mélangés en tant que matières premières, a une sélectivité pour un produit d'éthérification qui peut atteindre 98 % ou plus, et le catalyseur a une bonne stabilité ; le procédé de production fourni par la présente invention n'a pas d'effet de corrosion sur l'équipement, le catalyseur étant écologique, et présente de bonnes perspectives d'application industrielle.
PCT/CN2017/117811 2017-12-21 2017-12-21 Procédé de production d'éther mixte à partir de phénol mixte et de méthol par éthérification en phase gazeuse WO2019119363A1 (fr)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1377334A (zh) * 1999-10-13 2002-10-30 哈尔曼及赖默股份有限公司 芳基烷基醚的制备方法
CN105316034A (zh) * 2014-07-10 2016-02-10 神华集团有限责任公司 一种煤焦油中含酚油的加工方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1377334A (zh) * 1999-10-13 2002-10-30 哈尔曼及赖默股份有限公司 芳基烷基醚的制备方法
CN105316034A (zh) * 2014-07-10 2016-02-10 神华集团有限责任公司 一种煤焦油中含酚油的加工方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BHATTACHARYYA, K.G. ET AL.: "Al-MCM-41 Catalysed Alkylation of Phenol with Methano l", JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL, vol. 197, no. 1-2, 31 December 2003 (2003-12-31), pages 255, XP055620093 *
WANG, LIJUN ET AL.: "Research on . Zeolite . Catalyst for Synthesis of Methyl Phenyl Ether with Phenol and Methanol", ACTA PETROLEI SINICA (PETROLEUM PROCESSING SECTION, vol. 14, no. 2, 30 June 1998 (1998-06-30) *

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