WO2019119363A1

WO2019119363A1 - Method for producing mixed ether from mixed phenol and methol by gas phase etherification

Info

Publication number: WO2019119363A1
Application number: PCT/CN2017/117811
Authority: WO
Inventors: 王坤院; 刘中民
Original assignee: 中国科学院大连化学物理研究所
Priority date: 2017-12-21
Filing date: 2017-12-21
Publication date: 2019-06-27

Abstract

Disclosed is a method for producing a mixed ether from a mixed phenol and methol by gas phase etherification, at least comprising the following steps: a mixture containing the mixed phenol and methol is passed through a reaction zone containing an etherification catalyst for reaction, so as to obtain the ether. The method for producing a mixed ether from a mixed phenol and methol uses the mixed phenol and methol as raw materials, has a selectivity for an etherification product which can reach 98% or more, and the catalyst has a good stability; and the production process has no equipment corrosion, with the catalyst being environmentally friendly, and has good industrial application prospects.

Description

Method for producing mixed ether by gas phase etherification of mixed phenol methanol

Technical field

The invention relates to a method for producing mixed ether by gas phase etherification of mixed phenol methanol, belonging to the field of catalysis.

Background technique

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. However, 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. In addition, the phenol impurity obtained from coal tar is more limited to its industrial application. In order to obtain high-purity phenol products, it is necessary to increase the processes of recrystallization and purification, which greatly reduce the economical utilization of phenolic compounds in coal tar. . Similarly, in the mixed cresol in phenol oil, there are components which are not easily separated, which makes it difficult to obtain a high-purity cresol product and has poor economic efficiency. Anisole, methylanisole, and dimethylanisole are high octane gasoline components. The phenolic oil in the phenol-containing fraction of less than 220 °C in medium-low temperature coal tar is mainly phenol, methylphenol and xylenol. The phenolic fraction containing less than 220 °C is directly reacted with methanol to prepare a high-octane gasoline component. There is potential to clean the way to use coal tar phenolic compounds. 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.

Summary of the invention

According to an aspect of the present application, a method for producing a mixed ether by gas phase etherification of mixed phenol methanol is provided, which 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%. Above, 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;

Wherein, the weight percentage of the molecular sieve in the etherification catalyst is 20%-85%.

Optionally, 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.

Optionally, the raw material mixed phenol includes phenol, cresol and xylenol.

Optionally, the mixed phenol is at least two of phenol, cresol and xylenol.

Preferably, 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.

Optionally, the method at least includes the following steps:

Premixing the mixed phenol and methanol, mixing with the diluent gas and continuously passing through the multi-stage solid catalyst bed to obtain an ether;

Wherein 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.

Optionally, 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.

Optionally, the forming is spray forming or extrusion molding.

Alternatively, the etherification catalyst can be used as a fluidized bed catalyst or a fixed bed catalyst. After the spray molding, 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.

Alternatively, 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.

Optionally, 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 .

Optionally, 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.

Optionally, 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 .

Preferably, the molar ratio of the mixed phenol to methanol is 1:5.

As a specific embodiment, 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. Next, 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.

Optionally, the molecular sieve has a molar silicon to aluminum ratio of from 20:1 to 80:1.

Optionally, the molecular sieve has a molar silicon to aluminum ratio of from 20:1 to 60:1.

Optionally, 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.

Optionally, the molecular sieve has a molar silicon to aluminum ratio of from 20:1 to 40:1.

Optionally, the molecular sieve has a molar silicon to aluminum ratio of from 30:1 to 60:1.

Optionally, the molecular sieve has a molar silicon to aluminum ratio of from 30:1 to 40:1.

Optionally, 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.

Optionally, 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.

Alternatively, the weight percentage of oxide in the etherification catalyst is from 0.1 to 10%.

Optionally, 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 .

Optionally, 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.

Optionally, the molecular sieve in the etherification catalyst is an active ingredient, and the oxide and the binder are modifiers.

Optionally, 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%.

Optionally, 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%. Or 10%, the lower limit is selected from 0.1%, 0.2%, 0.5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8% or 9%.

Optionally, 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.

Optionally, 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.

Alternatively, 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.

Preferably, 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.

Optionally, 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:

Oxidation modification and steam treatment of the molecular sieve; or

Molecular sieves are subjected to oxide modification, steam treatment and acid treatment;

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.

Optionally, 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.

Optionally, the etherification catalyst preparation comprises:

(1) mixing the molecular sieve and the binder, drying, and calcining at 550 ° C - 700 ° C for 4-10 hours;

(2) treating the calcined catalyst at 300-700 ° C with steam;

(3) 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;

(4) 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.

Optionally, the method for preparing the etherification catalyst comprises at least the following steps:

(a1) forming a mixture containing the molecular sieve and the binder, drying, and baking;

(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;

Alternatively, the method for preparing the etherification catalyst comprises at least the following steps:

(a2) forming a mixture containing molecular sieves, a binder and an oxide, drying, and calcining;

(b2) The product in the step (a2) is subjected to steam treatment, followed by acid treatment, and calcination to obtain the etherification catalyst.

Optionally, 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.

Alternatively, 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.

Alternatively, 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.

Alternatively, the calcination conditions in the step (b1) and the step (b2) are calcined at 600 ° C for 2 hours.

Optionally, 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. .

Alternatively, the calcination conditions are calcined at 600-700 ° C for 3 hours.

Optionally, 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.

Optionally, 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.

Optionally, 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.

Alternatively, the immersion time is from 20 to 36 hours.

Optionally, 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.

Optionally, the salt solution of the metal in the oxide is the nitrate corresponding to the metal.

Optionally, 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.

Optionally, 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.

Optionally, 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.

Optionally, 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.

Optionally, 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.

Optionally, 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.

Optionally, the acidic solution is selected from at least one of dilute nitric acid, sulfuric acid, phosphoric acid, oxalic acid, and citric acid.

Alternatively, the concentration of the acidic solution is from 0.1 to 0.5 mol/L.

Optionally, the acidic solution has a mass concentration of 10%-20%.

Optionally, the drying is performed before the acid treatment in the step (b1) and the step (b2), and the drying temperature is 100-150 °C.

Further preferably, the drying temperature is 120 °C.

As a specific embodiment, the preparation method of the etherification catalyst comprises the following steps:

(2) 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;

(3) treating the product obtained in the step (2) with steam at 300-700 ° C;

(4) 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.

(2) The product catalyst obtained in the step (1) is steam-treated at 300-700 ° C for 0.5-10 hours;

(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;

(4) 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.

It should be noted that various modification methods of the catalyst differ depending on the acid strength of the parent molecular sieve and the density of different acid sites, and various modification methods used in the present invention are combined and modified to obtain a desired catalyst. For the molecular sieve precursor having a small acid density of the catalyst, the desired acid bit density can be obtained by one or both modification methods of the present invention. Therefore, various elements The single modification method also belongs to the field of coverage of the present invention. For example, a single modification such as metal oxide modification or steam treatment is within the scope of the present invention.

As a specific embodiment, 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. Prepared by the preparation method, and the mixed phenol comprises phenol, cresol, xylenol.

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 . Gas phase reaction under normal pressure reaction conditions to form a mixed ether. 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.

All conditions in the application that are within the range of values may be independently selected from any point within the stated range.

All numbers expressing feature sizes, quantities, and physicochemical properties used in the specification and claims are to be understood as being modified in all instances by the term "about" unless otherwise indicated. Accordingly, the numerical parameters set forth in the above description and the appended claims are approximations, unless otherwise indicated, and those skilled in the art are able to utilize the teachings disclosed herein. approximation. The use of a range of values by endpoints includes all numbers in the range and any range within the range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, etc. .

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 beneficial effects that can be produced by this application include:

(1) 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.

(2) 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.

(3) Since the preparation process considers the characteristics of the molecular sieve structure and the number of acid sites on the inner and outer surfaces of the molecular sieve, the modification step and the percentage of the modifier in the catalyst are optimized and controlled in the present application. Acid treatment, steam treatment enhances the hydrothermal stability of the catalyst, it is the synergistic effect of these several modification processes, so that the catalyst has good catalytic performance, the strength of the catalyst is good, and can fully meet the industrial use requirements.

(4) 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.

Detailed ways

The present application is described in detail below with reference to the embodiments, but the application is not limited to the embodiments.

The starting materials and catalysts in the examples of the present application are commercially available unless otherwise stated.

The "%" mentioned is "% by weight", and the "parts" referred to are "parts by weight".

Example 1

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. To 20 g of A1, 50 ml of a 5% aqueous solution of phosphoric acid was added and immersed at 30 ° C for 4 hours. 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%.

Example 2

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. 20 g of B1 was added to 50 ml of a 3% phosphoric acid solution, and immersed for 10 hours at room temperature. The catalyst B was obtained by drying at 120 ° C and calcination at 600 ° C for 2 hours. The molecular sieve content of the catalyst is 85%.

Example 3

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. 20 g of the precursor catalyst D0 sample was immersed in an aqueous solution of cerium nitrate solution for 24 hours, dried at 120 ° C, and calcined at 600 ° C for 3 hours, and the weight percentage of cerium oxide in the catalyst was 0.1%. D1 is obtained, and 20 g of D1 is introduced in a 100% steam atmosphere. The steam was treated for 10 hours, the treatment temperature was 350 ° C, and calcination was carried out at 550 ° C for 3 hours to obtain D 2 . 20 g of D 2 was added to 50 ml of a 10% by weight nitric acid solution, and immersed at room temperature for 24 hours. It was dried at 120 ° C and calcined at 600 ° C for 3 hours. Catalyst D was obtained. The molecular sieve content of the catalyst was 80%.

Example 4

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%.

Example 5

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%.

Example 6

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. 20 g of the mother catalyst H0 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 H1, and 20 g of H1 in 100% water. The steam was treated in a steam atmosphere for 4 hours, the treatment temperature was 550 ° C, and calcination was carried out at 550 ° C for 3 hours to obtain H 2 . 20 g of the H 2 sample was added to 150 ml of a 0.5 mol/L oxalic acid solution, and soaked at 80 ° C for 24 hours. It was dried at 120 ° C and calcined at 500 ° C for 2 hours. Catalyst H was prepared in an amount of 0.1% by weight of cerium oxide. The molecular sieve content of the catalyst was 70%.

Example 7

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%.

Example 8

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%.

Example 9

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. 20 g of K1 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%.

Example 10

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. 20 g of L1 was added to 50 ml of a 3% phosphoric acid solution, and immersed for 24 hours at room temperature. The catalyst L was obtained by drying at 120 ° C and calcination at 500 ° C for 2 hours. The cerium oxide content is 5% by weight, and the molecular sieve content in the catalyst is 80%.

Example 11

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. 20 g of M1 was added to 50 ml of a 1% by weight sulfuric acid solution and immersed for 24 hours at room temperature. It is dried at 120 ° C and calcined at 500 ° C for 2 hours to obtain M1. Catalyst M. The molecular sieve content of the catalyst was 85%.

Example 12

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. 20 g of N1 was added to 50 ml of a 15% by weight nitric acid solution and immersed for 12 hours at room temperature. The catalyst N was obtained by drying at 120 ° C and calcination at 500 ° C for 2 hours. The cerium oxide content is 3% by weight, and the molecular sieve content in the catalyst is 85%.

Example 13

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. 20 g of P1 was added to 50 ml of a 2% by weight phosphoric acid solution and immersed for 24 hours at room temperature. The catalyst P was obtained by drying at 120 ° C and calcination at 500 ° C for 2 hours. The cerium oxide content is 3% by weight, and the molecular sieve content in the catalyst is 20%.

Example 14

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%.

Example 15

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. 20 g of S1 was added to 50 ml, a citric acid solution having a weight content of 0.5 mol/L was added, and immersed at 80 ° C for 8 hours. The catalyst S was prepared by drying at 120 ° C and calcination at 500 ° C for 2 hours. The molecular sieve content of the catalyst was 85%.

Example 16

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. 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%.

Example 17

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 μm. 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, and the molar ratio of diluent gas to mixed phenol is The results of the reaction of the catalyst for 72 hours in various examples are shown in Table 1.

Table 1 Reaction conditions and reaction properties

Example 18-21

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. The results of the reaction of the catalysts in the various examples are shown in Table 2.

Table 2 Catalyst performance

From the results of the above Examples 1-21, it is known that 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.

The embodiments of the present invention are only described for the preferred embodiments of the present invention, and are not intended to limit the scope and scope of the present invention. Various modifications and improvements of the present invention are intended to be included within the scope of the present invention.

Claims

A method for producing mixed ether by gas phase etherification of mixed phenol methanol, characterized in that it comprises at least the following steps: passing a mixture containing mixed phenol and methanol 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;

Wherein, the weight percentage of the molecular sieve in the etherification catalyst is 20%-85%.
The method of claim 1 wherein said method comprises at least the following steps:

Premixing the mixed phenol and methanol, mixing with the diluent gas and continuously passing through the multi-stage solid catalyst bed to obtain an ether;

Wherein 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 method of claim 1 wherein said mixed phenol is at least two of phenol, cresol and xylenol.
The method according to claim 1, wherein the reaction conditions are: atmospheric pressure, a reaction temperature of 250 to 450 ° C, and a feed weight space velocity of 0.5 to 20 h -1 .
The method of claim 1 wherein said molecular sieve has a molar silicon to aluminum ratio of from 20:1 to 80:1.
The method according to claim 1, wherein 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, At least one of a hydrogen type MCM-22 molecular sieve, a hydrogen type ZSM-5 molecular sieve, and a hydrogen type beta molecular sieve.
The method according to claim 1, wherein the etherification catalyst further comprises a modifier;

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 method according to claim 7, wherein the weight percentage of the oxide in the etherification catalyst is from 0.1 to 10%.
The method according to claim 7, wherein the molecular weight of the molecular sieve in the etherification catalyst is from 20% to 85%; the weight percentage of the oxide is from 3 to 10%; and the weight of the molecular sieve and the binder The ratio is 20:80-85:15.
The method according to any one of claims 7 to 9, wherein the preparation method of the etherification catalyst comprises at least: using molecular sieve as an active component, steam treatment, oxide modification and acid treatment for acidity Bit modulation is prepared.
The method according to any one of claims 7 to 9, wherein the method for preparing the etherification catalyst comprises at least the following steps:

Oxidation modification and steam treatment of the molecular sieve; or

Molecular sieves are subjected to oxide modification, steam treatment and acid treatment;

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 method according to any one of claims 7 to 9, wherein the method for preparing the etherification catalyst comprises at least:

(1) mixing the molecular sieve and the binder, drying, and calcining at 550 ° C - 700 ° C for 4-10 hours;

(2) treating the calcined catalyst at 300-700 ° C with steam;

(3) 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;

(4) 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.
Method according to any one of claims 7 to 9, characterized in that the etherification The preparation method of the catalyst includes at least the following steps:

(a1) forming a mixture containing the molecular sieve and the binder, drying, and baking;

(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;

Alternatively, the method for preparing the etherification catalyst comprises at least the following steps:

(a2) forming a mixture containing molecular sieves, a binder and an oxide, drying, and calcining;

(b2) The product in the step (a2) is subjected to steam treatment, followed by acid treatment, and calcination to obtain the etherification catalyst.
The method according to claim 13, wherein 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 method according to claim 13, wherein 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, and drying. Baking at 550 ° C - 700 ° C for 3-10 hours.
The method according to claim 13, wherein the steam treatment in the step (b1) and the step (b2) comprises: placing the object to be treated in a 100% steam atmosphere at 300-800 ° C for steam treatment 0.5 - 10 hours; then calcined at 500-700 ° C for 3-5 hours.
The method according to claim 13, wherein the acid treatment in the step (b1) and the step (b2) comprises: adding the object to be treated to an acidic solution, and immersing at room temperature - 80 ° C for 4 to 24 hours.