CN110721732B - Method for producing p-tert-butylphenol - Google Patents
Method for producing p-tert-butylphenol Download PDFInfo
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
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- B01J29/40—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
- B01J29/405—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 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- 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
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
- C07C37/16—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
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Abstract
The application discloses a method for producing p-tert-butylphenol, belonging to the field of chemical engineering. The method for producing the p-tert-butyl phenol at least comprises the following steps: the raw material containing phenol and tertiary butyl alcohol or isobutene passes through a reactor containing an alkylation catalyst to react to generate p-tertiary butyl phenol; the alkylation catalyst comprises a molecular sieve; the molecular sieve is an active component; wherein the weight percentage of the molecular sieve in the alkylation catalyst is 30-85%. The method for producing the p-tert-butylphenol has the advantages of simple process, less side reaction, capability of realizing continuous production, weak corrosion to equipment and environmental protection. The alkylation catalyst has high selectivity and good stability of p-tert-butylphenol, is convenient and flexible to use and is easy to recycle; the preparation method has the advantages of cheap and easily-obtained raw materials, simple preparation process, low cost and easy industrial application.
Description
Technical Field
The application relates to a method for producing p-tert-butylphenol, in particular to a method for producing p-tert-butylphenol by alkylating phenol and tert-butyl alcohol or isobutene, belonging to the field of chemical engineering.
Background
The p-tert-butylphenol is an important product and an intermediate in fine chemical production, and is widely used for the production of p-tert-butylphenol aldehyde resin, a surfactant, an antioxidant, a polymerization inhibitor, a stabilizer, paint and coating.
The traditional process for producing p-tert-butyl phenol is mainly batch reaction, and the catalyst comprises liquid acid, clay and ion exchange resin. The liquid acid catalysis process using sulfuric acid and phosphoric acid has the defects of more side reactions, difficult recycling of the catalyst, corrosion of equipment, large amount of waste water and the like. The clay catalysis process has the defect of difficult treatment of a large amount of catalyst waste residues in the production process. The ion exchange resin process has mild reaction conditions and no corrosiveness, but has the defects of low reaction selectivity, easy inactivation of the catalyst, inconvenience for continuous operation and the like. Therefore, research and development of solid acid catalysts with friendly environment and good catalytic performance and continuous production processes are generally concerned at home and abroad. At present, most researches take modified molecular sieves such as ZSM-5, BETA, Y, MCM-41, SBA-15 and the like as active components, however, the obtained catalyst has the defects of poor selectivity and stability of the p-tert-butylphenol, and industrialization is difficult to realize.
Disclosure of Invention
According to one aspect of the application, the method for producing the p-tert-butylphenol is provided, the method takes phenol and tert-butyl alcohol or isobutene as raw materials, the selectivity of the p-tert-butylphenol can reach 85%, and the catalyst has good stability; and no equipment corrosion exists in the production process, so that the method is an environment-friendly process and has good industrial application prospect.
The method for producing the p-tert-butylphenol is characterized by at least comprising the following steps: the raw material containing phenol and tertiary butyl alcohol or isobutene passes through a reactor containing an alkylation catalyst to react to generate p-tertiary butyl phenol;
the alkylation catalyst comprises a molecular sieve; the molecular sieve is an active component;
wherein the weight percentage of the molecular sieve in the alkylation catalyst is 30-85%.
Optionally, the weight percent of molecular sieve in the alkylation catalyst has an upper limit selected from 85%, 80%, 75%, 70%, 65%, 60%, 55%, 50%, 45%, 40%, 35%, and a lower limit selected from 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%.
Optionally, the process for producing p-tert-butylphenol comprises at least the steps of:
preheating phenol and tert-butyl alcohol or isobutene, mixing with diluted gas, and continuously passing through alkylation catalyst bed layer to make alkylation reaction to obtain p-tert-butyl phenol.
Optionally, the reaction conditions are: normal pressure, reaction temperature of 180-400 ℃, and feeding weight airspeed of 0.5-20 h-1。
Preferably, the upper limit of the reaction temperature is selected from the group consisting of 400 ℃, 380 ℃, 350 ℃, 330 ℃, 300 ℃, 280 ℃, 270 ℃, 260 ℃, 250 ℃, 220 ℃ and 200 ℃, and the lower limit is selected from the group consisting of 180 ℃, 200 ℃ and 22 ℃0 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 300 ℃, 330 ℃, 350 ℃ and 380 ℃; the upper limit of the feed weight space velocity is selected from 20h-1、17h-1、14h-1、12h-1、10h-1、8h-1、6h-1、5h-1、4h-1、3h-1、2h-1、1h-1The lower limit is selected from 0.5h-1、1h-1、2h-1、3h-1、4h-1、5h-1、6h-1、8h-1、10h-1、12h-1、14h-1、17h-1。
More preferably, the reaction temperature is 200-300 ℃, and the feeding weight space velocity is 1-10 h-1。
Optionally, the diluent gas is nitrogen or water vapor.
Optionally, the molar ratio of the dilution gas to phenol is 0.5-20: 1.
Preferably, the upper limit of the molar ratio of the dilution gas to phenol is selected from 20:1, 17:1, 14:1, 12:1, 10:1, 8:1, 6:1, 5:1, 4:1, 3:1, 2:1, 1:1, and the lower limit is selected from 0.5:1, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 8:1, 10:1, 12:1, 14:1, 17: 1.
Optionally, the molar ratio of tert-butanol or isobutylene to phenol is 4:1 to 1: 4.
Preferably, the molar ratio of tert-butanol or isobutylene to phenol has an upper limit selected from 4:1, 3:1, 2:1, 1:2, 1:3 and a lower limit selected from 1:4, 1:3, 1:2, 1:1, 2:1, 3: 1.
Optionally, the molar silica-alumina ratio of the molecular sieve is 20-200: 1.
Preferably, the molecular sieve has an upper limit of molar silicon to aluminum ratio selected from 200:1, 170:1, 140:1, 120:1, 100:1, 80:1, 70:1, 60:1, 50:1, 40:1, 30:1 and a lower limit selected from 20:1, 30:1, 40:1, 50:1, 60:1, 70:1, 80:1, 100:1, 120:1, 140:1, 170: 1.
Optionally, the molecular sieve is at least one selected from ZSM-5 molecular sieve, MCM-22 molecular sieve and BETA molecular sieve.
Optionally, the molecular sieve is a hydrogen type molecular sieve or an ammonium type molecular sieve.
Optionally, the alkylation catalyst further comprises a binder.
Optionally, the binder is selected from at least one of silica sol, diatomaceous earth, silica, boehmite, alumina sol, alumina, kaolin.
Optionally, the weight ratio of the molecular sieve to the binder is 180: 20-60: 140.
Preferably, the weight ratio of the molecular sieve to the binder has an upper limit selected from 180:20, 170:30, 160:40, 150:50, 140:60, 130:70, 120:80, 100:100, 80:120, 70:130 and a lower limit selected from 60:140, 70:130, 80:120, 100:100, 120:80, 130:70, 140:60, 150:50, 160:40, 170: 30.
Optionally, the method of preparing the alkylation catalyst comprises at least the steps of: the mixture comprising the molecular sieve and the binder is shaped, calcined, and then subjected to at least one selected from the group consisting of oxide modification, steam treatment, and acid treatment.
In a preferred embodiment, the product obtained by calcination is subjected to oxide modification and steam treatment.
In another preferred embodiment, the product obtained by calcination is subjected to oxide modification and acid treatment.
In yet another preferred embodiment, the product obtained by calcination is subjected to steam treatment and acid treatment.
In yet another preferred embodiment, the product obtained by calcination is subjected to oxide modification, steam treatment and acid treatment.
The various modification methods of the catalyst are different depending on the acid strength of the parent molecular sieve and the density of different acid sites, and the various modification methods used in the present application are compositely modified to obtain a desired catalyst. For molecular sieve precursors with lower acid site density of the catalyst, the ideal acid strength can be obtained by one or two modification methods of the application. Therefore, single modification methods of various elements also belong to the coverage field of the application. For example, single modifications such as metal oxide modification, acid treatment, steam treatment, and the like are all within the scope of the present application.
It should be noted that, in the present application, the order of the oxide modification, the steam treatment, and the acid treatment performed on the molded calcined product of the mixture containing the molecular sieve and the binder is not particularly limited. However, it is preferable to perform the oxide modification, the steam treatment, and the acid treatment in this order.
It should be noted that, in the present application, the number of times of oxide modification, steam treatment, and acid treatment performed on the molded calcined product of the mixture containing the molecular sieve and the binder is not particularly limited. For example, when the oxide modification is performed, the oxide modification may be performed two or more times.
Optionally, the shaping is selected from spray shaping and extrusion. According to different molding modes, the correspondingly prepared catalyst can be used as a fluidized bed catalyst or a fixed bed catalyst. The fluidized bed catalyst can be prepared by the preparation steps after spray forming, and the fixed bed catalyst can be prepared by the preparation steps after extrusion molding to form a matrix.
Optionally, the roasting condition is roasting at 500-700 ℃ for 4-10 hours.
Preferably, the roasting temperature has an upper limit selected from 700 ℃, 650 ℃, 600 ℃, 550 ℃, and a lower limit selected from 500 ℃, 550 ℃, 600 ℃, 650 ℃; the upper limit of the time is selected from 10 hours, 8 hours and 6 hours, and the lower limit is selected from 4 hours, 6 hours and 8 hours.
Optionally, the oxide modification comprises: and soaking the roasted product in a solution containing an oxide precursor for 10-36 hours, drying, and roasting at 550-700 ℃ for 3-10 hours.
For the purposes of the present application, the term "oxide precursor" is understood in the context of the present application to mean a substance which generates the corresponding oxide under the process and conditions of the above-described oxide modification. The oxide may be a metal oxide or a non-metal oxide. In one example, in the case of a metal oxide, the solution of its oxide precursor may be a salt solution of the metal, such as an aqueous nitrate solution.
Optionally, the oxide modification comprises a composite modification of one or more metal oxides and non-metal oxides. In one example, the shaped calcined product of the mixture comprising the molecular sieve and the binder is subjected to metal oxide modification and non-metal oxide modification, respectively.
Optionally, the oxide is selected from at least one of calcium oxide, strontium oxide, barium oxide and lanthanum oxide, and the weight percentage of the oxide in the alkylation catalyst is 0.1-15%, the upper limit of the weight percentage is selected from 15%, 12%, 10%, 7%, 5%, 3%, 1%, 0.5%, 0.2%, and the lower limit is selected from 0.1%, 0.2%, 0.5%, 1%, 3%, 5%, 7%, 10%, 12%; and at least one selected from phosphorus pentoxide and cerium oxide, wherein the weight percentage of the phosphorus pentoxide and the cerium oxide in the alkylation catalyst is 0.1-10%, the upper limit of the weight percentage is selected from 10%, 8%, 6%, 5%, 3%, 1%, 0.5%, 0.2%, and the lower limit is selected from 0.1%, 0.2%, 0.5%, 1%, 3%, 5%, 6%, 8%.
Preferably, in the oxide modification, the upper limit of the dipping time is selected from 36 hours, 32 hours, 28 hours, 24 hours, 20 hours, 16 hours, 12 hours, and the lower limit is selected from 10 hours, 12 hours, 16 hours, 20 hours, 24 hours, 28 hours, 32 hours; the upper limit of the roasting temperature is selected from 700 ℃, 675 ℃, 650 ℃, 625 ℃, 600 ℃ and 575 ℃, and the lower limit is selected from 550 ℃, 575 ℃, 600 ℃, 625 ℃, 650 ℃ and 675 ℃; the upper limit of the roasting time is selected from 10 hours, 8 hours, 6 hours and 4 hours, and the lower limit is selected from 3 hours, 4 hours, 6 hours and 8 hours.
Optionally, the conditions of the water vapor treatment include: the reaction is carried out in 100% steam at 300-800 ℃ for 0.5-10 hours under 1.0-3.0 MPa.
Preferably, in the steam treatment, the upper temperature limit is selected from 800 ℃, 750 ℃, 700 ℃, 650 ℃, 600 ℃, 550 ℃, 500 ℃, 450 ℃, 400 ℃, 350 ℃, and the lower temperature limit is selected from 300 ℃, 350 ℃, 400 ℃, 450 ℃, 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃; the upper limit of time is selected from 10 hours, 8 hours, 6 hours, 5 hours, 4 hours, 3 hours, 2 hours, 1 hour, and the lower limit is selected from 0.5 hours, 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 8 hours; the upper limit of the pressure is selected from 3.0MPa, 2.5MPa, 2.0MPa and 1.5MPa, and the lower limit is selected from 1.0MPa, 1.5MPa, 2.0MPa and 2.5 MPa.
Optionally, the acid treatment comprises: 0.1-0.5 mol/L citric acid aqueous solution, 0.1-0.5 mol/L nitric acid aqueous solution or 0.1-0.5 mol/L sulfuric acid aqueous solution are used, the weight ratio of the object to be treated and the aqueous solution is 1:5, the dipping time is 2-10 hours, and the dipping temperature is 20-80 ℃.
Preferably, in the acid treatment, the upper concentration limit of the acid aqueous solution is selected from 0.5mol/L, 0.4mol/L, 0.3mol/L and 0.2mol/L, and the lower concentration limit is selected from 0.1mol/L, 0.2mol/L, 0.3mol/L and 0.4 mol/L; the upper limit of the dipping time is selected from 10 hours, 8 hours, 6 hours and 4 hours, and the lower limit is selected from 2 hours, 4 hours, 6 hours and 8 hours; the impregnation temperature is selected from the upper limit of 80 deg.C, 70 deg.C, 60 deg.C, 50 deg.C, 40 deg.C, 30 deg.C, and the lower limit of 20 deg.C, 30 deg.C, 40 deg.C, 50 deg.C, 60 deg.C, 70 deg.C.
Optionally, the acid treatment further comprises: and drying and roasting the product obtained by impregnation.
Preferably, the roasting condition is roasting at 500-800 ℃ for 2-10 hours.
More preferably, the roasting temperature is selected from the upper limit of 800 ℃, 750 ℃, 700 ℃, 650 ℃, 600 ℃, 550 ℃, and the lower limit of 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃; the upper limit of time is selected from 10 hours, 8 hours, 6 hours, 4 hours, 3 hours, and the lower limit is selected from 2 hours, 3 hours, 4 hours, 6 hours, 8 hours.
In a specific embodiment, the alkylation catalyst is comprised of a molecular sieve and a binder, and is prepared by oxide modification, steam treatment, and acid treatment.
In another specific embodiment, the process for preparing the alkylation catalyst comprises the steps of:
(1) forming and drying a mixture containing the molecular sieve and the binder, and roasting at 500-700 ℃ for 4-10 hours;
(2) carrying out oxide modification on the mixture obtained in the step (1), drying, and roasting at 550-700 ℃ for 3-10 hours;
(3) performing steam treatment on the mixture obtained in the step (2) at the temperature of 300-800 ℃ for 0.5-10 hours;
(4) and (4) carrying out acid treatment on the mixture obtained in the step (3), drying, and roasting at 500-800 ℃ for 2-10 hours.
According to another aspect of the present application, an alkylation catalyst is provided, which has high selectivity of p-tert-butylphenol, good stability, convenient and flexible use, and easy recycling.
According to still another aspect of the present application, a method for preparing the alkylation catalyst is provided, wherein the method has the advantages of cheap and easily available raw materials, simple preparation process, low cost and easy industrial application.
The alkylation catalyst and the method of preparation thereof are described above.
According to yet another aspect of the present application, there is provided the use of the alkylation catalyst for the alkylation reaction of phenol to produce p-tert-butylphenol from phenol and tert-butanol or isobutylene.
The beneficial effects that this application can produce include:
1) the method for producing the p-tert-butylphenol has the advantages of simple production flow and few reaction byproducts, and the p-tert-butylphenol product with the purity of more than 99 percent can be obtained by simple distillation; the method can realize continuous production, can greatly reduce the cost and improve the efficiency, and has good economic benefit; and the method has weak corrosion to equipment and small pollution in the production process, and is a new green and environment-friendly process technology.
2) The alkylation catalyst provided by the application has excellent performance, high selectivity of p-tert-butylphenol and good stability; and the use is convenient and flexible, and the recycling is easy.
3) The alkylation catalyst preparation method provided by the application has the advantages of cheap and easily-obtained raw materials, simple preparation process, low preparation cost and easy industrial application.
Detailed Description
As described above, in view of the disadvantages of batch reaction and high production labor intensity in the conventional p-tert-butylphenol production technology, the application provides a method for producing p-tert-butylphenol, which uses phenol and tert-butyl alcohol or isobutene as raw materials, produces p-tert-butylphenol with high selectivity by using a molecular sieve catalyst, does not corrode equipment in the production process, does not generate a large amount of industrial wastewater, and is an environment-friendly green process.
According to the application, the acidity site and the acid strength of the molecular sieve are modulated by different modification methods and combinations thereof.
According to the application, the characteristics of the catalyst structure and the number of acid sites are considered in the preparation process, the modification step and the percentage of the modifier in the catalyst are optimized and controlled, silica sol, diatomite, alumina and alumina sol are used during molding, and the strength of the catalyst is increased after roasting. The acid treatment, the oxide modification and the steam treatment are carried out to enhance the hydrothermal stability of the catalyst, and the synergistic effect of the modification processes ensures that the catalyst has good catalytic performance and good strength, and can completely meet the industrial use requirements.
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise stated, the starting materials and reagents in the examples of the present application were purchased commercially, wherein the MCM-22 molecular sieve was synthesized according to the method described in patent US 4954325; ZSM-5 molecular sieves were manufactured by catalyst works of southern Kaiki university under the trade name NKF-5; BETA molecular sieve is produced by catalyst works of southern Kao university under the trade name NKF-6.
The analysis method in the examples of the present application is as follows:
the chromatographic analysis was carried out using an agilent 7890A gas chromatograph. The chromatographic column is a cyclodextrin column, 30m × 0.25mm × 0.25 μm. Chromatographic analysis conditions: column temperature: the initial temperature is 150 ℃, the temperature is kept for 15 minutes, the temperature is increased to 180 ℃ at the heating rate of 10 ℃/minute, and the temperature is kept for 5.3 minutes; carrier gas: high-purity nitrogen; pressing the column in front: 6.5 pisa.
The conversion, selectivity in the examples of the present application are calculated as follows:
example 1
The alkylation catalyst was prepared as follows: 120 g of hydrogen type ZSM-5 molecular sieve with the molar ratio of 20:1, 60 g of diatomite and 100g of silica sol with the weight percentage of 20 percent of silica are mixed, and a proper amount of 10 percent of dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 500 deg.C for 10 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor A0. 20 g of A0 is soaked in 15 percent by weight of calcium nitrate water solution for 12 hours, dried at 120 ℃ and roasted at 700 ℃ for 3 hours to obtain A1, wherein the weight percent of calcium oxide is 5 percent. 20 g of A1 was subjected to steam treatment in an atmosphere of 100% steam at 350 ℃ and 1.0MPa for 10 hours to obtain A2. 20 g of A2 is soaked by 0.5mol/L citric acid aqueous solution at 80 ℃, the weight ratio of A2 to the solution is 1:5, the soaking time is 2 hours, and the solution is roasted at 550 ℃ for 3 hours to prepare the alkylation catalyst A, wherein the weight percentage of the molecular sieve is 60 percent.
Example 2
The alkylation catalyst was prepared as follows: 60 g of hydrogen type ZSM-5 molecular sieve with the molar ratio of silicon to aluminum of 30:1, 100g of silica sol with the weight percentage of silicon dioxide of 40 percent and 100g of alumina are mixed, and a proper amount of 10 percent dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 700 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor B0. 20 g of B0 is dipped in 30 percent by weight of strontium nitrate water solution for 12 hours, dried at 120 ℃ and roasted at 550 ℃ for 10 hours to obtain B1, wherein the weight percent of strontium oxide is 15 percent. 20 g of B1 was subjected to steam treatment in a 100% steam atmosphere at 800 ℃ under 2.0MPa for 0.5 hour to obtain B2. 20 g of B2 was impregnated with 0.5mol/L aqueous nitric acid at 20 ℃ for 8 hours, the weight ratio of B2 to the solution was 1:5, and calcined at 650 ℃ for 3 hours to produce alkylation catalyst B, wherein the weight percentage of the molecular sieve was 30%.
Example 3
The alkylation catalyst was prepared as follows: 200 g of hydrogen type ZSM-5 molecular sieve with the mol ratio of 40:1, 20 g of diatomite and 30 g of kaolin are mixed, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for strip extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor D0. 20 g of D0 is dipped in 0.15 percent by weight of barium nitrate water solution for 24 hours, dried at 120 ℃ and roasted at 600 ℃ for 3 hours to obtain D1, wherein the weight percent of barium oxide is 0.1 percent. 20 g of D1 was subjected to steam treatment in a 100% steam atmosphere at 350 ℃ under 3.0MPa for 10 hours to obtain D2. 20 g of D2 was impregnated with 0.5mol/L aqueous sulfuric acid at 40 ℃ for 10 hours at a weight ratio of D2 to the solution of 1:5 and calcined at 550 ℃ for 3 hours to produce alkylation catalyst D, wherein the weight percentage of the molecular sieve was 80%.
Example 4
The alkylation catalyst was prepared as follows: 200 g of ammonia type ZSM-5 molecular sieve with the molar ratio of 30:1, 10 g of diatomite and 100g of silica sol with the weight percentage of silica being 40 percent are mixed, and a proper amount of 10 percent of dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor F0. 20 g of F0 is soaked in 20 weight percent calcium nitrate water solution for 24 hours, dried at 120 ℃ and roasted at 700 ℃ for 3 hours to obtain F1, wherein the weight percent of calcium oxide is 10 percent. 20 g of F1 was subjected to steam treatment in an atmosphere of 100% steam at 450 ℃ and 3.0MPa for 10 hours to obtain F2. 20 g of F2 is immersed in 0.5mol/L nitric acid water solution for 6 hours at 30 ℃, the weight ratio of F2 to the solution is 1:5, and the solution is roasted for 3 hours at 500 ℃ to prepare the alkylation catalyst F, wherein the weight percentage of the molecular sieve is 80%.
Example 5
The alkylation catalyst was prepared as follows: 200 g of ammonia type ZSM-5 molecular sieve with the mol ratio of 40:1 is mixed with 50 g of boehmite, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for strip extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor G0. 20G of G0 is dipped in 20 percent by weight of barium nitrate water solution for 36 hours, dried at 120 ℃ and roasted at 700 ℃ for 3 hours to obtain G1, wherein the weight percent of barium oxide is 15 percent. 20G of G1 was subjected to steam treatment in an atmosphere of 100% steam at 450 ℃ under 2.0MPa for 10 hours to obtain G2. 20G of G2 was impregnated with 0.2mol/L aqueous sulfuric acid at 30 ℃ for 8 hours, the weight ratio of G2 to the solution was 1:5, and the catalyst was calcined at 800 ℃ for 3 hours to produce an alkylation catalyst G, wherein the weight percentage of the molecular sieve was 80%.
Example 6
The alkylation catalyst was prepared as follows: 140 g of ammonia type ZSM-5 molecular sieve with the molar ratio of 30:1, 20 g of silicon oxide and 40 g of aluminum oxide are mixed, and a proper amount of 10 percent dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor H0. 20 g of H0 is soaked in 8 percent by weight of cerous nitrate water solution for 20 hours, dried at 120 ℃, and roasted at 700 ℃ for 3 hours to obtain H1, wherein the weight percent of cerium oxide is 3 percent. 20 g of H1 was subjected to steam treatment in an atmosphere of 100% steam at 550 ℃ and 1.0MPa for 4 hours to obtain H2. 20 g of H2 was immersed in 0.5mol/L aqueous citric acid at 80 ℃ for 10 hours, the weight ratio of H2 to the solution was 1:5, and the solution was calcined at 600 ℃ for 3 hours to produce alkylation catalyst H, wherein the weight percentage of the molecular sieve was 70%.
Example 7
The alkylation catalyst was prepared as follows: 170 g of hydrogen type ZSM-5 molecular sieve with the molar ratio of 30:1 is mixed with 100g of silica sol with the weight percentage of silica being 30 percent, and a proper amount of 10 percent of dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor I0. 20 g of I0 was immersed in 26 wt% aqueous cerium nitrate solution for 20 hours, dried at 120 ℃ and calcined at 700 ℃ for 3 hours to obtain I1, wherein the weight percentage of cerium oxide was 10%. 20 g of I1 were treated with steam at 350 ℃ and 1.0MPa in an atmosphere of 100% steam for 10 hours to give I2. 20 g of I2 was immersed in 0.5mol/L aqueous nitric acid at 20 ℃ for 10 hours, I2 was calcined at 550 ℃ for 3 hours at a weight ratio of 1:5 to the solution, to produce alkylation catalyst I, wherein the weight percentage of the molecular sieve was 85%.
Example 8
The alkylation catalyst was prepared as follows: 180 g of hydrogen type ZSM-5 molecular sieve with the molar ratio of 80:1 is mixed with 100g of silica sol with the weight percentage of 20 percent of silicon dioxide, and a proper amount of 10 percent of dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor J0. 20 g of J0 is soaked in 8 percent by weight of ammonium dihydrogen phosphate aqueous solution for 24 hours, dried at 120 ℃ and roasted at 700 ℃ for 3 hours to obtain J1, wherein the weight percent of phosphorus pentoxide is 5 percent. 20 g of J1 was subjected to steam treatment in a 100% steam atmosphere at 350 ℃ and 3.0MPa for 4 hours to obtain J2. 20 g of J2 was immersed in 0.5mol/L citric acid aqueous solution at 60 ℃ for 8 hours, the weight ratio of J2 to solution was 1:5, and calcined at 650 ℃ for 3 hours to produce alkylation catalyst J, wherein the weight percentage of the molecular sieve was 80%.
Example 9
The alkylation catalyst was prepared as follows: 160 g of hydrogen type ZSM-5 molecular sieve with the molar ratio of silicon to aluminum of 30:1 is mixed with 100g of silica sol with the weight percentage of silicon dioxide of 40 percent, and a proper amount of 10 percent of dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst parent body K0. 20 g of K0 is soaked in 0.26 percent by weight of cerous nitrate water solution for 24 hours, dried at 120 ℃ and roasted at 600 ℃ for 3 hours to obtain K1, wherein the weight percent of cerium oxide is 0.1 percent. 20 g of K1 was subjected to steam treatment in an atmosphere of 100% steam at 350 ℃ and 1.0MPa for 4 hours to obtain K2. 20 g of K2 is soaked in 0.2mol/L nitric acid water solution for 10 hours at 30 ℃, the weight ratio of K2 to the solution is 1:5, and the mixture is roasted for 3 hours at 550 ℃, so that the alkylation catalyst K is prepared, wherein the weight percentage of the molecular sieve is 80%.
Example 10
The alkylation catalyst was prepared as follows: 160 g of hydrogen type ZSM-5 molecular sieve with the molar ratio of silicon to aluminum of 30:1 is mixed with 40 g of alumina, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for strip extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor L0. 20 g of L0 was immersed in 29% by weight aqueous calcium nitrate solution for 24 hours, dried at 120 ℃ and calcined at 600 ℃ for 3 hours to obtain L1, wherein the weight percentage of calcium oxide was 10%. 20 g of L1 was subjected to steam treatment in an atmosphere of 100% steam at 600 ℃ under 1.0MPa for 2 hours to obtain L2. 20 g of L2 was immersed in 0.1mol/L aqueous sulfuric acid at 20 ℃ for 10 hours, the weight ratio of L2 to the solution was 1:5, and calcined at 550 ℃ for 3 hours to produce an alkylation catalyst L, wherein the weight percentage of the molecular sieve was 80%.
Example 11
The alkylation catalyst was prepared as follows: 100g of hydrogen MCM-22 molecular sieve with the molar silica-alumina ratio of 20:1, 70 g of hydrogen ZSM-5 molecular sieve with the molar silica-alumina ratio of 30:1 and 30 g of kaolin are mixed, and a proper amount of 10 percent dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor M0. 20 g of M0 is soaked in 29 percent by weight of calcium nitrate water solution for 24 hours, dried at 120 ℃ and roasted at 600 ℃ for 3 hours to obtain M1, wherein the weight percent of calcium oxide is 10 percent. 20 g of M1 is soaked in 8 percent phosphoric acid aqueous solution for 24 hours, dried at 120 ℃ and roasted at 600 ℃ for 3 hours to obtain M2, wherein the weight percentage of phosphorus pentoxide is 5 percent. 20 g of M2 was immersed in 0.1mol/L aqueous sulfuric acid at 30 ℃ for 10 hours, the weight ratio of M2 to the solution was 1:5, and calcined at 650 ℃ for 3 hours to produce alkylation catalyst M, wherein the weight percentage of the molecular sieve was 85%.
Example 12
The alkylation catalyst was prepared as follows: 170 g of hydrogen MCM-22 molecular sieve with the molar silica-alumina ratio of 60:1 is mixed with 100g of silica sol with the weight percentage of 30 percent of silica, and a proper amount of 10 percent of dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor N0. 20 g of N0 is soaked in 8 percent by weight of calcium acetate aqueous solution for 10 hours, dried at 120 ℃, roasted at 650 ℃ for 3 hours to obtain N1, wherein the weight percent of calcium oxide is 3 percent. 20 g of N1 was subjected to steam treatment in an atmosphere of 100% steam at 350 ℃ and 2.0MPa for 10 hours to obtain N2. 20 g of N2 was immersed in 0.5mol/L aqueous sulfuric acid at 20 ℃ for 10 hours, the weight ratio of N2 to the solution was 1:5, and calcined at 550 ℃ for 3 hours to produce alkylation catalyst N, wherein the weight percentage of the molecular sieve was 85%.
Example 13
The alkylation catalyst was prepared as follows: 170 g of hydrogen MCM-22 molecular sieve with the molar silica-alumina ratio of 50:1 is mixed with 100g of silica sol with the weight percentage of silica being 30 percent, and a proper amount of 10 percent of dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor P0. 20 g of P0 is dipped in 5 percent by weight of barium nitrate water solution for 36 hours, dried at 120 ℃ and roasted at 700 ℃ for 3 hours to obtain P1, wherein the weight percent of barium oxide is 3 percent. 20 g of P1 was subjected to steam treatment in an atmosphere of 100% steam at 350 ℃ and 2.0MPa for 10 hours to obtain P2. 20 g of P2 is immersed in 0.2mol/L nitric acid water solution for 6 hours at 30 ℃, the weight ratio of P2 to the solution is 1:5, and the solution is roasted for 3 hours at 550 ℃, so as to prepare the alkylation catalyst P, wherein the weight percentage of the molecular sieve is 85 percent.
Example 14
The alkylation catalyst was prepared as follows: 160 g of hydrogen MCM-22 molecular sieve with the molar silica-alumina ratio of 40:1, 20 g of diatomite and 100g of silica sol with the weight percentage of 20 percent of silica are mixed, and a proper amount of 10 percent of dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor R0. 20 g of R0 is soaked in 5 percent phosphoric acid aqueous solution by weight percent for 20 hours, dried at 120 ℃, and roasted at 700 ℃ for 3 hours to obtain R1, wherein the weight percent of phosphorus pentoxide is 3 percent. 20 grams of R1 was steamed for 6 hours at 350 ℃ and 1.0MPa in a 100% steam atmosphere and then calcined at 550 ℃ for 3 hours to produce the alkylation catalyst R, wherein the weight percent of the molecular sieve was 80%.
Example 15
The alkylation catalyst was prepared as follows: 170 g of hydrogen type beta molecular sieve with the molar ratio of silicon to aluminum of 20:1 is mixed with 100g of silica sol with the weight percentage of silicon dioxide of 30 percent, and a proper amount of 10 percent of dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor S0. 20 g of S0 is dipped in 10 percent by weight of ammonium ceric nitrate aqueous solution for 20 hours, dried at 120 ℃ and roasted at 700 ℃ for 3 hours to obtain S1, wherein the weight percent of cerium oxide is 3 percent. 20 g of S1 was subjected to steam treatment in a 100% steam atmosphere at 550 ℃ under 2.0MPa for 4 hours to obtain S2. 20 g of S2 was immersed in 0.2mol/L aqueous nitric acid at 30 ℃ for 8 hours, the weight ratio of S2 to the solution was 1:5, and calcined at 550 ℃ for 3 hours to produce alkylation catalyst S, wherein the weight percentage of the molecular sieve was 85%.
Example 16
The alkylation catalyst was prepared as follows: 60 g of hydrogen MCM-22 molecular sieve with the molar silica-alumina ratio of 30:1, 100g of silica sol with the weight percentage of silica being 40% and 100g of alumina are mixed, and a proper amount of 10% dilute nitric acid is added to be used as an extrusion aid for extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst precursor T0. 20 g of T0 was immersed in 2.6 wt% aqueous lanthanum nitrate solution for 20 hours, dried at 120 ℃ and calcined at 700 ℃ for 3 hours to obtain T1, in which the lanthanum oxide content was 1 wt%. 20 g of T1 was subjected to steam treatment in an atmosphere of 100% steam at 550 ℃ and 1.0MPa for 4 hours to obtain T2. 20 g of T2 was immersed in 0.5mol/L citric acid aqueous solution at 60 ℃ for 6 hours, the weight ratio of T2 to the solution was 1:5, and calcined at 550 ℃ for 3 hours to obtain an alkylation catalyst T, wherein the weight percentage of the molecular sieve was 30%.
Example 17
The alkylation catalyst was prepared as follows: 160 g of hydrogen type ZSM-5 molecular sieve with the molar ratio of 100:1 is mixed with 40 g of alumina, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for strip extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst parent body U0. 20 g of U0 is soaked in 15 percent by weight of calcium nitrate water solution for 24 hours, dried at 120 ℃ and roasted at 600 ℃ for 3 hours to obtain U1, wherein the weight percentage of calcium oxide is 5 percent. 20 g of U1 was subjected to steam treatment in a 100% steam atmosphere at 400 ℃ under 3.0MPa for 5 hours to obtain U2. 20 g of U2 was immersed in 0.5mol/L aqueous sulfuric acid at 20 ℃ for 10 hours at a weight ratio of U2 to solution of 1:5 and calcined at 550 ℃ for 3 hours to produce alkylation catalyst U, wherein the weight percentage of the molecular sieve was 80%.
Example 18
The alkylation catalyst was prepared as follows: 140 g of hydrogen type ZSM-5 molecular sieve with the molar ratio of 200:1 is mixed with 60 g of alumina, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for strip extrusion molding. Drying at 120 deg.C, and calcining at 550 deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst parent V0. 20 g of V0 is soaked in 8 percent by weight of cerous nitrate water solution for 24 hours, dried at 120 ℃ and roasted at 600 ℃ for 3 hours to obtain V1, wherein the weight percent of cerium oxide is 3 percent. 20 g of V1 was subjected to steam treatment in an atmosphere of 100% steam at 600 ℃ under 1.0MPa for 2 hours to obtain V2. 20 g of V2 was immersed in 0.5mol/L aqueous citric acid at 80 ℃ for 10 hours, the weight ratio of V2 to the solution was 1:5, and calcined at 550 ℃ for 3 hours to obtain alkylation catalyst V, wherein the weight percentage of the molecular sieve was 70%.
Example 19
The alkylation catalysts obtained in examples 1 to 18 were subjected to alkylation of phenol with tert-butyl alcohol or isobutylene in a fixed bed reaction apparatus. The raw materials of phenol, tertiary butanol or isobutene and water vapor enter a reactor for reaction after being preheated, and the reaction product is subjected to online chromatographic analysis. The loading amount of the reaction catalyst is 20.0 g, and the weight space velocity is 0.5-20 h-1On the contraryThe temperature is 180-400 ℃, the diluent gas is steam, and the molar ratio of the diluent gas to the phenol is 0.5-20: 1. The molar ratio of the tert-butyl alcohol or the isobutene to the phenol is 1: 4-4: 1. Wherein the reaction raw materials of the examples 1 to 9 are tert-butanol and phenol;
the starting materials for the reactions of examples 10-18 were isobutylene and phenol. The results of the 72 hour reaction of the alkylation catalysts of each example are shown in Table 1.
TABLE 1 catalytic reaction conditions and catalytic performance of alkylation catalysts
Examples 20 to 23
The catalyst evaluation apparatus and the test method were the same as in example 19. The loading of the reaction catalyst was 20.0 g. Wherein the molar ratio of the tert-butyl alcohol fed in the example 20 and the tert-butyl alcohol fed in the example 21 to the phenol is 1:1, and the molar ratio of the isobutene fed in the example 22 and the isobutene fed in the example 23 to the phenol is 1: 1. The space velocity of the feeding weight is 3h-1The dilution gas is water vapor or nitrogen, and the molar ratio of the dilution gas to the fed phenol is 5: 1. The reaction results of the alkylation catalysts in the examples are shown in Table 2.
TABLE 2 catalytic reaction conditions and catalytic performance of alkylation catalysts
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (16)
1. A process for the production of p-tert-butylphenol, characterized in that it comprises at least the following steps: the raw material containing phenol and tertiary butyl alcohol or isobutene passes through a reactor containing an alkylation catalyst to react to generate p-tertiary butyl phenol;
the alkylation catalyst comprises a molecular sieve; the molecular sieve is an active component;
wherein the weight percentage of the molecular sieve in the alkylation catalyst is 30-85%;
the alkylation catalyst further comprises a binder;
the preparation method of the alkylation catalyst at least comprises the following steps: forming and roasting a mixture containing a molecular sieve and a binder, and then modifying a roasted product, wherein the modification comprises the steps of carrying out oxide modification, water vapor treatment and acid treatment on the roasted product, or carrying out oxide modification and acid treatment on the roasted product;
the oxide modification comprises: dipping the roasted product in a solution containing an oxide precursor for 10-36 hours, drying, and roasting at 550-700 ℃ for 3-10 hours;
the oxide is at least one of calcium oxide, strontium oxide, barium oxide and lanthanum oxide, and the weight percentage of the oxide in the alkylation catalyst is 0.1-15%; and at least one selected from phosphorus pentoxide and cerium oxide, wherein the weight percentage of the phosphorus pentoxide and the cerium oxide in the alkylation catalyst is 0.1-10%;
the conditions of the water vapor treatment include: the reaction is carried out in 100% steam at the temperature of 300-800 ℃ for 0.5-10 hours and under the pressure of 1.0-3.0 MPa;
the acid treatment comprises: 0.1-0.5 mol/L citric acid aqueous solution, 0.1-0.5 mol/L nitric acid aqueous solution or 0.1-0.5 mol/L sulfuric acid aqueous solution are used, the weight ratio of the object to be treated and the aqueous solution is 1:5, the dipping time is 2-10 hours, and the dipping temperature is 20-80 ℃.
2. Method according to claim 1, characterized in that it comprises at least the following steps:
preheating phenol and tert-butyl alcohol or isobutene, mixing with diluted gas, and continuously passing through alkylation catalyst bed layer to make alkylation reaction to obtain p-tert-butyl phenol.
3. The process according to claim 1, characterized in that the reaction conditions are: normal pressure, reaction temperature of 180-400 ℃, and feeding weight airspeed of 0.5-20 h-1。
4. The method of claim 3, wherein the reaction temperature is 200-300 ℃, and the feed weight space velocity is 1-10 h-1。
5. The method of claim 2, wherein the diluent gas is nitrogen or water vapor.
6. The method according to claim 2, wherein the molar ratio of the dilution gas to the phenol is 0.5 to 20: 1.
7. The method of claim 1, wherein the molar ratio of tert-butanol or isobutylene to phenol is 4:1 to 1: 4.
8. The method according to claim 1, wherein the molar silica-alumina ratio of the molecular sieve is 20-200: 1.
9. The method of claim 1, wherein the molecular sieve is at least one selected from the group consisting of ZSM-5 molecular sieve, MCM-22 molecular sieve, BETA molecular sieve.
10. The method of claim 1, wherein the molecular sieve is a hydrogen type molecular sieve or an ammonium type molecular sieve.
11. The method of claim 1, wherein the binder is selected from at least one of silica sol, diatomaceous earth, silica, boehmite, alumina sol, alumina, kaolin.
12. The method of claim 1, wherein the weight ratio of the molecular sieve to the binder is 180:20 to 60: 140.
13. The method according to claim 1, wherein the roasting is performed at 500 to 700 ℃ for 4 to 10 hours.
14. The method of claim 1, wherein the acid treatment further comprises: and drying and roasting the product obtained by impregnation.
15. The method as claimed in claim 14, wherein the roasting is carried out at 500 to 800 ℃ for 2 to 10 hours.
16. Method according to any one of claims 1 to 15, characterized in that it comprises the following steps:
(1) forming and drying a mixture containing the molecular sieve and the binder, and roasting at 500-700 ℃ for 4-10 hours;
(2) carrying out oxide modification on the mixture obtained in the step (1), drying, and roasting at 550-700 ℃ for 3-10 hours;
(3) performing steam treatment on the mixture obtained in the step (2) at the temperature of 300-800 ℃ for 0.5-10 hours;
(4) and (4) carrying out acid treatment on the mixture obtained in the step (3), drying, and roasting at 500-800 ℃ for 2-10 hours.
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| CN1546235A (en) * | 2003-12-09 | 2004-11-17 | 南开大学 | Novel catalyst for synthesizing tertiary-butyl substituted benzene phenols and its preparation process |
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| CN1546235A (en) * | 2003-12-09 | 2004-11-17 | 南开大学 | Novel catalyst for synthesizing tertiary-butyl substituted benzene phenols and its preparation process |
| CN102000604A (en) * | 2010-10-12 | 2011-04-06 | 江苏大学 | Method for synthesizing composite molecular sieve by microwave method and catalytic performance application thereof |
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