CN116496145A - Method for producing 2, 4-di-tert-butylphenol - Google Patents

Method for producing 2, 4-di-tert-butylphenol Download PDF

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CN116496145A
CN116496145A CN202310519872.8A CN202310519872A CN116496145A CN 116496145 A CN116496145 A CN 116496145A CN 202310519872 A CN202310519872 A CN 202310519872A CN 116496145 A CN116496145 A CN 116496145A
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molecular sieve
oxide
solid acid
acid catalyst
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请求不公布姓名
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Nuoqiying Fine Chemical Technology Dalian Co ltd
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/14—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 addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • 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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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7049—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
    • B01J29/7088—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The application discloses a method for producing 2, 4-di-tert-butylphenol, which belongs to the field of chemistry and chemical industry. The method for producing 2, 4-di-tert-butylphenol at least comprises the following steps: raw materials containing phenol and tertiary butyl alcohol or isobutene are reacted by a reactor containing a solid acid catalyst to generate 2, 4-di-tertiary butyl phenol; the solid acid 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 30-80%. The method for preparing the 2, 4-di-tert-butylphenol has the advantages of simple process, less side reaction, capability of realizing continuous production, weak corrosion to equipment and environment friendliness. The 2, 4-di-tert-butylphenol of the solid acid catalyst has high selectivity, good stability, convenient and flexible use and easy recycling; the preparation method has the advantages of cheap and easily obtained raw materials, simple preparation process, low cost and easy industrialized application.

Description

Method for producing 2, 4-di-tert-butylphenol
Technical Field
The application relates to a method for producing 2, 4-di-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 chemistry and chemical industry.
Background
2,4 di-tert-butylphenol is an important product and intermediate in fine chemical production, and is widely used for synthesizing antioxidants 168, P-EPQ, light stabilizers 120UV-327 and UV-320, ultraviolet absorbers, plasticizers and the like.
The traditional process for producing 2, 4-di-tert-butylphenol is mainly batch reaction, and the catalyst comprises liquid acid, clay and ion exchange resin. The sulfuric acid and phosphoric acid liquid acid catalysis process has the defects of more side reactions, difficult recycling of the catalyst, equipment corrosion, large wastewater amount and the like. The clay catalysis technology has the defect that a large amount of catalyst waste residues are difficult to treat in the production process. The ion exchange resin process has the defects of mild reaction condition, no corrosiveness, low reaction selectivity, easy deactivation of the catalyst, inconvenient continuous operation and the like. At present, most researches use modified ZSM-5, BETA, Y, MCM-41, SBA-15 and other molecular sieves as active components, however, the obtained catalyst has the defects of poor selectivity to tert-butylphenol and poor catalyst stability, and industrialization is difficult to realize.
Disclosure of Invention
According to one aspect of the application, a method for preparing 2, 4-di-tert-butylphenol is provided, phenol and tert-butyl alcohol or isobutene are used as raw materials, the selectivity of the 2, 4-di-tert-butylphenol can reach 95%, and the catalyst stability is good; and no equipment corrosion exists in the production process, so that the method is an environment-friendly process and has good industrial application prospect. A process for producing 2, 4-di-tert-butylphenol, comprising at least the steps of: passing a feedstock comprising phenol and t-butanol or isobutylene through a reactor comprising a bed of a solid acid catalyst to produce 2, 4-di-t-butylphenol;
the solid acid catalyst comprises a molecular sieve; the molecular sieve is an active component;
wherein the weight percentage of the molecular sieve in the solid acid catalyst is 30-80%.
A process for producing 2, 4-di-tert-butylphenol, comprising at least the steps of:
preheating phenol and tertiary butyl alcohol or isobutene, mixing the preheated phenol and tertiary butyl alcohol or isobutene with diluent gas, continuously passing through a solid acid catalyst bed layer, and reacting to generate 2, 4-di-tertiary butyl phenol;
the reaction conditions are as follows: the reaction pressure is 0.3-3.0 MPa, the reaction temperature is 180-350 ℃, and the feeding weight airspeed is 0.5-10 h -1 ；
The dilution gas is carbon dioxide or water vapor;
the mole ratio of the diluent gas to the phenol is 0.5-10:1;
the molar silicon-aluminum ratio of the molecular sieve is 20-200:1;
the molecular sieve is at least one selected from ZSM-5 molecular sieve, MCM-22 molecular sieve, and BETA molecular sieve;
the solid acid catalyst further comprises a binder;
the binder is at least one selected from silica sol, alumina and kaolin;
the preparation method of the solid acid catalyst at least comprises the following steps: shaping and roasting a mixture comprising a molecular sieve and a binder, and then performing at least one selected from the group consisting of oxide modification, steam treatment and acid treatment;
the oxide modification includes: immersing 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 modification includes a complex modification of one or more metal oxides and non-metal oxides;
the oxide is at least one of calcium oxide, strontium oxide and lanthanum oxide, and the weight percentage of the oxide in the alkylation catalyst is 0.1-10%; and at least one selected from phosphorus pentoxide and cerium oxide, wherein the weight percentage of the at least one selected from phosphorus pentoxide and cerium oxide in the solid acid catalyst is 0.1-5%.
The conditions of the water vapor treatment include: the method is carried out in 100% water vapor, the temperature is 300-800 ℃, the time is 0.5-10 hours, and the pressure is 1.0-3.0 MPa;
the acid treatment includes: the method is carried out by using 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, wherein the weight ratio of the to-be-treated substance to the aqueous solution is 1:5, the soaking time is 2-24 hours, and the soaking temperature is 20-80 ℃.
The preparation of the solid acid catalyst comprises the following steps:
(1) Molding a mixture containing a molecular sieve and a binder, drying, and roasting at 500-700 ℃ for 4-10 hours;
(2) Performing oxide modification on the mixture obtained in the step (1), drying, and roasting at 550-700 ℃ for 3-10 hours;
(3) Carrying out steam treatment on the mixture obtained in the step (2) for 0.5-10 hours at the temperature of 300-800 ℃;
(4) And (3) carrying out acid treatment on the mixture obtained in the step (3), drying and roasting at 550-800 ℃ for 2-10 hours. .
In the present application, the number of times of oxide modification, water vapor treatment, and acid treatment to be performed on the molded calcined product containing the mixture of the molecular sieve and the binder is not particularly limited. For example, in performing the oxide modification, the oxide modification may be performed two or more times.
Optionally, the forming means is selected from spray forming and extrusion forming. The correspondingly prepared catalyst can be used as a fluidized bed catalyst or a fixed bed catalyst according to different molding modes. The fluidized bed catalyst can be prepared through the preparation steps after spray molding, and the fixed bed catalyst can be prepared through the preparation steps after extrusion molding into a matrix.
For the purposes of this application, the term "oxide precursor" is understood in the context of this application to mean a substance which generates the corresponding oxide under the above-described oxide modification processes and conditions. 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.
According to a further aspect of the application, a preparation method of the alkylation catalyst is provided, and the method has the advantages of low-cost and easily-obtained raw materials, simple preparation process, low cost and easy industrial application.
The description of the alkylation catalyst and the method of preparing the same is as described above.
According to a further aspect of the present application there is provided the use of the alkylation catalyst for the alkylation of 2, 4-di-tert-butylphenol by synthesis of phenol and tert-butanol or isobutylene.
The beneficial effects that this application can produce include:
1) The method for producing 2, 4-di-tert-butylphenol has the advantages of simple production flow, less reaction byproducts and capability of obtaining 2, 4-di-tert-butylphenol products with purity more than 99 percent through simple distillation; the method can realize continuous production, can greatly reduce cost and improve efficiency, and has good economic benefit; and the corrosion to equipment is weak, and the pollution in the production process is small, so that the method is a novel environment-friendly process technology.
2) The solid acid catalyst provided by the application has excellent performance, high selectivity of 2, 4-di-tert-butylphenol and good stability; and the use is convenient and flexible, and the recycling is easy.
3) The preparation method of the solid acid catalyst provided by the application has the advantages of low-cost and easily-obtained raw materials, simple preparation process, low preparation cost and easiness in industrial application.
Description of the embodiments
As described above, in view of the disadvantages of the conventional 2, 4-di-t-butylphenol production technology, such as batch reaction and high labor intensity, the present application provides a method for producing 2, 4-di-t-butylphenol, which uses phenol and t-butanol or isobutylene as raw materials, produces p-t-butylphenol with high selectivity by means of a molecular sieve catalyst, and does not corrode equipment and produce a large amount of industrial wastewater during the production process, thus being an environmentally friendly green process.
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials and reagents in the examples of this application were purchased commercially, and were synthesized as described in patent US 4954325; ZSM-5 molecular sieve is manufactured by Nanka university catalyst plant under the trade name NKF-5; BETA molecular sieves are manufactured by Nanka university catalyst plant under the trade name NKF-6.
The analytical method in the examples of the present application is as follows:
chromatographic analysis was performed using a Tianmei GC 7900-type gas chromatograph. The chromatographic column is cyclodextrin column, 30 m ×0.25×0.25 μm. Chromatographic conditions: column temperature: the initial temperature is 150 ℃, the temperature stays for 15 minutes, the temperature rises to 180 ℃ at the heating rate of 10 ℃/minute, and the temperature is kept constant for 5.3 minutes; carrier gas: high purity nitrogen.
The conversion, selectivity in the examples of the present application were calculated as follows:
example 1
The preparation process of the solid acid catalyst comprises the following steps: 120 g of HZSM-5 molecular sieve with the mol silicon aluminum ratio of 30:1 is mixed with 60 g of alumina and 100 g of silica sol with the weight percentage of 20 percent, and a proper amount of 10 percent dilute nitric acid is added as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 500deg.C for 6 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix A0. 20 g of A0 is soaked in 10 weight percent calcium nitrate aqueous solution for 12 hours, dried at 120 ℃ and roasted at 600 ℃ 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 a 100% steam atmosphere for 10 hours at a temperature of 350℃and a pressure of 1.0 MPa to obtain A2. 20 g of A2 is soaked by adopting 0.5 mol/L citric acid aqueous solution at 80 ℃, the weight ratio of A2 to the solution is 1:5, the soaking time is 6 hours, and the roasting is carried out at 650 ℃ for 3 hours, so that the alkylation catalyst A is prepared, wherein the weight percentage of the molecular sieve is 60%.
Example 2
The preparation process of the solid acid catalyst comprises the following steps: 60 g of HZSM-5 molecular sieve with the molar silicon-aluminum ratio of 100:1 is mixed with 140 g of alumina, and a proper amount of 10% dilute nitric acid is added as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 700deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix B0. 20 g of B0 is soaked in 10 weight percent strontium nitrate aqueous solution for 10 hours, dried at 120 ℃ and roasted at 600 ℃ for 8 hours to obtain B1, wherein the weight percent of the strontium oxide is 5 percent. 20 g of B1 was subjected to steam treatment in a 100% steam atmosphere for 0.5 hours at 800℃under a pressure of 1.0 MPa to obtain B2. 20 g of B2 is immersed for 2 hours at 20 ℃ by using 0.5 mol/L nitric acid aqueous solution, the weight ratio of the B2 to the solution is 1:5, and the catalyst B is prepared by roasting for 3 hours at 700 ℃, wherein the weight percentage of the molecular sieve is 30%.
Example 3
The preparation process of the solid acid catalyst comprises the following steps: 200 g of HZSM-5 molecular sieve with the molar silicon-aluminum ratio of 50:1 is mixed with 200 g of kaolin, and a proper amount of 10% dilute nitric acid is added as an extrusion aid to be extruded into strips. Oven drying at 120deg.C, and calcining at 550deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix D0. 20 g of D0 is immersed in 0.15 weight percent aqueous solution of lanthanum nitrate for 24 hours, dried at 120 ℃ and roasted at 600 ℃ for 3 hours to obtain D1, wherein the weight percent of lanthanum oxide is 0.1 percent. D2 was prepared by subjecting 20 g of D1 to steam treatment in a 100% steam atmosphere for 10 hours at a temperature of 300 ℃ and a pressure of 3.0 MPa. 20 g of D2 is immersed for 10 hours at 40 ℃ by using 0.5 mol/L sulfuric acid aqueous solution, the weight ratio of the D2 to the solution is 1:5, and the catalyst D is prepared by roasting for 10 hours at 550 ℃, wherein the weight percentage of the molecular sieve is 50%.
Example 4
The preparation process of the solid acid catalyst comprises the following steps: 160 g of HZSM-5 molecular sieve with the mol silicon aluminum ratio of 30:1 is mixed with 100 g of silica sol with the weight percentage of 40 percent of silicon dioxide, and a proper amount of 10 percent of dilute nitric acid is added as extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 550deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix F0. 20 g of F0 is immersed in 10 weight percent of calcium nitrate aqueous 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 5 percent. 20 g of F1 was subjected to steam treatment in a 100% steam atmosphere for 6 hours at a temperature of 450℃and a pressure of 3.0MPa to obtain F2. 20 g of F2 is immersed for 6 hours at 30 ℃ by using 0.5 mol/L nitric acid aqueous solution, the weight ratio of F2 to the solution is 1:5, and the catalyst F is prepared by roasting for 3 hours at 600 ℃, wherein the weight percentage of the molecular sieve is 80%.
Example 5
The preparation process of the solid acid catalyst comprises the following steps: 160 g of HMCM-22 molecular sieve with the mol silicon aluminum ratio of 30:1 is mixed with 40 g of kaolin, and a proper amount of 10% dilute nitric acid is added as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 650deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix G0. 20G of G0 is immersed in 20% calcium acetate aqueous solution for 36 hours, dried at 120 ℃ and roasted at 600 ℃ for 10 hours to obtain G1, wherein the weight percentage of calcium oxide is 10%. 20G of G1 was subjected to steam treatment in a 100% steam atmosphere for 10 hours at a temperature of 350℃and a pressure of 2.0 MPa to obtain G2. 20G of G2 is immersed for 24 hours at 30 ℃ by using 0.2 mol/L sulfuric acid aqueous solution, the weight ratio of the G2 to the solution is 1:5, and the catalyst G is prepared by roasting for 2 hours at 800 ℃, wherein the weight percentage of the molecular sieve is 80%.
Example 6
The preparation process of the solid acid catalyst comprises the following steps: 140 g of HZSM-5 molecular sieve with the molar silicon aluminum ratio of 200:1 is mixed with 20 g of silicon oxide and 40 g of aluminum oxide, and a proper amount of 10% dilute nitric acid is added as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 550deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix H0. 20 g of H0 is immersed in 8 weight percent aqueous solution of cerium nitrate for 12 hours, dried at 120 ℃ and roasted at 700 ℃ for 5 hours to prepare H1, wherein the weight percent of cerium oxide is 3 percent. 20 g of H1 was subjected to steam treatment in a 100% steam atmosphere for 4 hours at a temperature of 500℃and a pressure of 1.0 MPa to obtain H2. 20 g of H2 is immersed for 12 hours at 80 ℃ by using 0.5 mol/L citric acid aqueous solution, the weight ratio of H2 to the solution is 1:5, and the catalyst H is prepared by roasting for 3 hours at 600 ℃, wherein the weight percentage of the molecular sieve is 70%.
Example 7
The preparation process of the solid acid catalyst comprises the following steps: 160 g of HZSM-5 molecular sieve with the mol silicon aluminum ratio of 50:1 is mixed with 100 g of silica sol with the weight percentage of 40 percent of silicon dioxide, and a proper amount of 10 percent of dilute nitric acid is added as extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 550deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix I0. 20 g of I0 is immersed in a cerium nitrate aqueous solution with the weight percentage of 13% for 24 hours, dried at 120 ℃ and roasted at 650 ℃ for 3 hours to obtain I1, wherein the weight percentage of cerium oxide is 5%. 20 g of I1 was subjected to steam treatment in a 100% steam atmosphere for 10 hours at 380℃under a pressure of 1.0 MPa to obtain I2. 20 g of I2 is immersed for 10 hours at 20 ℃ by using 0.5 mol/L nitric acid aqueous solution, the weight ratio of the I2 to the solution is 1:5, and the catalyst I is prepared by roasting for 3 hours at 600 ℃, wherein the weight percentage of the molecular sieve is 80%.
Example 8
The preparation process of the solid acid catalyst comprises the following steps: 160 g of HZSM-5 molecular sieve with the molar silicon-aluminum ratio of 100:1 is mixed with 100 g of silica sol with the weight percentage of 40 percent of silicon dioxide, and a proper amount of 10 percent of dilute nitric acid is added as extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 550deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix J0. 20 g of J0 is immersed in 8 weight percent of ammonium dihydrogen phosphate aqueous solution for 24 hours, dried at 120 ℃ and roasted at 650 ℃ for 5 hours to prepare 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 for 4 hours at a temperature of 450℃and a pressure of 2.0 MPa to obtain J2. 20 g of J2 is immersed for 12 hours at 60 ℃ by using 0.5 mol/L citric acid aqueous solution, the weight ratio of J2 to the solution is 1:5, and the catalyst J is prepared by roasting for 5 hours at 650 ℃, wherein the weight percentage of the molecular sieve is 80%.
Example 9
The preparation process of the solid acid catalyst comprises the following steps: 140 g of HZSM-5 molecular sieve with the mol silicon aluminum ratio of 30:1 is mixed with 150 g of silica sol with the weight percentage of 40 percent of silicon dioxide, and a proper amount of 10 percent of dilute nitric acid is added as extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 550deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix K0. 20 g of K0 is immersed in 0.26 percent cerium nitrate aqueous 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 a 100% steam atmosphere for 8 hours at a temperature of 350℃and a pressure of 1.0 MPa to obtain K2. 20 g of K2 is immersed for 8 hours at 30 ℃ by using 0.2 mol/L nitric acid aqueous solution, the weight ratio of the K2 to the solution is 1:5, and the catalyst K is prepared by roasting for 8 hours at 550 ℃, wherein the weight percentage of the molecular sieve is 70%.
Example 10
The preparation process of the solid acid catalyst comprises the following steps: 100 g of HZSM-5 molecular sieve with the mol silicon aluminum ratio of 30:1 is mixed with 100 g of alumina, and a proper amount of 10% dilute nitric acid is added as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 600deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix L0. 20 g of L0 is immersed in 29 percent calcium nitrate aqueous solution for 24 hours, dried at 120 ℃ and roasted at 650 ℃ for 3 hours to obtain L1, wherein the weight percent of calcium oxide is 10 percent. 20 g of L1 was subjected to steam treatment in a 100% steam atmosphere for 8 hours at 400℃under a pressure of 1.0 MPa to obtain L2. 20 g of L2 is immersed for 10 hours at 20 ℃ by using 0.1 mol/L sulfuric acid aqueous solution, the weight ratio of the L2 to the solution is 1:5, and the alkylation catalyst L is prepared by roasting for 10 hours at 550 ℃, wherein the weight percentage of the molecular sieve is 50%.
Example 11
The preparation process of the solid acid catalyst comprises the following steps: 90 g of HMCM-22 molecular sieve with the molar silicon-aluminum ratio of 20:1, 70 g of HZSM-5 molecular sieve with the molar silicon-aluminum ratio of 30:1 and 40 g of kaolin are mixed, and a proper amount of 10% dilute nitric acid is added as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 550deg.C for 10 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix M0. 20 g of M0 is immersed in 29% calcium nitrate aqueous solution for 24 hours, dried at 120 ℃ and roasted at 650 ℃ for 3 hours to obtain M1, wherein the weight percentage of calcium oxide is 10%. 20 g of M1 is immersed in 8 weight percent phosphoric acid aqueous solution for 24 hours, dried at 120 ℃ and roasted at 600 ℃ for 10 hours to prepare M2, wherein the weight percent of phosphorus pentoxide is 5 percent. 20 g of M2 was immersed in a 0.1 mol/L aqueous sulfuric acid solution at 30℃for 24 hours, the weight ratio of M2 to the solution was 1:5, and calcined at 650℃for 5 hours to obtain an alkylation catalyst M, wherein the weight percentage of molecular sieve was 80%.
Example 12
The preparation process of the solid acid catalyst comprises the following steps: 160 g of HMCM-22 molecular sieve with the molar silicon-aluminum ratio of 60:1 is mixed with 100 g of silica sol with the weight percentage of 40 percent of silicon dioxide, and a proper amount of 10 percent of dilute nitric acid is added as extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 550deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix N0. 20 g of N0 is immersed in 8 weight percent calcium acetate aqueous solution for 10 hours, dried at 120 ℃ and roasted at 550 ℃ 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 a 100% steam atmosphere for 8 hours at 400℃under a pressure of 2.0 MPa to obtain N2. 20 g of N2 is immersed for 12 hours at 20 ℃ by using 0.5 mol/L sulfuric acid aqueous solution, the weight ratio of the N2 to the solution is 1:5, and the catalyst N is prepared by roasting for 6 hours at 550 ℃, wherein the weight percentage of the molecular sieve is 80%.
Example 13
The preparation process of the solid acid catalyst comprises the following steps: 120 g of HMCM-22 molecular sieve with the molar ratio of silicon to aluminum of 50:1 is mixed with 50 g of alumina and 100 g 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 as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 600deg.C for 8 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix P0. 20 g of P0 is immersed in 5 weight percent aqueous solution of lanthanum nitrate for 36 hours, dried at 120 ℃ and roasted at 700 ℃ for 3 hours to obtain P1, wherein the weight percent of lanthanum oxide is 3 percent. 20 g of P1 was subjected to steam treatment in a 100% steam atmosphere for 6 hours at a temperature of 450℃and a pressure of 1.0 MPa to obtain P2. 20 g of P2 is immersed for 6 hours at 30 ℃ by using 0.2 mol/L nitric acid aqueous solution, the weight ratio of P2 to the solution is 1:5, and the alkylation catalyst P is prepared by roasting for 3 hours at 550 ℃, wherein the weight percentage of the molecular sieve is 60%.
Example 14
The preparation process of the solid acid catalyst comprises the following steps: 50 g of HMCM-22 molecular sieve with the molar silicon-aluminum ratio of 40:1, 50 g of hydrogen-type ZSM-5 molecular sieve with the molar silicon-aluminum ratio of 100:1, 80 g of kaolin and 100 g of silica sol with the weight percentage of 20% of silica are mixed, and a proper amount of 10% dilute nitric acid is added as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 550deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix R0. 20 g of R0 is immersed in 5 weight percent phosphoric acid aqueous solution for 20 hours, dried at 120 ℃ and roasted at 650 ℃ for 5 hours to prepare R1, wherein the weight percent of phosphorus pentoxide is 3 percent. 20 g of R1 was subjected to steam treatment in a 100% steam atmosphere at 360℃under 2.0 MPa for 8 hours, and then calcined at 550℃for 3 hours to obtain catalyst R, wherein the weight percentage of the molecular sieve was 50%.
Example 15
The preparation process of the solid acid catalyst comprises the following steps: 140 g of hydrogen type beta molecular sieve with the molar silicon-aluminum ratio of 20:1, 30 g of alumina and 30% of silica sol with the weight percentage of 100 g silica are mixed, and a proper amount of 10% dilute nitric acid is added as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 650deg.C for 5 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix S0. 20 g of S0 is immersed in 10 weight percent aqueous solution of ammonium cerium nitrate for 20 hours, dried at 120 ℃ and roasted at 600 ℃ for 5 hours to prepare S1, wherein the weight percent of cerium oxide is 3 percent. S2 was prepared by subjecting 20 g of S1 to steam treatment in a 100% steam atmosphere at 500℃under a pressure of 2.0 MPa for 8 hours. 20 g of S2 is immersed for 8 hours at 30 ℃ by using 0.2 mol/L nitric acid aqueous solution, the weight ratio of S2 to the solution is 1:5, and the alkylation catalyst S is prepared by roasting for 3 hours at 550 ℃, wherein the weight percentage of the molecular sieve is 70%.
Example 16
The preparation process of the solid acid catalyst comprises the following steps: 60 g of HZSM-5 molecular sieve with the molar ratio of silicon to aluminum of 200:1 is mixed with 100 g of silica sol with the weight percentage of 40 percent of silicon dioxide and 100 g of alumina, and a proper amount of 10 percent of dilute nitric acid is added as an extrusion aid for extrusion molding. Oven drying at 120deg.C, and calcining at 550deg.C for 4 hr. Cutting the obtained product into 1-3 mm to obtain a columnar catalyst matrix T0. 20 g of T0 is immersed in 2.6 weight percent diammonium hydrogen phosphate aqueous solution for 20 hours, dried at 120 ℃ and roasted at 700 ℃ for 3 hours to obtain T1, wherein the weight percent of phosphorus pentoxide is 1.5 percent. T2 was prepared by subjecting 20 g of T1 to steam treatment in a 100% steam atmosphere at 650℃under a pressure of 1.0 MPa for 4 hours. 20 g of T2 is immersed for 6 hours at 60 ℃ by using 0.5 mol/L citric acid aqueous solution, the weight ratio of the T2 to the solution is 1:5, and the catalyst T is prepared by roasting for 3 hours at 650 ℃, wherein the weight percentage of the molecular sieve is 30%.
Example 17
The catalysts prepared in examples 1 to 16 were subjected to the reaction of phenol with tert-butanol or isobutene in a fixed-bed reactor. The raw material phenol and tertiary butyl alcohol or isobutene or diluent gas are preheated and enter a reactor for reaction, and the reaction product is subjected to online colorAnd (5) spectrum analysis. The loading of the reaction catalyst is 20.0 g, and the weight space velocity is 0.5-10 h -1 The reaction temperature is 180-350 ℃, the diluent gas is water vapor, and the molar ratio of the diluent gas to the phenol is 0.5-10:1. The molar ratio of the raw material tert-butanol or isobutene to phenol is 2:1. Wherein the reaction raw materials of the catalyst prepared in the examples 1-8 are tertiary butanol and phenol, and the diluent gas is water vapor; examples 9-16 the catalyst was prepared from isobutylene and phenol as the reaction feed and carbon dioxide as the diluent gas. The reaction results of the solid acid catalyst in each example after 72 hours of reaction are shown in Table 1.
TABLE 1 catalytic reaction conditions and catalytic Properties of solid acid catalysts
Catalyst Reaction temperature (. Degree. C.) Reaction pressure (MPa) Weight space velocity (h) -1 ） Feed dilution gas/phenol (molar ratio) Phenol conversion (%) 2,4 Di-tert-butylphenol Selectivity (%)
A 200 1.0 1 3 80 95
B 350 0.3 10 5 30 90
D 180 1.5 0.5 2 70 96
F 220 2.0 3 5 75 95
G 250 1.0 5 5 70 96
H 300 0.3 10 10 50 95
I 180 3.0 1 3 55 97
J 270 0.5 2 10 75 93
K 240 1.0 3 5 50 95
L 280 0.3 5 10 35 94
M 250 2.0 3 5 55 95
N 350 0.3 10 0.5 60 90
P 220 1.0 2 5 50 95
R 260 0.5 1 10 60 95
S 230 1.0 2 2 75 95
T 350 0.3 1 10 40 93
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.

Claims (8)

1. A process for producing 2, 4-di-tert-butylphenol, comprising at least the steps of: passing a feedstock comprising phenol and t-butanol or isobutylene through a reactor comprising a bed of a solid acid catalyst to produce 2, 4-di-t-butylphenol;
the solid acid catalyst comprises a molecular sieve; the molecular sieve is an active component;
wherein the weight percentage of the molecular sieve in the solid acid catalyst is 30-80%.
2. Method according to claim 1, characterized in that it comprises at least the following steps:
preheating phenol and tertiary butyl alcohol or isobutene, mixing the preheated phenol and tertiary butyl alcohol or isobutene with diluent gas, continuously passing through a solid acid catalyst bed layer, and reacting to generate 2, 4-di-tertiary butyl phenol;
the reaction conditions are as follows: the reaction pressure is 0.3-3.0 MPa, the reaction temperature is 180-350 ℃, and the feeding weight airspeed is 0.5-10 h -1 ；
The dilution gas is carbon dioxide or water vapor;
the mole ratio of the diluent gas to the phenol is 0.5-10:1.
3. The method according to claim 1, wherein the molar ratio of silicon to aluminum of the molecular sieve is 20-200:1;
the molecular sieve is at least one selected from ZSM-5 molecular sieve, MCM-22 molecular sieve, and BETA molecular sieve.
4. The method of claim 1, wherein the solid acid catalyst further comprises a binder;
the binder is at least one selected from silica sol, alumina and kaolin.
5. The method according to claim 4, wherein the preparation method of the solid acid catalyst comprises at least the following steps: the mixture containing the molecular sieve and the binder is molded, calcined, and then subjected to at least one selected from the group consisting of oxide modification, water vapor treatment, and acid treatment.
6. The method of claim 5, wherein the oxide modification comprises: immersing 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 modification includes a complex modification of one or more metal oxides and non-metal oxides;
the oxide is at least one of calcium oxide, strontium oxide and lanthanum oxide, and the weight percentage of the oxide in the alkylation catalyst is 0.1-10%; and at least one selected from phosphorus pentoxide and cerium oxide, wherein the weight percentage of the at least one selected from phosphorus pentoxide and cerium oxide in the solid acid catalyst is 0.1-5%.
7. The method of claim 5, wherein the conditions of the steam treatment comprise: the method is carried out in 100% water vapor, the temperature is 300-800 ℃, the time is 0.5-10 hours, and the pressure is 1.0-3.0 MPa;
the acid treatment includes: the method is carried out by using 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, wherein the weight ratio of the to-be-treated substance to the aqueous solution is 1:5, the soaking time is 2-24 hours, and the soaking temperature is 20-80 ℃.
8. The method according to any one of claims 1 to 8, wherein the preparation of the solid acid catalyst comprises the steps of:
(1) Molding a mixture containing a molecular sieve and a binder, drying, and roasting at 500-700 ℃ for 4-10 hours;
(2) Performing oxide modification on the mixture obtained in the step (1), drying, and roasting at 550-700 ℃ for 3-10 hours;
(3) Carrying out steam treatment on the mixture obtained in the step (2) for 0.5-10 hours at the temperature of 300-800 ℃;
(4) And (3) carrying out acid treatment on the mixture obtained in the step (3), drying and roasting at 550-800 ℃ for 2-10 hours.
CN202310519872.8A 2023-05-10 2023-05-10 Method for producing 2, 4-di-tert-butylphenol Pending CN116496145A (en)

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