阅读说明：本技术 一种生产对叔丁基苯酚的方法 (Method for producing p-tert-butylphenol ) 是由 王坤院 黄为 陈兆安 刘中民 于 2018-07-16 设计创作，主要内容包括：本申请公开了一种生产对叔丁基苯酚的方法,属于化学化工领域。所述生产对叔丁基苯酚的方法至少包括以下步骤：将含有苯酚和叔丁醇或异丁烯的原料通过含有烷基化催化剂的反应器,反应生成对叔丁基苯酚；所述烷基化催化剂包含分子筛；所述分子筛为活性组分；其中,所述烷基化催化剂中分子筛的重量百分比为30～85％。所述生产对叔丁基苯酚的方法过程简单,副反应少,可实现连续生产,且对设备腐蚀性弱,绿色环保。所述烷基化催化剂的对叔丁基苯酚选择性高,稳定性好,且使用方便灵活,易于回收再利用；其制备方法的原料廉价易得,制备过程简单,成本低,易于工业化应用。(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.)

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%.

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 the diluent gas, continuously passing through an alkylation catalyst bed layer, and carrying out alkylation reaction to generate p-tert-butyl phenol;

preferably, the reaction conditions are: normal pressure, reaction temperature of 180-400 ℃, and feeding weight airspeed of 0.5-20 h^-1；

More preferably, the reaction temperature is 200-300 ℃, and the feeding weight space velocity is 1-10 h^-1；

Preferably, the diluent gas is nitrogen or water vapor;

preferably, the mol ratio of the dilution gas to the phenol is 0.5-20: 1;

preferably, the molar ratio of the tert-butyl alcohol or the isobutene to the phenol is 4: 1-1: 4.

3. The method according to claim 1, wherein the molar silica-alumina ratio of the molecular sieve is 20-200: 1;

preferably, the molecular sieve is at least one selected from ZSM-5 molecular sieve, MCM-22 molecular sieve and BETA molecular sieve;

preferably, the molecular sieve is a hydrogen type molecular sieve or an ammonium type molecular sieve.

4. The process of claim 1, wherein the alkylation catalyst further comprises a binder;

preferably, the binder is selected from at least one of silica sol, diatomaceous earth, silica, boehmite, alumina sol, alumina, kaolin;

preferably, the weight ratio of the molecular sieve to the binder is 180: 20-60: 140.

5. The process according to claim 4, characterized in that the preparation process of the alkylation catalyst comprises at least the following steps: forming and roasting a mixture containing the molecular sieve and a binder, and then carrying out at least one selected from oxide modification, water vapor treatment and acid treatment;

preferably, the product obtained by roasting is subjected to oxide modification and water vapor treatment;

preferably, the product obtained by roasting is subjected to oxide modification and acid treatment;

preferably, the product obtained by roasting is subjected to steam treatment and acid treatment;

preferably, the product obtained by calcination is subjected to oxide modification, steam treatment and acid treatment.

6. The method according to claim 5, wherein the roasting is performed at 500 to 700 ℃ for 4 to 10 hours.

7. The method of claim 5, wherein 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;

preferably, the oxide modification comprises a composite modification of one or more metal oxides and non-metal oxides;

preferably, 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%.

8. The method of claim 5, wherein the conditions of the water vapor treatment comprise: 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 ℃.

9. The method of claim 8, wherein the acid treatment further comprises: drying and roasting the product obtained by impregnation;

preferably, the roasting condition is roasting at 500-800 ℃ for 2-10 hours.

10. Method according to any one of claims 1 to 9, 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.

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 400 ℃, 380 ℃, 350 ℃, 330 ℃, 300 ℃, 280 ℃, 270 ℃, 260 ℃, 250 ℃, 220 ℃, 200 ℃, and the lower limit is selected from 180 ℃, 200 ℃, 220 ℃, 250 ℃, 260 ℃, 270 ℃, 280 ℃, 300 ℃, 330 ℃, 350 ℃, 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: