CN111099971B - Method for preparing p-tert-butylphenol by using MTBE as raw material - Google Patents

Method for preparing p-tert-butylphenol by using MTBE as raw material Download PDF

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CN111099971B
CN111099971B CN201811262148.7A CN201811262148A CN111099971B CN 111099971 B CN111099971 B CN 111099971B CN 201811262148 A CN201811262148 A CN 201811262148A CN 111099971 B CN111099971 B CN 111099971B
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catalyst
mtbe
reactor
sulfuric acid
feeding
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CN111099971A (en
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刘野
赵亮
王岩
于庆志
党雷
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Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
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    • 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
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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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053—Sulfates
    • B01J27/055—Sulfates with alkali metals, copper, gold or silver
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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Abstract

A method for preparing p-tert-butylphenol by taking MTBE as a raw material adopts a fixed bed tubular reactor, the middle part of the reactor is a catalyst bed layer, the upper part of the reactor is provided with a clapboard along the axial direction, the lower end of the clapboard extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts, the two sides of the clapboard are an upper feeding section and a discharging section, and a lower feeding section is arranged below a catalyst filling layer; MTBE and phenol enter from the raw material inlet of the upper feeding section as feeding I, MTBE and nitrogen enter from the raw material inlet of the lower feeding section as feeding II, the feeding I reacts on the catalyst bed layer, the reacted material is mixed with the feeding II from bottom to top for further reaction, and the product is discharged from the discharge hole of the discharging section. The reaction mode of the method enables the materials to react more fully, improves the reaction conversion rate, enables the feeding at the upper end to pass through the catalyst bed layer repeatedly, reacts more fully, and improves the MTBE conversion rate.

Description

Method for preparing p-tert-butylphenol by using MTBE as raw material
Technical Field
The invention relates to a method for preparing p-tert-butylphenol, in particular to a method for preparing p-tert-butylphenol by using MTBE (methyl tert-butyl ether) and phenol as raw materials.
Background
The p-tert-butylphenol is also known as 4-tert-butylphenol and is abbreviated as PTBP. P-tert-butylphenol is a white or essentially white flaky solid at room temperature and has a specific alkylphenol odor. Is easily soluble in organic solvents such as alcohols, esters, alkanes, aromatic hydrocarbons, etc., such as ethanol, acetone, butyl acetate, gasoline, toluene, etc. Slightly soluble in water and soluble in strong alkaline solution. P-tert-butylphenol has antioxidant properties and can be used as a stabilizer for rubber, soap, chlorinated hydrocarbons and digestive fibers. Ultraviolet absorbent, and cracking-preventing agent such as pesticide, rubber, and paint. The stabilizer is used for polycarbonate resin, tert-butyl phenolic resin, epoxy resin, polyvinyl chloride and styrene. In addition, the raw materials for preparing the medical insect repellent, the pesticide acaricide propargite, the perfume and the plant protective agent are also used. It can also be used as the additive of softening agent, solvent, dye and paint, the antioxidant of lubricating oil, the additive of oil field demulsifier and vehicle fuel.
The preparation method of the p-tert-butylphenol mainly comprises the following steps:
phenol isobutylene method: taking phenol and isobutene as raw materials, taking cation exchange resin as a catalyst, carrying out alkylation reaction at normal pressure and 110 ℃, and carrying out reduced pressure distillation on the product to obtain a product;
phenol diisobutylene process: adopting a silicon-aluminum catalyst, carrying out the reaction under a liquid phase condition to obtain p-octyl phenol and o-tert-butyl phenol besides the p-tert-butyl phenol, and separating the reaction product to obtain the p-tert-butyl phenol;
carbon four-cut process: the cracking carbon four fraction and phenol are taken as raw materials, titanium-molybdenum oxide is taken as a catalyst, a mixture of phenol alkylation reaction mainly comprising p-tert-butylphenol is obtained through reaction, and a product is obtained through separation;
phenol tert-butanol method: phenol and tert-butyl alcohol are used as raw materials, and the product can be prepared by washing, crystallizing and separating.
In recent years, MTBE has been favored by regulators as a high octane additive and antiknock agent for gasoline. However, with the development of substitutes such as alkylate and ethanol gasoline, the market demand of MTBE is greatly influenced. In addition, there are studies that indicate that MTBE has potential threats to the environment and human health. After the environmental protection agency of the united states lists MTBE as a carcinogen, several countries in north america and europe have developed a series of policies that prohibit or limit the use of MTBE in gasoline. China will gradually limit the application of MTBE in gasoline, so that the MTBE capacity is excessive, and the development and utilization of the downstream technology of MTBE products will become a future development trend. The synthesis of p-tert-butylphenol by using MTBE as an alkylating agent and phenol can be used as one of the approaches for downward development and utilization of MTBE.
According to the reports of the literature, sulfuric acid or phosphoric acid is mostly used as a catalyst in the production process of the p-tert-butylphenol, and the problems of serious corrosion of equipment, environmental pollution, difficult separation and recovery of products and the like exist. Domestic documents report that HY molecular sieve and temperature-resistant resin are used as catalysts, MTBE is used as an alkylating agent to synthesize p-tert-butylphenol, but the reaction temperature is high, and the conversion rate and the product selectivity of phenol are low.
Disclosure of Invention
Aiming at the problems of strong catalyst corrosivity, environmental pollution, harsh reaction conditions and low MTBE conversion rate in the method for preparing p-tert-butylphenol by using MTBE and phenol as raw materials in the prior art, the invention provides the method for preparing the p-tert-butylphenol. The method takes MTBE and phenol as raw materials, a fixed bed tubular reactor with a partition plate in the middle is adopted as the reactor, the reaction is carried out under the action of a solid super acidic catalyst, and the feeding mode adopts a mode of feeding materials simultaneously from top to bottom. The method can effectively improve the conversion rate of MTBE, and has the advantages of simple process, high efficiency, no pollution, mild conditions, stable catalyst activity and long-period operation.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a method for preparing p-tert-butylphenol by taking MTBE as a raw material adopts a fixed bed tubular reactor, wherein a catalyst bed layer is arranged in the middle of the fixed bed tubular reactor, a partition plate is arranged on the upper part of the fixed bed tubular reactor along the axial direction, the lower end of the partition plate extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts by the partition plate and the catalyst bed layer, an upper feeding section and a discharging section are arranged above two sides of the partition plate, and a lower feeding section is arranged below the catalyst bed layer; MTBE and phenol enter the reactor as feed I from the raw material inlet of the upper feeding section, MTBE and nitrogen enter the reactor as feed II from the raw material inlet of the lower feeding section, the feed I reacts on the catalyst bed layer in the middle of the reactor, the reacted material is mixed with the feed II from bottom to top for further reaction, and the reaction product is discharged from the discharge hole of the discharging section.
In the method, the length of the partition plate is 1/2-2/3 of the length of the reactor, and the top of the partition plate and two side edges of the partition plate are hermetically connected with the wall of the reactor.
In the method, the molar ratio of MTBE to phenol in the feed I is 1: 1-5: 1, preferably 3: 1-4: 1, the total liquid hourly space velocity is 1-4 h -1 Preferably 2 to 3 hours -1 。
In the method, the liquid hourly space velocity of MTBE in the feed II on the catalyst is 1-2 h -1 Preferably 1 to 1.5 hours -1 The molar ratio of nitrogen to phenol is 100-200: 1.
in the process of the present invention, the total liquid hourly space velocity of feed I is greater than the total liquid hourly space velocity of feed II.
According to the method, quartz sand is filled at two ends of a reactor, and a mixture of the catalyst and the quartz sand is filled in a catalyst bed section, wherein the granularity range of the quartz sand is 1.5-2.0 mm, and the catalyst accounts for 60-70 v% of the total filling amount.
In the method of the invention, the reaction conditions are as follows: the reaction temperature is 80-120 ℃, and preferably 90-110 ℃; the reaction pressure is 2-5 MPa, preferably 3-4 MPa.
In the method of the invention, temperature-resistant resin and a modified molecular sieve are generally used as catalysts.
In the method of the present invention, the solid super acidic catalyst is most preferably used, and the preparation method of the solid super acidic catalyst comprises the following steps:
(1) ZrOCl 2 Dissolving in ethanol to obtain ZrOCl 2 Titrating with ammonia water until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, molding, drying, and roasting to obtain white solid particles;
(2) and (2) respectively soaking the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, a nickel nitrate sulfuric acid solution and a palladium nitrate sulfuric acid solution, drying and roasting after each step of soaking, and finally obtaining the metal-doped solid super acidic catalyst.
In the preparation method of the catalyst, the ZrOCl in the step (1) 2 The mass concentration of the ethanol solution is 30-50%.
The drying temperature in the step (1) is 70-90 ℃, the drying time is 4-6 hours, the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
The white solid particles obtained in the step (1) are cylindrical particles with the particle size of 1.0-1.5 mm.
The preparation process of the nitrate sulfuric acid solution in the step (2) is as follows: dissolving nitrate in dilute sulfuric acid to obtain a nitrate sulfuric acid solution; wherein the concentration of the dilute sulfuric acid is 0.3-0.6 mol/L, the concentration of the silver nitrate sulfuric acid solution is 2-4 mol/L, the concentration of the nickel nitrate sulfuric acid solution is 5-10 mol/L, and the concentration of the palladium nitrate sulfuric acid solution is 0.1-0.3 mol/L.
As a further preferable mode, the impregnation in the step (2) is performed by a spray impregnation method using a gas-liquid mixture of the impregnation liquid and nitrogen.
As a more specific embodiment, the impregnation process in step (2) is: a. filling the white particles obtained in the step (1) into a fine steel wire mesh bag, wherein the thickness of the steel wire mesh bag is 1-5 mm, preferably 2-3 mm, and flatly paving the steel wire mesh bag in an ultrasonic vibrator; b. under the condition that the ultrasonic vibration frequency is 50-60 kHz, spraying solid particles on a gas-liquid mixture of a silver nitrate sulfuric acid solution and nitrogen through an atomizing nozzle, wherein the spraying distance is 0-2 cm, preferably 0.5-1 cm, the spraying pressure is 0.02-0.2 MPa, preferably 0.05-0.1 MPa, and the spraying time is 1-4 hours, preferably 2-3 hours; c. then drying and roasting to obtain particles I; d. b, repeating the operation process of the step b by using a sulfuric acid solution of nickel nitrate, and then drying and roasting to obtain particles II; e. and (c) repeating the operation process of the step (b) by using a sulfuric acid solution of palladium nitrate, and drying and roasting to obtain the metal-doped solid super acidic catalyst.
The drying conditions in the step (2) are as follows: the drying temperature is 80-100 ℃, and the drying time is 6-8 hours; the roasting conditions are as follows: the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours.
Compared with the prior art, the invention has the following advantages:
(1) the reaction is carried out on a fixed bed continuous reactor with a partition plate, the materials are fed in an upper and lower simultaneous feeding mode, the reaction materials fed in the upper mode enter the reactor and pass through a catalyst bed layer under a certain airspeed condition, part of reactants firstly react to a certain degree and move downwards, the reaction materials fed in the lower mode enter the reactor under a certain airspeed condition, are mixed with the materials moving downwards, pass through the catalyst bed layer and move upwards, the reaction is further carried out after the materials are mixed, and the reaction conversion rate is improved.
(2) The upper feeding and the lower feeding have an airspeed difference (the upper feeding airspeed is greater than the lower feeding airspeed), so that the feeding at the upper end of the reactor passes through the catalyst bed layer in a reciprocating manner, the reaction is more sufficient, and the conversion rate of the MTBE is improved.
(3) The catalyst filling section is filled by mixing with quartz sand, the lower feeding is the mixed feeding of phenol and nitrogen, and the catalyst is continuously boiled in a gap formed by the quartz sand under the driving action of the nitrogen with certain air flow and air speed, so that the contact probability and mass transfer efficiency of reaction materials and the active center of the catalyst are increased, and the reaction efficiency and the conversion rate are improved.
(4) The axial partition plate is added in the reactor, so that the moving path of the feeding material at the inlet I is limited, the process that the feeding material at the inlet I is partially reacted firstly and then is further reacted with the feeding material at the inlet II is realized, the reaction is more sufficient, and the conversion rate of MTBE is higher.
(5) In the preparation process of the solid super acidic catalyst, a method of respectively dipping different metal solutions in a certain sequence is adopted, nitrogen and dipping solution are sprayed to treat the catalyst, SO that tiny impurities in pore channels of the catalyst are blown out, and SO is generated 4 2- The coordination with the metal ions on the surface of the oxide is rapid and uniform, so that the catalyst has stronger acidity. Ag + Is pre-doped to ZrO 2 The crystal grains tend to exist in a monoclinic type (M), and the monoclinic type (M) is a relatively stable crystal phase structure, so that the catalyst has higher activity and better stability.
Drawings
FIG. 1 is a schematic diagram of the process for preparing p-tert-butylphenol according to the invention.
Wherein: 1-an upper feeding section; 2-a lower feeding section; 3-discharging section; 4-a separator; 5-catalyst bed layer.
Detailed Description
The preparation process of the solid super acidic catalyst of the present invention is specifically described as follows: firstly, 50-100 g ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with the mass concentration of 30-50% 2 And (2) titrating the ethanol solution with 20-25% ammonia water until no white precipitate exists, washing the solution with deionized water for several times, wherein the washing time is 5-10 minutes each time, the washing temperature is 40-50 ℃, washing the solution until no chloride ion exists, drying the solution in a vacuum drying oven for 4-6 hours at the temperature of 80-90 ℃, extruding the solution into strips, and roasting the strips for 8 hours at the temperature of 500 ℃ to obtain white solid particles for later use. Secondly, filling the obtained white solid particles into a steel wire mesh bag, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the thickness of the steel wire mesh bag is 2mm, spraying a silver nitrate sulfuric acid solution and nitrogen gas with a certain concentration by using an atomizing nozzle under the ultrasonic vibration condition, wherein the spraying distance is 1-2 cm, the spraying pressure is 0.05-0.1 MPa, the spraying time is 1-2 h, drying and roasting are carried out to obtain particles I, the drying temperature is 80-100 ℃, and the drying time is 6-8 h; the roasting temperature is 450-550 ℃, and the roasting time is 4-6 hours. . Thirdly, repeating the operation process of the second step by using a sulfuric acid solution of nickel nitrate, and then drying and roasting to obtain particles II; e. and (4) repeating the operation process of the second step by using a sulfuric acid solution of palladium nitrate, and drying and roasting to obtain the metal-doped solid super acidic catalyst.
The following examples are provided to illustrate specific embodiments of the present invention. In the following examples and comparative examples,% represents mass unless otherwise specified. The ultrasonic vibrator used in the preparation of the supported heteropolyacid catalyst is KQ-550B, and the atomizing nozzle is JLN-G type high-pressure fine atomizing nozzle, and is purchased from Jining Jun atomizing equipment Co.
The p-tert-butylphenol prepared in the invention is reacted as shown in the process flow diagram of figure 1: the method comprises the steps of carrying out reaction on a fixed bed continuous reactor with a partition plate, wherein a catalyst bed layer 5 is arranged in the middle of the fixed bed continuous reactor, a partition plate 4 is arranged on the upper portion of the fixed bed continuous reactor along the axial direction, the length of the partition plate is 1/2 of the length of the reactor, the lower end of the partition plate 4 extends into the catalyst bed layer 5 and does not completely penetrate through the catalyst bed layer 5, the reactor is divided into three parts by the partition plate 4 and the catalyst bed layer 5, an upper feeding section 1 and a discharging section 3 are arranged on two sides of the partition plate, and a lower feeding section 2 is arranged below the catalyst bed layer 5; the mixed solution of MTBE and phenol is used as a feed I and is pumped into the reactor from a raw material inlet of an upper feeding section 1 by a Rewa micro-metering pump, the MTBE is used as a feed II and is pumped into the reactor from a raw material inlet of a lower feeding section 2 by a high-pressure plunger pump, the feed I is reacted on a catalyst bed layer 5 in the middle of the reactor, the reacted material is mixed with the feed II from bottom to top and is further reacted, and the reaction product is discharged from a discharge hole of a discharging section 3.
Example 1
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 30% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b, filling the obtained white solid particles into a steel wire mesh bag, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the thickness of the steel wire mesh bag is 2mm, spraying silver nitrate sulfuric acid solution with the molar concentration of 3mol/L and nitrogen into the solid particles by using an atomizing nozzle under the ultrasonic vibration condition, wherein the spraying distance is 1.5cm, the spraying pressure is 0.08MPa, the spraying time is 2 hours, drying and roasting are carried out to obtain particles I, the drying temperature is 80 ℃, and the drying time is 6 hours; the roasting temperature is 450 ℃, and the roasting time is 6 hours. c: and (c) repeating the operation of the step (b) by using a nickel nitrate sulfuric acid solution with the molar concentration of 6mol/L and nitrogen to obtain particles II. d: and (c) repeating the operation of the step (b) by using a palladium nitrate sulfuric acid solution with the molar concentration of 0.1mol/L and nitrogen to obtain the solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plateThe mixture of the reagent and quartz sand is filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 90 ℃, the reaction pressure is 3MPa, and the upper feeding total liquid hourly space velocity is 3h -1 The molar ratio of MTBE to phenol is 3: 1; the liquid hourly space velocity of MTBE in the lower feed to the catalyst was 1.5h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 2
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 35% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 450 ℃ for 8 hours to obtain white solid particles for later use. b, filling the obtained white solid particles into a steel wire mesh bag, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the thickness of the steel wire mesh bag is 2mm, spraying silver nitrate sulfuric acid solution with the molar concentration of 4mol/L and nitrogen gas on the solid particles by using an atomizing nozzle under the ultrasonic vibration condition, wherein the spraying distance is 1.5cm, the spraying pressure is 0.07MPa, the spraying time is 2 hours, drying and roasting are carried out to obtain particles I, the drying temperature is 80 ℃, and the drying time is 6 hours; the roasting temperature is 450 ℃, and the roasting time is 6 hours. c: and (c) repeating the operation of the step (b) by using a nickel nitrate sulfuric acid solution with the molar concentration of 8mol/L and nitrogen to obtain particles II. d: and (c) repeating the operation of the step (b) by using a palladium nitrate sulfuric acid solution with the molar concentration of 0.1mol/L and nitrogen to obtain the solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 90 ℃, the reaction pressure is 4MPa, and the upper feeding total liquid hourly space velocity is 3h -1 The molar ratio of MTBE to phenol is 3: 1; the liquid hourly space velocity of MTBE to the catalyst in the lower feed is 1.0 h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 3
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain extractZrOCl with a quantitative concentration of 40% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b, filling the obtained white solid particles into a steel wire mesh bag, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the thickness of the steel wire mesh bag is 2mm, spraying silver nitrate sulfuric acid solution with the molar concentration of 2mol/L and nitrogen into the solid particles by using an atomizing nozzle under the ultrasonic vibration condition, wherein the spraying distance is 1.5cm, the spraying pressure is 0.06MPa, the spraying time is 2 hours, drying and roasting are carried out to obtain particles I, the drying temperature is 80 ℃, and the drying time is 6 hours; the roasting temperature is 500 ℃, and the roasting time is 6 hours. c: and (c) repeating the operation of the step (b) by using a nickel nitrate sulfuric acid solution with the molar concentration of 8mol/L and nitrogen to obtain particles II. d: and (c) repeating the operation of the step (b) by using a palladium nitrate sulfuric acid solution with the molar concentration of 0.2mol/L and nitrogen to obtain the solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 100 ℃, the reaction pressure is 4MPa, and the upper feeding total liquid hourly space velocity is 4h -1 The molar ratio of MTBE to phenol is 3: 1; the liquid hourly space velocity of MTBE to the catalyst in the lower feed is 1.5h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 4
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 30% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b, filling the obtained white solid particles into a steel wire mesh bag, flatly paving the steel wire mesh bag in an ultrasonic vibrator with the thickness of 2mm, and using an atomizing nozzle to atomize the white solid particlesSpraying solid particles by using silver nitrate sulfuric acid solution with the temperature of 3mol/L and nitrogen under the condition of ultrasonic vibration, wherein the spraying distance is 1.5cm, the spraying pressure is 0.08MPa, the spraying time is 2 hours, drying and roasting are carried out to obtain particles I, the drying temperature is 80 ℃, and the drying time is 6 hours; the roasting temperature is 500 ℃, and the roasting time is 6 hours. c: and (c) repeating the operation of the step (b) by using a nickel nitrate sulfuric acid solution with the molar concentration of 10mol/L and nitrogen to obtain particles II. d: and (c) repeating the operation of the step (b) by using a palladium nitrate sulfuric acid solution with the molar concentration of 0.3mol/L and nitrogen to obtain the solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 110 ℃, the reaction pressure is 4MPa, and the upper feeding total liquid hourly space velocity is 3h -1 MTBE and phenol molar ratio of 4: 1; the liquid hourly space velocity of MTBE in the lower feed to the catalyst was 1.5h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 5
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 30% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b, filling the obtained white solid particles into a steel wire mesh bag, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the thickness of the steel wire mesh bag is 2mm, spraying silver nitrate sulfuric acid solution with the molar concentration of 3mol/L and nitrogen into the solid particles by using an atomizing nozzle under the ultrasonic vibration condition, wherein the spraying distance is 1.5cm, the spraying pressure is 0.08MPa, the spraying time is 2 hours, drying and roasting are carried out to obtain particles I, the drying temperature is 80 ℃, and the drying time is 6 hours; the roasting temperature is 450 ℃, and the roasting time is 6 hours. c: and (c) repeating the operation of the step (b) by using a nickel nitrate sulfuric acid solution with the molar concentration of 6mol/L and nitrogen to obtain particles II. d: repeating the step b by using a palladium nitrate sulfuric acid solution with the molar concentration of 0.2mol/L and nitrogenThe solid super acidic catalyst is obtained by operation.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 110 ℃, the reaction pressure is 3MPa, and the upper feeding total liquid hourly space velocity is 3h -1 The molar ratio of MTBE to phenol is 3: 1; the liquid hourly space velocity of MTBE to the catalyst in the lower feed is 1.5h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 6
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with mass concentration of 50% 2 And (3) titrating the ethanol solution with 20% ammonia water until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at the washing temperature of 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at the temperature of 90 ℃, extruding and forming, and roasting at the temperature of 500 ℃ for 8 hours to obtain white solid particles for later use. b, filling the obtained white solid particles into a steel wire mesh bag, flatly paving the steel wire mesh bag in an ultrasonic vibrator, wherein the thickness of the steel wire mesh bag is 2mm, spraying silver nitrate sulfuric acid solution with the molar concentration of 2mol/L and nitrogen into the solid particles by using an atomizing nozzle under the ultrasonic vibration condition, wherein the spraying distance is 1.5cm, the spraying pressure is 0.08MPa, the spraying time is 2 hours, drying and roasting are carried out to obtain particles I, the drying temperature is 80 ℃, and the drying time is 6 hours; the roasting temperature is 450 ℃, and the roasting time is 6 hours. c: and (c) repeating the operation of the step (b) by using a nickel nitrate sulfuric acid solution with the molar concentration of 6mol/L and nitrogen to obtain particles II. d: and (c) repeating the operation of the step (b) by using a palladium nitrate sulfuric acid solution with the molar concentration of 0.3mol/L and nitrogen to obtain the solid super acidic catalyst.
(2) The reaction is carried out on a fixed bed continuous reactor with a partition plate, the catalyst and quartz sand are mixed and filled in 30mL, and the filling volume ratio is 1: 1; the reaction temperature is 110 ℃, the reaction pressure is 4MPa, and the upper feeding total liquid hourly space velocity is 3h -1 MTBE and phenol molar ratio of 4: 1; the liquid hourly space velocity of MTBE to the catalyst in the lower feed is 1.5h -1 The molar ratio of nitrogen to water was 200 and the reaction results are shown in Table 1.
Example 7
During the reaction, only the feeding mode is adopted, other conditions are the same as example 4, and the reaction results are shown in table 1.
Example 8
In the reaction process, the fixed bed reactor has no partition plate in the middle, other conditions are the same as example 4, and the reaction results are shown in Table 1.
Example 9
During the reaction, only MTBE was fed into the lower feed without nitrogen, the other conditions were the same as in example 4, and the reaction results are shown in Table 1.
Example 10
The preparation process of the used catalyst has no ultrasonic vibration and mixed spraying process of the modification liquid and nitrogen, only the catalyst is modified by adopting a conventional supersaturated impregnation method, other conditions are the same as those of the example 4, and the reaction results are shown in the table 1.
TABLE 1 reaction results (conversion in moles) of examples and comparative examples
Figure 503002DEST_PATH_IMAGE001

Claims (11)

1. A method for preparing p-tert-butylphenol by taking MTBE as a raw material adopts a fixed bed tubular reactor, and is characterized in that a catalyst bed layer is arranged in the middle of the fixed bed tubular reactor, a partition plate is axially arranged on the upper part of the fixed bed tubular reactor, the lower end of the partition plate extends into the catalyst bed layer and does not completely penetrate through the catalyst bed layer, the reactor is divided into three parts by the partition plate and the catalyst bed layer, an upper feeding section and a discharging section are arranged above two sides of the partition plate, and a lower feeding section is arranged below the catalyst bed layer; MTBE and phenol enter the reactor from a raw material inlet of an upper feeding section as a feeding I, MTBE and nitrogen enter the reactor from a raw material inlet of a lower feeding section as a feeding II, the feeding I reacts on a catalyst bed layer in the middle of the reactor, the reacted materials are mixed with the feeding II from bottom to top for further reaction, and a reaction product is discharged from a discharge hole of a discharging section;
the reaction conditions were as follows: the reaction temperature is 80-120 ℃, and the reaction pressure is 2-5 Mpa;
the catalyst used in the reaction is a solid super acidic catalyst, and the preparation method of the solid super acidic catalyst comprises the following steps:
(1) ZrOCl 2 Dissolving in ethanol to obtain ZrOCl 2 Titrating with ammonia water until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, molding, drying, and roasting to obtain white solid particles;
(2) and (2) respectively soaking the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, a nickel nitrate sulfuric acid solution and a palladium nitrate sulfuric acid solution, drying and roasting after each step of soaking, and finally obtaining the metal-doped solid super acidic catalyst.
2. The method of claim 1, wherein the length of the partition is 1/2-2/3 of the length of the reactor, and the top of the partition and the two sides of the partition are hermetically connected with the wall of the reactor.
3. The process according to claim 1, characterized in that the molar ratio of MTBE to phenol in feed I is 1: 1-5: 1.
4. the method according to claim 3, wherein the total liquid hourly space velocity of the feed I is 1-4 h -1 。
5. The method of claim 1, wherein the liquid hourly space velocity of MTBE to the catalyst in the feed II is 1-2 h -1 。
6. The process of any one of claims 1 to 5, wherein the total liquid hourly space velocity of feed I is greater than the total liquid hourly space velocity of feed II.
7. The process according to claim 5, wherein the molar ratio of nitrogen to MTBE in feed II is between 100 and 200: 1.
8. the method as claimed in claim 1, wherein the catalyst is loaded by filling quartz sand at both ends of the reactor, and the catalyst bed section is filled with a mixture of the catalyst and the quartz sand, wherein the particle size of the quartz sand is 1.5-2.0 mm, and the catalyst accounts for 60-70 v% of the total loading amount of the catalyst bed.
9. The method of claim 1, wherein said ZrOCl of step (1) 2 The mass concentration of the ethanol solution is 30-50%.
10. The method according to claim 1, wherein the nitrate sulfuric acid solution in the step (2) is prepared by: dissolving nitrate in dilute sulfuric acid to obtain a nitrate sulfuric acid solution; wherein the concentration of the dilute sulfuric acid is 0.3-0.6 mol/L, the concentration of the silver nitrate sulfuric acid solution is 2-4 mol/L, the concentration of the nickel nitrate sulfuric acid solution is 5-10 mol/L, and the concentration of the palladium nitrate sulfuric acid solution is 0.1-0.3 mol/L.
11. The method according to claim 1, wherein the impregnation in step (2) is carried out by spray impregnation using a gas-liquid mixture of an impregnation liquid and nitrogen.
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