CN111099967A - Preparation method of tert-butyl phenol - Google Patents

Preparation method of tert-butyl phenol Download PDF

Info

Publication number
CN111099967A
CN111099967A CN201811262124.1A CN201811262124A CN111099967A CN 111099967 A CN111099967 A CN 111099967A CN 201811262124 A CN201811262124 A CN 201811262124A CN 111099967 A CN111099967 A CN 111099967A
Authority
CN
China
Prior art keywords
catalyst
reaction
reactor
feeding
catalyst bed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201811262124.1A
Other languages
Chinese (zh)
Other versions
CN111099967B (en
Inventor
刘野
赵亮
王岩
于庆志
党雷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Dalian Petrochemical Research Institute Co ltd
China Petroleum and Chemical Corp
Original Assignee
China Petroleum and Chemical Corp
Sinopec Dalian Research Institute of Petroleum and Petrochemicals
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Petroleum and Chemical Corp, Sinopec Dalian Research Institute of Petroleum and Petrochemicals filed Critical China Petroleum and Chemical Corp
Priority to CN201811262124.1A priority Critical patent/CN111099967B/en
Publication of CN111099967A publication Critical patent/CN111099967A/en
Application granted granted Critical
Publication of CN111099967B publication Critical patent/CN111099967B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11Preparation 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
    • C07C37/14Preparation 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
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/02Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/053Sulfates
    • B01J27/055Sulfates with alkali metals, copper, gold or silver
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/0201Impregnation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02Impregnation, coating or precipitation
    • B01J37/03Precipitation; Co-precipitation
    • B01J37/031Precipitation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/34Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Health & Medical Sciences (AREA)
  • Plasma & Fusion (AREA)
  • Toxicology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

A preparation method of tert-butyl phenol adopts a fixed bed tubular reactor, wherein the middle part of the reactor is a catalyst bed layer, the upper part of the reactor is provided with a partition plate 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, the two sides of the partition plate are an upper feeding section and a discharging section, and a lower feeding section is arranged below a catalyst filling layer; isobutene and p-methyl phenol enter from a raw material inlet of an upper feeding section as a feeding material I, isobutene and nitrogen enter from a raw material inlet of a lower feeding section as a feeding material II, the feeding material I is subjected to an ammoniation reaction in a catalyst bed layer, the reacted material is mixed with the feeding material II from bottom to top for further reaction, and a product is discharged from a discharge hole of a discharging section. The reaction mode of the method ensures that the materials react more fully, improves the reaction conversion rate, and the feeding at the upper end passes through the catalyst bed layer repeatedly, so that the reaction is more fully, and the conversion rate of the isobutene is improved.

Description

Preparation method of tert-butyl phenol
Technical Field
The invention relates to a preparation method of tert-butyl phenol, in particular to a method for preparing 2, 6-di-tert-butyl 4-methylphenol by using isobutene and p-methylphenol as raw materials.
Background
2, 6-di-tert-butyl-4-methylphenol is white or light yellow crystal, and the molecular formula is C15H24And O. It is easily soluble in toluene, soluble in organic solution such as acetone, ethanol, benzene, diethyl ether, isopropanol, methanol, 2-butanone, ethylene glycol ethyl ether, petroleum ether, etc., and insoluble in water and alkali solution. 2, 6-tert-butyl 4-methyl phenol is a general antioxidant, mainly used as antioxidant additive of various petroleum products, antioxidant and stabilizer of some high molecular materials, antioxidant of food processing industry, phenol anti-aging agent for rubber, widely used in natural rubber, various synthetic rubbers and latex thereof, and stabilizer for synthetic rubber and post-treatment and storage, such as styrene-butadiene rubber, chloroprene rubber, ethylene-propylene rubber and the like.
The synthesis method of 2, 6-di-tert-butyl-4-methylphenol mainly comprises the following steps:
the p-cresol process. The paracresol and the alkylating agent are subjected to Friedel-crafts reaction and then purified. The method is widely adopted in China.
The mixed phenol method. The mixed phenol and the alkylating agent are subjected to Friedel-crafts reaction, then are rectified and separated, and finally are crystallized. The process requirement is higher, and the method is more suitable for German factories at present.
The scherdam method. The product can be directly obtained by catalytic hydrogenation after the mannich reaction of phenol. The cost is low because phenol is used as a main raw material, but the product quality is the most unstable of the three processes, and the Russian factory mostly adopts the method.
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, and the MTBE capacity will be surplus, so the production of MTBE will be limited, and thus, a large amount of isobutene will be left, and the utilization of isobutene will become a future development trend. Isobutene is used as a raw material, and the isobutene and p-methylphenol are synthesized into 2, 6-di-tert-butyl-4-methylphenol which can be used as one of effective ways for utilizing isobutene.
Patent CN106631705A discloses a production process for alkylating 2, 6-di-tert-butyl-4-methylphenol antioxidant, which takes isobutene and p-methylphenol as raw materials, adopts three alkylation reaction kettles to carry out continuous, intermittent and continuous operation modes respectively for reaction, and has longer process flow and more complex operation. According to the report of the literature, isobutene and p-methyl phenol are used as raw materials, concentrated sulfuric acid is used as a catalyst, the reaction is carried out in an autoclave, the problems of discontinuous reaction, serious corrosion of equipment and environmental pollution exist, and the reaction conversion rate and the selectivity are low.
Disclosure of Invention
Aiming at the problems of strong catalyst corrosivity, environmental pollution, low reaction conversion rate, poor selectivity, complex flow and operation and the like in the method for preparing 2, 6-tert-butyl 4-methylphenol by using isobutene and p-methylphenol as raw materials in the prior art, the invention provides the method for preparing tert-butylphenol. The method takes isobutene and p-methylphenol as raw materials to prepare 2, 6-di-tert-butyl 4-methylphenol, 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 supported heteropoly acid 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 the isobutene, 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 preparation method of p-tert-butylphenol 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; isobutene and p-methyl phenol enter the reactor from a raw material inlet of an upper feeding section as feeding I, isobutene and nitrogen enter the reactor from a raw material inlet of a lower feeding section as 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 reaction products are discharged from a discharge hole of a 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 isobutene to p-methyl phenol in the feed I is 1: 1-6: 1, preferably 2: 1-4: 1, the total liquid hourly space velocity is 0.5-5 h-1Preferably 1 to 2 hours-1
In the method, the liquid hourly space velocity of the isobutene in the feed II on the catalyst is 0.5-1 h-1Preferably 0.6 to 0.8h-1The molar ratio of nitrogen to p-methylphenol 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 80-140 ℃, and preferably 100-130 ℃; the reaction pressure is 0.01 to 0.1MPa, preferably 0.04 to 0.06 MPa.
In the method of the invention, the catalyst used is a solid super acidic catalyst.
In the method, the solid super acidic catalyst is prepared by the following steps:
(1) ZrOCl2And TiCl4Dissolving in ethanol to obtain ZrOCl2And TiCl4Titrating with ammonia water under stirring until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, drying, and roasting to obtain white solid particles;
(2) sequentially dipping the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, one or two solutions selected from a cobalt nitrate sulfuric acid solution and a molybdenum nitrate sulfuric acid solution and one or two solutions selected from a nickel nitrate sulfuric acid solution and a tungsten nitrate sulfuric acid solution, wherein drying and roasting are required after each step of dipping; finally obtaining the metal-doped solid super acidic catalyst.
ZrOCl in the step (1)2And TiCl4The mass concentration of the ethanol solution is 20-40% and 20-30% respectively.
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 in the step (1) are cylindrical particles with the diameter 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 cobalt nitrate/molybdenum sulfuric acid solution is 5-15 mol/L, and the concentration of the nickel nitrate/tungsten sulfuric acid solution is 3-6 mol/L.
The impregnation process in the step (2) is carried out under the conditions of reduced pressure and ultrasonic vibration. The decompression condition is 15000-20000 Pa; the ultrasonic condition is that the vibration frequency is 50-60 kHz; the dipping temperature is 55-60 ℃, and the dipping time is 4-6 h.
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 isobutene is improved.
(3) The catalyst filling section is filled by mixing with quartz sand, the lower feeding section is filled by mixing p-methyl phenol with 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 catalyst active centers are increased, and the reaction efficiency and the conversion rate are improved.
(4) The reactor is additionally provided with the axial partition plate, 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 isobutene is higher.
(5) In the preparation process of the solid super acidic catalyst, ZrO is adopted2-TiO2The composite carrier and different metal solutions are respectively impregnated in a certain order under the conditions of reduced pressure, ultrasonic vibration and a certain impregnation temperature, and the impregnating solution is continuously boiled, SO that the catalyst has uniform particle size and SO4 2-The coordination with the metal ions on the surface of the oxide is rapid and uniform, so that the catalyst has stronger acidity. ZrO (ZrO)2-TiO2Composite carrier at carrier interfaceA new active site is formed, and the active metal and the defect site of the carrier jointly activate a C = C bond, so that the reactivity is increased. Ag+Is pre-doped to ZrO2The 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 2, 6-di-tert-butyl-4-methylphenol according to the present 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, respectively mixing 50-100 g ZrOCl2And TiCl4Dissolving in ethanol to obtain ZrOCl2Mass concentration of 20-40 percent TiCl4The method comprises the steps of titrating an ethanol solution with the mass concentration of 20-30% with 20-25% ammonia water until no white precipitate exists, washing the solution for several times with deionized water, washing the solution for 5-10 minutes each time at the washing temperature of 40-50 ℃ until no chloride ion exists, then drying the solution in a vacuum drying oven for 4-6 hours at the temperature of 80-90 ℃, extruding the solution to form strips, and roasting the strips for 8 hours at the temperature of 500 ℃ to obtain white solid particles for later use. Secondly, dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2-4 mol/L, wherein the dipping temperature is 55-60 ℃, and the dipping time is 4-6 h; the decompression vacuum degree is 15000-20000 Pa; and (3) the ultrasonic vibration frequency is 50-60 kHz, then the solid particles are placed in a vacuum drying oven to be dried for 4-6 hours at the temperature of 80-90 ℃, and then the solid particles are roasted for 8 hours at the temperature of 500 ℃ to obtain particles I. And thirdly, repeating the impregnation process of the second step by using a cobalt nitrate (or molybdenum) sulfuric acid solution to obtain particles II. Fourthly, the process of the second step is repeated by using a nickel nitrate (or tungsten) sulfuric acid solution 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 model of an ultrasonic vibrator used in the preparation of the supported heteropolyacid catalyst is KQ-550B, the model of a circulating water type multipurpose vacuum pump is SHB-B95T, and the product is purchased from Zhengzhou great wall Korsao Co.
The preparation of 2, 6-di-tert-butyl 4-methylphenol in the invention is carried out according to the process flow diagram shown in 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; the mixed solution of methyl phenol and isobutene is used as a feeding I and is pumped into a reactor from a raw material inlet of an upper feeding section 1 by a Rewa micro-metering pump, isobutene is used as a feeding 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 feeding I is reacted on a catalyst bed layer 5 in the middle of the reactor, the reacted materials are mixed with the feeding II from bottom to top and are further reacted, and reaction products are discharged from a discharge hole of a discharging section 3.
Example 1
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 25%2Ethanol solution, 30 g of TiCl4Dissolved in ZrOCl2Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 15000 Pa; the ultrasonic vibration frequency was 55kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: repeating the dipping process of the second step by using a cobalt nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particlesAnd (II) granules. d: and (4) repeating the process of the second step by using a nickel nitrate sulfuric acid solution with the concentration of 3mol/L to obtain the metal-doped 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 0.05MPa, and the upper feeding total liquid hourly space velocity is 2h-1The molar ratio of isobutene to p-methylphenol is 2: 1; the volume space velocity of isobutene to the catalyst in the lower feed is 0.6 h-1The 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 ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 25%2Ethanol solution, 35 g of TiCl4Dissolved in ZrOCl2Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 16000 Pa; the ultrasonic vibration frequency was 55kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a cobalt nitrate sulfuric acid solution with the concentration of 6mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a nickel nitrate sulfuric acid solution with the concentration of 4mol/L to obtain the metal-doped 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 0.06MPa, and the upper feeding total liquid hourly space velocity is 1.5h-1The molar ratio of isobutene to p-methylphenol is 3: 1; the volume space velocity of isobutene to the catalyst in the lower feed is 0.6 h-1Nitrogen gas and waterThe molar ratio of (A) to (B) was 200, and the reaction results are shown in Table 1.
Example 3
(1) Preparing a solid super acidic catalyst: a: 50 g of ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 25%2Ethanol solution, 35 g of TiCl4Dissolved in ZrOCl2Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 58 ℃, and the dipping time is 6 hours; the vacuum degree is 18000 Pa; the ultrasonic vibration frequency was 58kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a cobalt nitrate sulfuric acid solution with the concentration of 8mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a nickel nitrate sulfuric acid solution with the concentration of 4mol/L to obtain the metal-doped 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 120 ℃, the reaction pressure is 0.06MPa, and the upper feeding total liquid hourly space velocity is 2h-1The molar ratio of isobutene to p-methylphenol is 3: 1; the volume space velocity of isobutene to the catalyst in the lower feed is 0.6 h-1The 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 ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 25%2Ethanol solution, 30 g of TiCl4Dissolved in ZrOCl2Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, each time for 10 minutes, at 40 deg.C until no chloride ion exists, and standing at 90 deg.CDrying in a vacuum drying oven for 6 hours, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 2mol/L, wherein the dipping temperature is 60 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 16000 Pa; the ultrasonic vibration frequency was 58kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a cobalt nitrate sulfuric acid solution with the concentration of 7mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a nickel nitrate sulfuric acid solution with the concentration of 5mol/L to obtain the metal-doped 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 130 ℃, the reaction pressure is 0.07MPa, and the upper feeding total liquid hourly space velocity is 1h-1The molar ratio of isobutene to p-methylphenol is 4: 1; the volume space velocity of isobutene to the catalyst in the lower feed is 0.6 h-1The 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 ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 25%2Ethanol solution, 30 g of TiCl4Dissolved in ZrOCl2Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 3mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 15000 Pa; the ultrasonic vibration frequency was 56kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: repeating the impregnation process of the second step by using a cobalt nitrate sulfuric acid solution with the concentration of 8mol/LGranules II were obtained. d: and (4) repeating the process of the second step by using a nickel nitrate sulfuric acid solution with the concentration of 4mol/L to obtain the metal-doped 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 120 ℃, the reaction pressure is 0.05MPa, and the upper feeding total liquid hourly space velocity is 2h-1The molar ratio of isobutene to p-methylphenol is 2: 1; the volume space velocity of isobutene to the catalyst in the lower feed is 0.6 h-1The 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 ZrOCl2Dissolving in ethanol to obtain ZrOCl with mass concentration of 25%2Ethanol solution, 30 g of TiCl4Dissolved in ZrOCl2Titrating with 20% ammonia water in ethanol solution until no white precipitate exists, washing with deionized water for 5 times, washing for 10 minutes each time at 40 ℃ until no chloride ion exists, drying in a vacuum drying oven for 6 hours at 90 ℃, extruding and molding, and roasting at 500 ℃ for 8 hours to obtain white solid particles for later use. b: dipping the white particles obtained in the first step by using a silver nitrate sulfuric acid solution with the concentration of 4mol/L, wherein the dipping temperature is 55 ℃, and the dipping time is 6 hours; the vacuum degree is reduced to 15000 Pa; the ultrasonic vibration frequency was 55kHz, and then the solid particles were dried in a vacuum oven at 90 ℃ for 6 hours and then calcined at 500 ℃ for 8 hours to give particles I. c: and (4) repeating the impregnation process in the second step by using a cobalt nitrate sulfuric acid solution with the concentration of 7mol/L to obtain particles II. d: and (4) repeating the process of the second step by using a nickel nitrate sulfuric acid solution with the concentration of 5mol/L to obtain the metal-doped 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 130 ℃, the reaction pressure is 0.08MPa, and the upper feeding total liquid hourly space velocity is 2h-1The molar ratio of isobutene to p-methylphenol is 3: 1; the volume space velocity of isobutene to the catalyst in the lower feed is 0.7h-1Nitrogen gas, nitrogen gasThe molar ratio 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 isobutene and no nitrogen were fed into the lower feed, 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 decompression process, only adopts the conventional supersaturated impregnation method to modify the catalyst, and the impregnation sequence is that the sulfuric acid solution of silver nitrate is put at the end, other conditions are the same as the example 4, and the reaction result is shown in the table 1.
TABLE 1 reaction results (conversion in moles) of examples and comparative examples
Figure DEST_PATH_IMAGE001

Claims (13)

1. A preparation method of p-tert-butylphenol 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; isobutene and p-methyl phenol enter the reactor from a raw material inlet of an upper feeding section as feeding I, isobutene and nitrogen enter the reactor from a raw material inlet of a lower feeding section as 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 reaction products are discharged from a discharge hole of a discharging section.
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, wherein the molar ratio of isobutylene to para-methylphenol in the feed I is 1: 1-6: 1.
4. the process according to claim 3, wherein the total liquid hourly space velocity of the feed I is 0.5 to 5h-1
5. The method of claim 1, wherein the liquid hourly space velocity of isobutene in the feed II on the catalyst is 0.5-1 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 isobutylene in feed II is from 100 to 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 according to claim 1, wherein the amination reaction is carried out under the following reaction conditions: the reaction temperature is 80-140 ℃, and the reaction pressure is 0.01-0.1 MPa.
10. The process of claim 1, wherein the catalyst used in the reaction is a solid super acidic catalyst.
11. The method of claim 10, wherein the solid super acid catalyst is prepared by:
(1) ZrOCl2And TiCl4Dissolving in ethanol to obtain ZrOCl2And TiCl4Titrating with ammonia water under stirring until no white precipitate is generated, filtering, washing until no chloride ion is generated, drying to obtain white solid powder, extruding into strips, drying, and roasting to obtain white solid particles;
(2) sequentially dipping the white solid particles obtained in the step (1) by using a silver nitrate sulfuric acid solution, one or two solutions selected from a cobalt nitrate sulfuric acid solution and a molybdenum nitrate sulfuric acid solution and one or two solutions selected from a nickel nitrate sulfuric acid solution and a tungsten nitrate sulfuric acid solution, wherein drying and roasting are required after each step of dipping; finally obtaining the metal-doped solid super acidic catalyst.
12. The method of claim 11, wherein ZrOCl is2And TiCl4The mass concentration of the ethanol solution is 20-40% and 20-30% respectively.
13. The method according to claim 11, wherein the impregnation process in step (2) is performed under reduced pressure and ultrasonic vibration; the decompression condition is 15000-20000 Pa; the ultrasonic condition is that the vibration frequency is 50-60 kHz.
CN201811262124.1A 2018-10-27 2018-10-27 Preparation method of tert-butyl phenol Active CN111099967B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811262124.1A CN111099967B (en) 2018-10-27 2018-10-27 Preparation method of tert-butyl phenol

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811262124.1A CN111099967B (en) 2018-10-27 2018-10-27 Preparation method of tert-butyl phenol

Publications (2)

Publication Number Publication Date
CN111099967A true CN111099967A (en) 2020-05-05
CN111099967B CN111099967B (en) 2023-01-10

Family

ID=70418468

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811262124.1A Active CN111099967B (en) 2018-10-27 2018-10-27 Preparation method of tert-butyl phenol

Country Status (1)

Country Link
CN (1) CN111099967B (en)

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1844071A (en) * 2006-03-24 2006-10-11 北京极易化工有限公司 Phenol ortho alkylation method with high-conversion and high-selectivity
CN101254464A (en) * 2008-03-06 2008-09-03 南京工业大学 Composite catalyst for flue gas denitration under low temperature condition and preparation method thereof
CN102260010A (en) * 2011-05-16 2011-11-30 苏州苏净环保工程有限公司 Integrated natural circulating and baffling reactor
CN106040258A (en) * 2016-05-27 2016-10-26 南京工程学院 Magnetic nano-alloy and mesoporous zirconium-titanium composite oxide core-shell catalytic material
CN107737605A (en) * 2017-09-30 2018-02-27 宝鸡文理学院 A kind of catalyst of DI-tert-butylphenol compounds of 4 methyl of selectivity synthesis 2,6 and its application
CN108285406A (en) * 2018-02-07 2018-07-17 常州大学 A kind of preparation method of antioxidant BHT

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1844071A (en) * 2006-03-24 2006-10-11 北京极易化工有限公司 Phenol ortho alkylation method with high-conversion and high-selectivity
CN101254464A (en) * 2008-03-06 2008-09-03 南京工业大学 Composite catalyst for flue gas denitration under low temperature condition and preparation method thereof
CN102260010A (en) * 2011-05-16 2011-11-30 苏州苏净环保工程有限公司 Integrated natural circulating and baffling reactor
CN106040258A (en) * 2016-05-27 2016-10-26 南京工程学院 Magnetic nano-alloy and mesoporous zirconium-titanium composite oxide core-shell catalytic material
CN107737605A (en) * 2017-09-30 2018-02-27 宝鸡文理学院 A kind of catalyst of DI-tert-butylphenol compounds of 4 methyl of selectivity synthesis 2,6 and its application
CN108285406A (en) * 2018-02-07 2018-07-17 常州大学 A kind of preparation method of antioxidant BHT

Also Published As

Publication number Publication date
CN111099967B (en) 2023-01-10

Similar Documents

Publication Publication Date Title
CN107107042A (en) Prepare catalyst of glycol ether and its preparation method and application
CN102211036B (en) A kind of modified molecular sieve catalyst and its precursor and preparation method thereof
CN111099968B (en) Method for preparing p-tert-butylphenol
CN111099966B (en) Method for preparing tert-butyl phenol
CN111099967B (en) Preparation method of tert-butyl phenol
CN111099969B (en) Method for preparing p-tert-butyl catechol
CN1463960A (en) Process for preparing ethandiol by catalyzing epoxyethane hydration
CN109772291B (en) Selective hydrogenation and dealkynization catalyst and preparation method and application thereof
CN109174168B (en) Catalyst for preparing 2-methylpyridine by pyridine alkylation, preparation method and application
CN111099972B (en) Method for preparing p-tert-butyl catechol from MTBE (methyl tert-butyl ether)
CN111100009B (en) Method for preparing tert-butylamine by using MTBE as raw material
CN111099971B (en) Method for preparing p-tert-butylphenol by using MTBE as raw material
CN111825556B (en) Preparation method of tert-butylamine
CN111100013B (en) Method for preparing tert-butylamine
CN111423309B (en) Method for synthesizing 1-butene-3, 4-diol through gas-solid phase continuous isomerization
CN104230633A (en) Liquid phase alkyl transfer method
CN112939924A (en) Process for producing cyclic carbonate
CN101602006B (en) Modified aluminum oxide catalyst for synthesizing dimethyl ether and preparation method thereof
CN109678670B (en) Method for preparing sec-butyl alcohol
CN112209791B (en) Method for producing propylene by tert-butyl alcohol conversion
CN110937982B (en) Method for preparing p-tert-butylphenol
CN1566050A (en) Process for preparing ethylene glycol by ethylene oxide catalytic hydration
CN104557380B (en) The method that extracting carbon four produces propylene
CN111100285B (en) Method for preparing polyetheramine
CN105413735A (en) Catalyst for reaction of preparing gasoline from methanol, preparation method and applications thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20231110

Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee after: CHINA PETROLEUM & CHEMICAL Corp.

Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd.

Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen

Patentee before: CHINA PETROLEUM & CHEMICAL Corp.

Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp.

TR01 Transfer of patent right