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