Method for preparing p-tert-butylphenol
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 isobutene and phenol as raw materials.
Background
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 solutions. 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 product can also be used as raw material for preparing medicinal insect repellent, pesticide acaricide propargite, perfume and plant protectant. It can also be used as softener, solvent, dye and paint additive, antioxidant of lubricating oil, oil field demulsifier and additive of vehicle fuel.
The common preparation methods of p-tert-butylphenol mainly comprise: (1) phenol isobutylene Process: taking phenol and isobutene as raw materials, taking cation exchange resin as a catalyst, carrying out alkylation reaction at the normal pressure and the temperature of 110 ℃, and carrying out reduced pressure distillation on the product to obtain a product; (2) 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; (3) carbon four-cut method: 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; (4) phenol tert-butanol method: the product is prepared by using phenol and tert-butyl alcohol as raw materials and through water washing, crystallization and separation.
MTBE is recently gaining favor as a high octane additive and an 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 the MTBE capacity is necessary to be surplus, the production of MTBE is limited, and a large amount of isobutene is left, so that the utilization of isobutene becomes a future development trend. Isobutene is used as an alkylating agent, and the isobutene and phenol are synthesized into p-tert-butylphenol which can be used as one of ways of isobutene utilization.
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 literature reports that solid superacid, temperature-resistant resin and the like are used as catalysts, isobutene is used as an alkylating agent to synthesize p-tert-butylphenol, but the reaction is a kettle type reaction, the reaction process is discontinuous, the temperature is high, and the conversion rate of phenol and the product selectivity are low.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for preparing p-tert-butylphenol. The method has the advantages that the conversion rate of the reaction can be effectively improved by the tubular reactor which is fed up and down simultaneously and the metal-doped solid super acidic catalyst, the process is simple, no pollution is caused, the condition is mild, and the reactor can stably run for a long period.
The method for preparing the p-tert-butylphenol comprises the following steps: under the condition of alkylation reaction, isobutene and phenol enter from the top of a reactor in a spray mode as a feed I, penetrate through a plurality of layers of horizontally staggered catalyst bed layers from top to bottom, react layer by layer, isobutene enters from the lower part of the reactor as a feed II, is rapidly gasified, ascends layer by layer from bottom to top, further reacts with material flows from top to bottom, and reaction products are discharged from the bottom of the reactor; wherein the catalyst bed layer comprises a bed plate with air holes and a catalyst on the bed plate.
In the method of the invention, the alkylation reaction conditions are as follows: the reaction temperature is 80-120 ℃, and the preferable temperature is 90-110 ℃; the reaction pressure is 2 to 5MPa, preferably 3 to 4MPa.
In the process of the present invention, the molar ratio of isobutylene to phenol in feed I is 1:1 to 5:1, preferably 3:1 to 4:1, the total volume airspeed is 1-4 h -1 Preferably 2 to 3 hours -1 。
In the method, the spray type feeding adopts a conventional atomizing nozzle for spray feeding.
In the method, the volume space velocity of the feed II (isobutene) is 1-2 h -1 Preferably 1 to 1.5h -1 。
The method of the invention also provides an alkylation reactor, wherein a plurality of layers of horizontally staggered bed plates are arranged along the axial direction of the reactor, one end of each bed plate is hermetically connected with the wall of the reactor, the other end of each bed plate is at a certain distance from the wall of the reactor and is provided with a baffle plate, and a plurality of air holes are formed in each bed plate; the top of the reactor is provided with an upper feed inlet, the upper feed inlet is provided with an atomizing nozzle, the lower part of the reactor is provided with a lower feed inlet, and the bottom of the reactor is provided with a feed inlet.
The length of the bed plate is 2/3-3/4 of the diameter of the reactor, and the edge of the bed plate is hermetically connected with the tube wall of the reactor.
The aperture of the air holes is 0.5-1 mm, and the air holes are uniformly distributed on the bed plate; the height of the baffle at the end of the bed board is 0.3-0.5 cm.
In the method of the present invention, the catalyst may be solid super acid or high temperature resistant resin, etc. well known in the art.
The invention also provides a preparation method of the solid super acidic catalyst, which 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 by a conventional method, drying, and roasting to obtain white solid particles for later use;
(2) Respectively preparing a silver nitrate sulfuric acid solution, a nickel nitrate sulfuric acid solution and a palladium nitrate sulfuric acid solution, impregnating the white solid particles obtained in the step (1) with the silver nitrate sulfuric acid solution, drying and roasting to obtain particles I, impregnating the particles I with the nickel nitrate sulfuric acid solution, drying and roasting to obtain particles II, impregnating the particles II with the palladium nitrate sulfuric acid solution, drying and roasting to obtain a metal-doped solid super acidic catalyst; the impregnation process is carried out under reduced pressure and ultrasonic vibration.
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 step (2) is that the preparation process of the silver nitrate sulfuric acid solution comprises the following steps: dissolving silver nitrate in dilute sulfuric acid to obtain a silver nitrate sulfuric acid solution; the preparation processes of the nickel nitrate sulfuric acid solution and the palladium nitrate sulfuric acid solution are the same as those of the silver 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.
The decompression condition in the step (2) is 15000 to 20000Pa; 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 to 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 alkylation reaction is carried out on a tubular reactor with a bed plate, the material is fed in an upper and lower simultaneous feeding mode, the reaction material fed in the upper mode enters the reactor through an atomizing nozzle under a certain airspeed condition, the material passing through the atomizing nozzle exists in a mixing state of mist small liquid drops under the reaction condition, the mixture and the distribution are more uniform, the material is in contact with and reacts with a catalyst on the bed plate, a reactant flows to a next bed plate step by step through air holes on the catalyst bed plate and reacts, the reaction material fed in the lower mode enters the reactor under a certain airspeed condition, the reaction material is gasified rapidly under the reaction condition, the air holes on the bed plate rise step by step and diffuse in the space of the reactor through gaps between the catalyst bed plates, the concentration and the flow rate of the gas fed in the reactor are improved, the reaction material is mixed with the reactant fed in the upper mode and then reacts on the catalyst bed plate, and the reaction process has the advantages of a trickle bed and catalytic rectification simultaneously through the reactor and the feeding mode, and the reaction conversion rate is improved.
(2) In the preparation process of the solid super acidic catalyst, different metal solutions are adopted to be respectively impregnated according to a certain sequence, the impregnation is carried out under the conditions of reduced pressure, ultrasonic vibration and a certain impregnation temperature, and the impregnation solution is continuously boiled, SO that the catalyst has uniform particle size and SO 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 grains tend to exist in a monoclinic type (M),the monoclinic type (M) has a 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 port; 2-lower feed inlet; 3-discharging port; 4-a catalyst; 5-a baffle plate; 6-bed board; 7-atomizing nozzle.
The alkylation reactor of the present invention works as follows: the feeding I enters the reactor from the upper feeding port 1, is atomized by the atomizing nozzle 7 to form a mist mixture, falls on the catalyst bed plate 6, reacts under certain reaction conditions and under the action of the catalyst 4, reactants flow to the next bed plate step by step through the air holes on the catalyst bed plate 6 and react, the feeding II enters the reactor from the lower feeding port 2, is rapidly gasified under the reaction conditions, rises step by step through the air holes on the bed plate, and permeates through the space between the catalyst bed plates to permeate into the space of the reactor, further reacts on the catalyst bed plate after being mixed with the reactants fed at the upper part, and finally the reaction product is discharged from the discharging port 3.
Detailed Description
The preparation process of the solid super acidic catalyst of the present invention is specifically described as follows: 1. reacting ZrOCl 2 Dissolving in ethanol to obtain ZrOCl with a mass concentration of 30-50% 2 The ethanol solution is titrated by ammonia water until no white precipitate is generated, is washed by deionized water and is filtered until no chloride ion is generated, the drying time is 4 to 6 hours under the condition of 70 to 90 ℃ to obtain white powder, the white powder is extruded by a conventional method, is dried for 4 to 6 hours under the condition of 70 to 90 ℃ after being molded, and is roasted for 4 to 6 hours under the condition of 450 to 550 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.3-0.6 mol/L to prepare silver nitrate sulfuric acid solution with the molar concentration of 2-4 mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.3-0.6 mol/L to prepare nickel nitrate sulfuric acid solution with the molar concentration of 5-10 mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.3-0.6 mol/L to prepare palladium nitrate sulfuric acid solution with the molar concentration of 0.1-0.3 mol/L. 3. Impregnating the solution in the first step with silver nitrate sulfuric acid solution to obtainWhite solid particles of (2) under the vacuum degree of 15000-20000 Pa; the ultrasonic vibration frequency is 50-60 kHz; the dipping temperature is 55-60 ℃, and the dipping time is 4-6 h; filtering, drying at the drying temperature of 80-100 ℃ for 6~8 hours, and roasting at the roasting temperature of 450-550 ℃ for 4~6 hours to obtain the particles I. 4. And (3) treating the particles I with a nickel nitrate sulfuric acid solution according to the method and conditions of the step three to obtain particles II, and treating the particles II with a palladium nitrate sulfuric acid solution according to the method and conditions of the step three to obtain the metal-doped solid super acidic catalyst.
The specific embodiment of the invention is as follows: the method comprises the steps of carrying out reaction on a fixed bed continuous reactor with a catalyst bed plate, pumping isobutene and phenol serving as a feed I into the reactor by a lining micro-dosage pump under the alkylation reaction condition, spraying the isobutene and the phenol from the top of the reactor, penetrating through a plurality of layers of horizontally staggered catalyst bed layers from top to bottom, reacting layer by layer, pumping the isobutene serving as a feed II into the reactor by a high-pressure plunger pump, quickly gasifying the isobutene, ascending layer by layer from bottom to top, further reacting with material flow from top to bottom, and discharging a reaction product from the bottom of the reactor; wherein the catalyst bed layer comprises a bed plate with air holes and a catalyst on the bed plate.
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 metal-doped solid super acidic catalyst is KQ-550B, and the model of an upper feeding atomization nozzle is JLN-G type high-pressure fine atomization nozzle, which is purchased from Jining Jun spray equipments, inc. The alkylation reactor has an internal diameter of 25mm and a height of 160cm. The length of the bed plate is 2/3-3/4 of the diameter of the reactor, and the edge of the bed plate is hermetically connected with the tube wall of the reactor. The aperture of the air holes is 0.5-1 mm, and the air holes are uniformly distributed on the bed plate; the height of the baffle at the end of the bed board is 0.3-0.5 cm.
Example 1
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanolZrOCl with mass concentration of 30% 2 And (2) titrating the ethanol solution by using ammonia water until no white precipitate is generated, washing by using deionized water, filtering until no chloride ion is generated, drying for 4 hours at the temperature of 70 ℃ to obtain white powder, extruding the white powder into strips by using a conventional method, drying for 4 hours at the temperature of 70 ℃, and roasting for 4 hours at the temperature of 450 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 2mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 5mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.1 mol/L. 3. Dipping the white solid particles obtained in the first step by using silver nitrate sulfuric acid solution, and keeping the vacuum degree at 15000Pa; the ultrasonic vibration frequency is 50kHz; dipping at 55 ℃ for 4 h; after filtration, the mixture was dried at 80 ℃ for 6 hours and then calcined at 450 ℃ for 4 hours to obtain granules I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain the metal-doped solid super acidic catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 90 ℃, the reaction pressure is 3.0MPa, and the molar ratio of isobutene to phenol in the feed I is 3:1, total volume space velocity of 2h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 2
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with mass concentration of 35% 2 Titrating with ammonia water to remove white precipitate, washing with deionized water, filtering to remove chloride ion, drying at 80 deg.C for 5 hr to obtain white powder, squeezing with conventional methodThe strands were dried at 80 ℃ for 4 hours after molding and then calcined at 450 ℃ for 4 hours to give white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 3mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 7mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.2 mol/L. 3. Dipping the white solid particles obtained in the first step by using a silver nitrate sulfuric acid solution, and keeping the vacuum degree at 17000Pa; the ultrasonic vibration frequency is 55kHz; the dipping temperature is 60 ℃, and the dipping time is 4 hours; after filtration, the mixture was dried at 80 ℃ for 6 hours and then calcined at 450 ℃ for 4 hours to obtain granules I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain the metal-doped solid super acidic catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 100 ℃, the reaction pressure is 3.0MPa, and the molar ratio of isobutene to phenol in the feed I is 4:1, total volume space velocity of 2h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 3
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with the mass concentration of 40 percent 2 And (3) titrating the ethanol solution by using ammonia water until no white precipitate is generated, washing by using deionized water, filtering until no chloride ion is generated, drying for 4 hours at 80 ℃ to obtain white powder, extruding and molding by using a conventional method, drying for 6 hours at 90 ℃, and roasting for 4 hours at 550 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare silver nitrate sulfuric acid solution with the molar concentration of 3mol/L,dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare nickel nitrate sulfuric acid solution with the molar concentration of 8mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare palladium nitrate sulfuric acid solution with the molar concentration of 0.2 mol/L. 3. Dipping the white solid particles obtained in the first step by using a silver nitrate sulfuric acid solution, and keeping the vacuum degree at 18000Pa; the ultrasonic vibration frequency is 56kHz; dipping at 55 ℃ for 4 h; after filtration, the mixture was dried at 80 ℃ for 6 hours and then calcined at 450 ℃ for 4 hours to obtain granules I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and conditions in the step three to obtain white particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and conditions in the step three to obtain the metal-doped solid super acid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 100 ℃, the reaction pressure is 3.0MPa, and the molar ratio of isobutene to phenol in the feed I is 3:1, total volume space velocity of 2h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 4
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with the mass concentration of 45% 2 And (2) titrating the ethanol solution by using ammonia water until no white precipitate is generated, washing by using deionized water, filtering until no chlorine ion is generated, drying for 4 hours at 90 ℃ to obtain white powder, extruding the white powder into strips by using a conventional method, drying for 4 hours at 80 ℃, and roasting for 4 hours at 500 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 4mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 8mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.4mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.3mol/L. 3. With silver nitrateDipping the white solid particles obtained in the first step by using a sulfuric acid solution under the vacuum degree of 18000Pa; the ultrasonic vibration frequency is 59kHz; the dipping temperature is 60 ℃, and the dipping time is 4 h; after filtration, the mixture was dried at 90 ℃ for 6 hours and then calcined at 500 ℃ for 4 hours to obtain granules I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain the metal-doped solid super acidic catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 110 ℃, the reaction pressure is 4.0MPa, and the molar ratio of isobutene to phenol in the feed I is 4:1, the total volume space velocity is 2.5h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 5
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with mass concentration of 50% 2 And (3) titrating the ethanol solution by using ammonia water until no white precipitate is generated, washing by using deionized water, filtering until no chloride ion is generated, drying for 4 hours at 90 ℃ to obtain white powder, extruding the white powder into strips by using a conventional method, drying for 6 hours at 90 ℃, and roasting for 6 hours at 450 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 2mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 5mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.5mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.1 mol/L. 3. Dipping the white solid particles obtained in the first step by using a silver nitrate sulfuric acid solution, wherein the vacuum degree is 16000Pa; the ultrasonic vibration frequency is 50kHz; dipping at 55 ℃ for 4 h; filtering, drying at 80 deg.C for 6 hr, and drying at 500 deg.CCalcining for 4 hours under the condition to obtain the particles I. 4. And (3) treating the particles I by using the nickel nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain particles II, and treating the particles II by using the palladium nitrate sulfuric acid solution prepared in the step two according to the method and the conditions in the step three to obtain the metal-doped solid super acidic catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 110 ℃, the reaction pressure is 4.0MPa, and the molar ratio of isobutene to phenol in the feed I is 4:1, the total volume space velocity is 2.5h -1 B, carrying out the following steps of; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Example 6
1. Preparing a metal-doped solid super acidic catalyst: 1. 50 g of ZrOCl 2 Dissolving in ethanol to prepare ZrOCl with mass concentration of 40% 2 Titrating the ethanol solution by ammonia water until no white precipitate is generated, washing by deionized water, filtering until no chloride ion is generated, drying for 4 hours at 80 ℃ to obtain white powder, extruding the white powder by a conventional method, drying for 5 hours at 70 ℃, and roasting for 5 hours at 450 ℃ to obtain white solid particles. 2. Dissolving silver nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a silver nitrate sulfuric acid solution with the molar concentration of 2mol/L, dissolving nickel nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a nickel nitrate sulfuric acid solution with the molar concentration of 5mol/L, and dissolving palladium nitrate in dilute sulfuric acid with the molar concentration of 0.3mol/L to prepare a palladium nitrate sulfuric acid solution with the molar concentration of 0.1 mol/L. 3. Dipping the white solid particles obtained in the first step by using a silver nitrate sulfuric acid solution, and keeping the vacuum degree at 17000Pa; the ultrasonic vibration frequency is 55kHz; dipping at 55 ℃ for 4 h; after filtration, the mixture was dried at 80 ℃ for 6 hours and then calcined at 550 ℃ for 4 hours to obtain granules I. 4. Treating the particles I with the nickel nitrate sulfuric acid solution prepared in the second step according to the method and conditions of the third step to obtain particles II, and treating with the palladium nitrate sulfuric acid solution prepared in the second step according to the method and conditions of the third stepThe particles II give the metal-doped solid superacid catalyst.
2. The reaction is carried out on a fixed bed continuous reactor with horizontally staggered catalyst bed plates, and 60ml of catalyst is filled in the reactor and uniformly filled on the catalyst bed plates; the reaction temperature is 100 ℃, the reaction pressure is 3.0MPa, and the molar ratio of isobutene to phenol in the feed I is 3:1, total volume space velocity of 2h -1 A step of,; the volume space velocity of isobutene to the catalyst in the feed II is 1.5h -1 The reaction results are shown in Table 1.
Comparative example 1
The catalyst used in the reaction was D005 II type resin catalyst, the other conditions were the same as in example 4, and the reaction results are shown in Table 1.
Comparative example 2
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.
Comparative example 3
In the reaction process, the fixed bed reactor has no bed plate in the middle, other conditions are the same as example 4, and the reaction results are shown in Table 1.
Comparative example 4
The preparation process of the catalyst used has no ultrasonic vibration and pressurization operation process, the modified solution is not impregnated according to the specified sequence, only the catalyst is modified by adopting the conventional impregnation method, the other conditions are the same as 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