CN111960925B - Preparation method of 2, 6-di-tert-butyl-p-cresol - Google Patents
Preparation method of 2, 6-di-tert-butyl-p-cresol Download PDFInfo
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- CN111960925B CN111960925B CN202010719165.XA CN202010719165A CN111960925B CN 111960925 B CN111960925 B CN 111960925B CN 202010719165 A CN202010719165 A CN 202010719165A CN 111960925 B CN111960925 B CN 111960925B
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Abstract
The invention relates to a preparation method of 2, 6-di-tert-butyl-p-cresol, belonging to the technical field of organic chemical synthesis. The invention utilizes a modified mesoporous silica-loaded Nb/Mo/Cu trimetal active center catalyst as a catalyst, mixes m-cresol and isobutylene as raw materials, and carries out ultrasonic cavitation in the catalytic reaction process to further prepare the 2, 6-di-tert-butyl-p-cresol. The mixed cresol is adopted as a raw material, the cost can be reduced, the m-cresol is separated while the 2, 6-di-tert-butyl-p-cresol is prepared, and researches show that the conversion rate of the mixed cresol and the selectivity of the di-tert-butyl cresol, particularly the selectivity of the 2, 6-di-tert-butyl-p-cresol are greatly improved under the synergistic catalytic action of a trimetallic active center in a modified mesoporous silica loaded Nb/Mo/Cu trimetallic active center catalyst, the generation of impurities such as the 2-tert-butyl-p-cresol and the 6-tert-butyl-m-cresol is reduced, meanwhile, a liquid-gas reaction is promoted to form a micro-reactor in micropores on a solid catalyst under the ultrasonic cavitation action, the catalytic activity is greatly improved, the mass transfer efficiency and the heat transfer area of a gas phase and a liquid-gas phase are increased, and the conversion rate.
Description
Technical Field
The invention relates to a preparation method of 2, 6-di-tert-butyl-p-cresol, belonging to the technical field of organic chemical synthesis.
Background
2, 6-di-tert-butyl-p-cresol (BHT) is a common phenolic antioxidant, is widely used in the industries of food processing, feed additives, petroleum products, plastic rubber and the like, and is a multipurpose, non-colored and largest-dosage phenolic antioxidant.
At present, the production process of producing antioxidant BHT by reaction of isobutene and p-cresol under the action of a catalyst is mostly adopted at home and abroad, and the catalyst is subjected to evolution of liquid concentrated sulfuric acid and solid sulfonic acid. Chinese patent CN 103694085B reports that p-cresol and isobutanol are used as raw materials, and concentrated sulfuric acid is added as a catalyst to synthesize antioxidant BHT; the method not only produces a large amount of waste water and has low synthesis efficiency, but also uses a concentrated sulfuric acid catalyst to seriously corrode equipment. Chinese patent CN102311318A reports that p-cresol and isobutylene are used as raw materials, and p-arylsulfonic acid is added as a catalyst to synthesize 2, 6-di-tert-butyl-p-cresol; although isobutene is used as an alkylating reagent in the method, although no waste water by-product exists, aryl sulfonic acid can generate larger corrosion to a reactor, and in addition, p-cresol is used as a raw material, so the cost is higher.
However, in the existing solid catalyst, as reported in chinese patent CN107737605A, a modified molecular sieve selected from any one of ammonium phosphate, ammonium hydrogen phosphate and ammonium dihydrogen phosphate is used as a carrier to load an active component a and an active component B, wherein the molecular sieve is an H β molecular sieve, a hydrogen mordenite, an HY molecular sieve, a USY molecular sieve, a REY molecular sieve or an SAPO-5 molecular sieve, the active component a is Co, Cu, Ni or Fe, and the active component B is at least one of phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid and sodium tungstate, but the problems of low conversion rate of raw materials and low selectivity of products still exist.
The problem that mixed cresol (m-cresol and p-cresol) is not easy to separate exists in the prior art, for example, Chinese patent CN102898281A reports that mixed m-cresol and p-cresol are mixed with isobutene in the presence of sulfuric acid or solid S-ZrO2The three products of 2, 6-di-tert-butyl-p-cresol, m-cresol and 6-tert-butyl-m-cresol are co-produced by alkylation reaction under the catalytic action of the catalyst and rectification, but the problem of equipment corrosion when sulfuric acid is adopted still exists in the patent, and S-ZrO is adopted2The conversion rate of raw materials is low, and the selectivity of 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol is low.
At present, the liquid catalyst still has great corrosivity, and the solid catalyst still has the problems of low conversion rate of raw materials and low selectivity of products.
Disclosure of Invention
The invention aims to provide a preparation method of 2, 6-di-tert-butyl-p-cresol, which utilizes a modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst as a catalyst, mixes m-p-cresol and isobutene as raw materials, and carries out ultrasonic cavitation in the catalytic reaction process to further prepare the 2, 6-di-tert-butyl-p-cresol. The mixed cresol is adopted as a raw material, the cost can be reduced, the m-cresol is separated while the 2, 6-di-tert-butyl-p-cresol is prepared, and researches show that the conversion rate of the mixed cresol and the selectivity of the product di-tert-butyl-cresol, particularly the selectivity of the 2, 6-di-tert-butyl-p-cresol, are greatly improved by the synergistic catalytic action of a trimetal active center in a modified mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst, the generation of impurities such as the 2-tert-butyl-p-cresol and the 6-tert-butyl-m-cresol is reduced, meanwhile, a microreactor is formed in micropores on a solid catalyst through liquid-gas reaction under the action of ultrasonic cavitation, the catalytic activity is greatly improved, the mass transfer efficiency and the heat transfer area of a gas phase and a liquid-gas phase are increased, and the conversion rate of the.
The technical scheme for solving the problems is as follows:
a preparation method of 2, 6-di-tert-butyl-p-cresol comprises the following specific steps:
(1) liquefied isobutene from a tank car is connected to a liquefied hydrocarbon loading arm, after safety facilities such as electrostatic grounding and the like are completely connected and checked to be correct, a liquefied hydrocarbon unloading pump is started, and the liquefied hydrocarbon loading arm is unloaded to an isobutene liquefied buried storage tank; conveying nitrogen to an isobutene liquefaction storage tank by adopting a pipeline, and pressing liquefied isobutene into an isobutene gasifier by using an adjusting valve; heating the isobutene gasifier by hot water at 75-80 ℃, and introducing the gasified isobutene into a gas storage tank under the pressure of 0.27-0.3 MPa; adding the modified mesoporous silica-loaded Nb/Mo/Cu trimetal active center catalyst into an alkylation reaction kettle after metering; the liquid mixed m-cresol and p-cresol enter an alkylation reaction kettle from an intermediate storage tank through a delivery pump, a regulating valve and a flowmeter, wherein the mass ratio of the mixed m-cresol and the modified mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst is 20-30: 1;
(2) after mixed m-cresol and p-cresol are added, the raw material isobutene is introduced after the flow is controlled by a flowmeter, ultrasonic cavitation is carried out, the ultrasonic power is 750-850W, the ultrasonic frequency is 30-35kHz, the water inflow is adjusted by a jacket circulating water flow adjusting valve of an alkylation reaction kettle, the temperature of the alkylation reaction kettle is controlled at 60-65 ℃, and alkylation reaction is carried out; the DCS is used for adjusting the isobutene adjusting valve to control the introduction speed of isobutene, and bubble-free isobutene in the vessel neck isobutene recovery tube sight glass is suitable; the alkylation reaction time is 6-7.5 h; after the reaction is finished, the temperature is reduced, the mixture is kept stand until the alkylated liquid and the catalyst are layered, the alkylated liquid is sprayed into an alkyl qualified liquid tank through a pump, the alkylated liquid is sent into a drying kettle through the pump to be subjected to intermittent distillation, the distillation temperature is 180 ℃, the reaction kettle adopts reduced pressure distillation, light component 2, 5-dimethyl hexane overflows to a distillation head extraction tank through tower top condensation, the light component extraction tank is sent to a light component storage tank through the pump to be sold as a product, the qualified alkylated liquid is subjected to multistage rectification, and goes to a 2, 6-di-tert-butyl-p-cresol refining workshop all the way to obtain 2, 6-di-tert-butyl-p-cresol, goes to a 4, 6-di-tert-butyl-m-cresol decomposition workshop all the way to decompose 4, 6-di-tert-butyl-m.
Further, the preparation method of the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst in the step (1) comprises the following steps: soaking 100g of mesoporous silica in aqueous solution of niobium pentachloride, molybdenum pentachloride and copper sulfate, continuously stirring for 5-6 hours, taking out, and heating and drying at 90-100 ℃ for 8-10 hours; roasting the loaded mesoporous silica in a high-temperature furnace at the roasting temperature of 350-400 ℃ for 1.5-2h, cooling to obtain a mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst, soaking the prepared catalyst in a silicotungstic acid solution with the mass concentration of 2.8-3.0% for 10 hours, filtering, washing, and drying at 100 ℃ to obtain a modified mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst, wherein the total niobium loading is 2.1-2.3% of the weight of the mesoporous silica by the weight of Nb; the total loading of molybdenum is 1.0-1.3% of the weight of the mesoporous silica, based on the weight of Mo; the total copper loading is 0.5-0.8% of the weight of the mesoporous silica, based on the weight of Cu; the specific surface area of the mesoporous silica is 345.5m2In g, the mean pore diameter is 15 nm.
Further, in the step (1), in the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst, the total niobium supported amount is 2.1% of the weight of the mesoporous silica, based on the weight of Nb;the total loading of molybdenum is 1.3 percent of the weight of the mesoporous silica, based on the weight of Mo; the total loading of copper is 0.8 percent of the weight of the mesoporous silica, and the specific surface area of the mesoporous silica is 345.5m2In g, the mean pore diameter is 15 nm.
In the preparation method of the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst, the catalyst is preferably immersed in the solution continuously stirred for 5 hours, then taken out and heated and dried at 90 ℃ for 10 hours.
Further, in the preparation method of the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst, the mass concentration of the silicotungstic acid solution is 3.0%.
Further, in the step (1), the mass ratio of the mixed m-cresol and the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst is 20: 1.
Further, in the step (1), the temperature of the hot water is 80 ℃, and the pressure of the storage tank is 0.3 MPa.
Further, in the step (2), the ultrasonic power is 850W, and the ultrasonic frequency is 35 kHz.
Further, in the step (2), the temperature of the alkylation reaction kettle is controlled at 65 ℃, and the alkylation reaction time is 7.5 hours.
Further, in the step (2), the conversion rate of the mixed m-cresol and p-cresol is more than 99.85%, the selectivity of the 2, 6-di-tert-butyl-p-cresol is more than 90.32%, and the total mass content of the 2, 6-di-tert-butyl-p-cresol and the 4, 6-di-tert-butyl-m-cresol in the alkylation liquid is more than 90%.
The invention has the beneficial effects that:
(1) the invention adopts the solid catalyst to replace the liquid catalyst, has simple process and no pollution, obviously reduces the corrosion to equipment caused by using the liquid catalyst, and obviously prolongs the service life of the equipment.
(2) The invention utilizes the synergistic catalytic action of the trimetal active center in the modified mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst to greatly improve the conversion rate of mixed m-cresol and the selectivity of a product 2, 6-di-tert-butyl-p-cresol, simultaneously utilizes the cavitation action of ultrasound and shock waves and micro-jet flow formed in a solution under the action of ultrasonic cavitation to promote liquid-gas reaction to form a micro-reactor in micropores on a solid catalyst, greatly improves the catalytic activity, increases the mass transfer efficiency and the heat transfer area of gas-liquid two phases, further improves the conversion rate of mixed m-cresol and the selectivity of the product 2, 6-di-tert-butyl-p-cresol, the conversion rate of mixed m-cresol is more than 99.85 percent, and the selectivity of 2, 6-di-tert-butyl-p-cresol is more than 90.32 percent, the content of the impurity, namely mono-tert-butyl cresol is obviously reduced, and the 4, 6-di-tert-butyl-m-cresol is decomposed to obtain an m-cresol product and isobutene, wherein the isobutene can be used as a raw material; the total mass content of 2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol in the alkylation liquid is more than 90 percent, and only a small amount of impurities such as 2-tert-butyl-p-cresol and 6-tert-butyl-m-cresol are contained.
Detailed Description
Example 1:
a preparation method of 2, 6-di-tert-butyl-p-cresol comprises the following specific steps:
(1) liquefied isobutene from a tank car is connected to a liquefied hydrocarbon loading arm, after safety facilities such as electrostatic grounding and the like are completely connected and checked to be correct, a liquefied hydrocarbon unloading pump is started, and the liquefied hydrocarbon loading arm is unloaded to an isobutene liquefied buried storage tank; conveying nitrogen to an isobutene liquefaction storage tank by adopting a pipeline, and pressing liquefied isobutene into an isobutene gasifier by using an adjusting valve; the isobutene gasifier is heated by hot water, the temperature of the hot water is 80 ℃, isobutene is gasified and then enters a gas storage tank, and the pressure of the storage tank is 0.3 MPa; adding the modified mesoporous silica-loaded Nb/Mo/Cu trimetal active center catalyst into an alkylation reaction kettle after metering; and the liquid mixed m-cresol and p-cresol enter an alkylation reaction kettle from an intermediate storage tank through a delivery pump, a regulating valve and a flowmeter, wherein the mass ratio of the mixed m-cresol to the modified catalyst is 20: 1.
(2) After adding mixed m-cresol and p-cresol, introducing isobutylene serving as a raw material after controlling the flow through a flow meter, performing ultrasonic cavitation, adjusting the water inlet flow by using a jacket circulating water flow adjusting valve of an alkylation reaction kettle, and controlling the temperature of the alkylation reaction kettle at 65 ℃ to perform alkylation reaction, wherein the ultrasonic power is 850W and the ultrasonic frequency is 35 kHz; the DCS is used for adjusting the isobutene adjusting valve to control the introduction speed of isobutene, and bubble-free isobutene in the vessel neck isobutene recovery tube sight glass is suitable; the alkylation reaction time is 7.5 h; after the reaction is finished, the temperature is reduced, the mixture is kept stand until the alkylated liquid and the catalyst are layered, the alkylated liquid is sprayed into an alkyl qualified liquid tank through a pump, the alkylated liquid is sent into a drying kettle through the pump to be subjected to intermittent distillation, the distillation temperature is 180 ℃, the reaction kettle adopts reduced pressure distillation, light component 2, 5-dimethyl hexane overflows to a distillation head extraction tank through tower top condensation, the light component extraction tank is sent to a light component storage tank through the pump to be sold as a product, the qualified alkylated liquid is subjected to multistage rectification, and goes to a 2, 6-di-tert-butyl-p-cresol refining workshop all the way to obtain 2, 6-di-tert-butyl-p-cresol, goes to a 4, 6-di-tert-butyl-m-cresol decomposition workshop all the way to decompose 4, 6-di-tert-butyl-m. Wherein the conversion rate of the mixed m-cresol and p-cresol is 99.85 percent, the selectivity of the 2, 6-di-tert-butyl-p-cresol is 90.80 percent, the total mass content of the 2, 6-di-tert-butyl-p-cresol and the 4, 6-di-tert-butyl-m-cresol in the alkylation liquid is more than 90 percent, and only a small amount of impurities such as the 2-tert-butyl-p-cresol, the 6-tert-butyl-m-cresol and the like are contained.
The preparation method of the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst comprises the following steps: 100g of mesoporous silica is soaked in aqueous solution of niobium pentachloride, molybdenum pentachloride and copper sulfate, continuously stirred for 5 hours, taken out and heated and dried for 10 hours at 90 ℃. Roasting the loaded mesoporous silica in a high-temperature furnace at 350 ℃ for 2 hours, cooling to obtain the mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst, soaking the catalyst in a silicotungstic acid solution with the mass concentration of 3.0% for 10 hours, filtering, washing, and drying at 100 ℃ to obtain the modified mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst. Wherein the total niobium loading is 2.1 percent of the weight of the mesoporous silica, based on the weight of Nb; the total loading of molybdenum is 1.3 percent of the weight of the mesoporous silica, based on the weight of Mo; the total copper loading is 0.8 percent of the weight of the mesoporous silica according to the weight of CuCounting; the specific surface area of the mesoporous silica is 345.5m2In g, the mean pore diameter is 15 nm.
Example 2: a preparation method of 2, 6-di-tert-butyl-p-cresol comprises the following specific steps:
(1) liquefied isobutene from a tank car is connected to a liquefied hydrocarbon loading arm, after safety facilities such as electrostatic grounding and the like are completely connected and checked to be correct, a liquefied hydrocarbon unloading pump is started, and the liquefied hydrocarbon loading arm is unloaded to an isobutene liquefied buried storage tank; conveying nitrogen to an isobutene liquefaction storage tank by adopting a pipeline, and pressing liquefied isobutene into an isobutene gasifier by using an adjusting valve; the isobutene gasifier is heated by hot water, the temperature of the hot water is 75 ℃, isobutene is gasified and then enters a gas storage tank, and the pressure of the storage tank is 0.27 MPa; adding the modified mesoporous silica-loaded Nb/Mo/Cu trimetal active center catalyst into an alkylation reaction kettle after metering; and the liquid mixed m-cresol and p-cresol enter an alkylation reaction kettle from an intermediate storage tank through a delivery pump, a regulating valve and a flowmeter, wherein the mass ratio of the mixed m-cresol to the modified catalyst is 30: 1.
(2) After adding mixed m-cresol and p-cresol, introducing isobutylene serving as a raw material after controlling the flow through a flow meter, performing ultrasonic cavitation, adjusting the water inlet flow by using a jacket circulating water flow adjusting valve of an alkylation reaction kettle, and controlling the temperature of the alkylation reaction kettle at 60 ℃ to perform alkylation reaction, wherein the ultrasonic power is 750W and the ultrasonic frequency is 30 kHz; the DCS is used for adjusting the isobutene adjusting valve to control the introduction speed of isobutene, and bubble-free isobutene in the vessel neck isobutene recovery tube sight glass is suitable; the alkylation reaction time is 6 hours; after the reaction is finished, the temperature is reduced, the mixture is kept stand until the alkylated liquid and the catalyst are layered, the alkylated liquid is sprayed into an alkyl qualified liquid tank through a pump, the alkylated liquid is sent into a drying kettle through the pump to be subjected to intermittent distillation, the distillation temperature is 180 ℃, the reaction kettle adopts reduced pressure distillation, light component 2, 5-dimethyl hexane overflows to a distillation head extraction tank through tower top condensation, the light component extraction tank is sent to a light component storage tank through the pump to be sold as a product, the qualified alkylated liquid is subjected to multistage rectification, and goes to a 2, 6-di-tert-butyl-p-cresol refining workshop all the way to obtain 2, 6-di-tert-butyl-p-cresol, goes to a 4, 6-di-tert-butyl-m-cresol decomposition workshop all the way to decompose 4, 6-di-tert-butyl-m. Wherein the conversion rate of the mixed m-cresol and p-cresol is 99.88 percent, the selectivity of the 2, 6-di-tert-butyl-p-cresol is 90.32 percent, the total mass content of the 2, 6-di-tert-butyl-p-cresol and the 4, 6-di-tert-butyl-m-cresol in the alkylation liquid is more than 90 percent, and the impurities such as the 2-tert-butyl-p-cresol, the 6-tert-butyl-m-cresol and the like are less.
The preparation method of the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst comprises the following steps: 100g of mesoporous silica is soaked in aqueous solution of niobium pentachloride, molybdenum pentachloride and copper sulfate, continuously stirred for 6 hours, taken out and heated and dried for 8 hours at 1000 ℃. Roasting the loaded mesoporous silica in a high-temperature furnace at 400 ℃ for 1.5h, cooling to obtain the mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst, soaking the catalyst in a silicotungstic acid solution with the mass concentration of 2.8% for 10h, filtering, washing, and drying at 100 ℃ to obtain the modified mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst. Wherein the total niobium loading is 2.3 percent of the weight of the mesoporous silica, based on the weight of Nb; the total loading of molybdenum is 1.0 percent of the weight of the mesoporous silica, based on the weight of Mo; the total loading of copper is 0.5 percent of the weight of the mesoporous silica, wherein the specific surface area of the mesoporous silica is 345.5m based on the weight of Cu2In g, the mean pore diameter is 15 nm.
Comparative example 1: the specific steps of the preparation method of 2, 6-di-tert-butyl-p-cresol are the same as those of the example 1, except that the ultrasonic cavitation is not carried out in the step (2), and other steps are the same. Wherein the conversion rate of the mixed m-cresol and p-cresol is 86.30 percent, the selectivity of the 2, 6-di-tert-butyl-p-cresol is 87.40 percent, and the alkylation liquid contains less impurities such as 2-tert-butyl-p-cresol, 6-tert-butyl-m-cresol and the like.
Comparative example 2: the specific steps of the preparation method of 2, 6-di-tert-butyl-p-cresol are the same as those of example 1, except that niobium pentachloride is not added in the preparation method of the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst, namely Nb is not supported, and other steps are the same. Wherein the conversion rate of the mixed m-cresol and p-cresol is 68.20 percent, the selectivity of the 2, 6-di-tert-butyl-p-cresol is 75.20 percent, and the alkylation liquid contains more impurities such as 2-tert-butyl-p-cresol, 6-tert-butyl-m-cresol and the like.
Comparative example 3: the specific steps of the preparation method of 2, 6-di-tert-butyl-p-cresol are the same as those of example 1, except that molybdenum pentachloride is not added in the preparation method of the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst, namely Mo is not supported, and other steps are the same. Wherein the conversion rate of mixed m-cresol and p-cresol is 70.35%, the selectivity of 2, 6-di-tert-butyl-p-cresol is 78.43%, and the alkylation liquid contains more 2-tert-butyl-p-cresol and 6-tert-butyl-m-cresol.
Comparative example 4: the specific steps of the preparation method of 2, 6-di-tert-butyl-p-cresol are the same as those of example 1, except that copper sulfate, namely no Cu is loaded in the preparation method of the modified mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst, and other steps are the same. Wherein the conversion rate of the mixed m-cresol and p-cresol is 71.33%, the selectivity of the 2, 6-di-tert-butyl-p-cresol is 76.56%, and the alkylation liquid contains more 2-tert-butyl-p-cresol and 6-tert-butyl-m-cresol.
From the above analysis, it is found that in the production method of example 1-2, the conversion of mixed m-p-cresol is 99.85% or more, and the selectivity of 2, 6-di-t-butyl-p-cresol is 90.32% or more; compared with the comparative example 1, the ultrasonic cavitation greatly improves the conversion rate of mixed m-cresol and p-cresol, and simultaneously improves the selectivity of 2, 6-di-tert-butyl-p-cresol, because under the action of the ultrasonic cavitation, liquid-gas reaction is promoted to form a micro-reactor in micropores on a solid catalyst, the catalytic activity is greatly improved, the mass transfer efficiency and the heat transfer area of gas-liquid two phases are increased, and the conversion rate of mixed m-cresol and p-cresol is further improved; compared with comparative examples 2-4, the modified mesoporous silica supported Nb/Mo/Cu trimetallic active center catalyst has synergistic effect of eliminating any one or two metals, obviously reduced catalytic activity, greatly reduced conversion rate of mixed m-cresol and selectivity of di-tert-butyl cresol (2, 6-di-tert-butyl-p-cresol and 4, 6-di-tert-butyl-m-cresol), especially selectivity of 2, 6-di-tert-butyl-p-cresol, and increased content of impurity mono-tert-butyl cresol (2-tert-butyl-p-cresol and 6-tert-butyl-m-cresol).
The present invention is not limited to the above exemplary embodiments, and any modifications, equivalent replacements, and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. A preparation method of 2, 6-di-tert-butyl-p-cresol comprises the following specific steps:
(1) liquefied isobutene from a tank car is connected to a liquefied hydrocarbon loading arm, after the electrostatic grounding safety facility is completely connected and is checked to be correct, a liquefied hydrocarbon unloading pump is started, and the liquefied hydrocarbon loading arm is unloaded to an isobutene liquefied buried storage tank; conveying nitrogen to an isobutene liquefaction storage tank by adopting a pipeline, and pressing liquefied isobutene into an isobutene gasifier by using an adjusting valve; heating the isobutene gasifier by hot water at 75-80 ℃, and introducing the gasified isobutene into a gas storage tank under the pressure of 0.27-0.3 MPa; adding the modified mesoporous silica-loaded Nb/Mo/Cu trimetal active center catalyst into an alkylation reaction kettle after metering; the liquid mixed m-cresol and p-cresol enter an alkylation reaction kettle from an intermediate storage tank through a delivery pump, a regulating valve and a flowmeter, wherein the mass ratio of the mixed m-cresol and the modified mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst is 20-30: 1;
(2) after mixed m-cresol and p-cresol are added, the raw material isobutene is introduced after the flow is controlled by a flowmeter, ultrasonic cavitation is carried out, the ultrasonic power is 750-850W, the ultrasonic frequency is 30-35kHz, the water inflow is adjusted by a jacket circulating water flow adjusting valve of an alkylation reaction kettle, the temperature of the alkylation reaction kettle is controlled at 60-65 ℃, and alkylation reaction is carried out; the DCS is used for adjusting the isobutene adjusting valve to control the introduction speed of isobutene, and bubble-free isobutene in the vessel neck isobutene recovery tube sight glass is suitable; the alkylation reaction time is 6-7.5 h; after the reaction is finished, cooling and standing until an alkylation liquid and a catalyst are layered, spraying the alkylation liquid into an alkyl qualified liquid tank through a pump, sending the alkyl qualified liquid tank into a drying kettle through the pump for intermittent distillation, wherein the distillation temperature is 180 ℃, the reaction kettle adopts reduced pressure distillation, light component 2, 5-dimethyl hexane overflows to a distillation head extraction tank through tower top condensation, and is sent to a light component storage tank through the pump to be sold as a product, the qualified alkylation liquid is subjected to multistage rectification, and goes to a 2, 6-di-tert-butyl-p-cresol refining workshop all the way to obtain 2, 6-di-tert-butyl-p-cresol, goes to a 4, 6-di-tert-butyl-m-cresol decomposition workshop all the way to decompose 4, 6-di-tert-butyl-m-cresol into m-cresol and isobutene, and the isobutene;
the preparation method of the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst in the step (1) comprises the following steps: soaking 100g of mesoporous silica in aqueous solution of niobium pentachloride, molybdenum pentachloride and copper sulfate, continuously stirring for 5-6 hours, taking out, and heating and drying at 90-100 ℃ for 8-10 hours; roasting the loaded mesoporous silica in a high-temperature furnace at the roasting temperature of 350-400 ℃ for 1.5-2h, cooling to obtain a mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst, soaking the prepared catalyst in a silicotungstic acid solution with the mass concentration of 2.8-3.0% for 10 hours, filtering, washing, and drying at 100 ℃ to obtain a modified mesoporous silica loaded Nb/Mo/Cu trimetal active center catalyst, wherein the total niobium loading is 2.1-2.3% of the weight of the mesoporous silica by the weight of Nb; the total loading of molybdenum is 1.0-1.3% of the weight of the mesoporous silica, based on the weight of Mo; the total copper loading is 0.5-0.8% of the weight of the mesoporous silica, based on the weight of Cu; the specific surface area of the mesoporous silica is 345.5m2In g, the mean pore diameter is 15 nm.
2. The preparation method according to claim 1, wherein in the step (1), the modified mesoporous silica supported Nb/Mo/Cu trimetallic active center catalyst has a total niobium loading of 2.1% by weight of the mesoporous silica, based on the weight of Nb; the total loading of molybdenum is 1.3 percent of the weight of the mesoporous silica, based on the weight of Mo; the total loading of copper is 0.8 percent of the weight of the mesoporous silica, and the specific surface area of the mesoporous silica is 345.5m2In g, the mean pore diameter is 15 nm.
3. The method according to claim 2, wherein the modified mesoporous silica supported Nb/Mo/Cu trimetal active center catalyst in the step (1) is prepared by continuously stirring for 5 hours, immersing, taking out, and heating and drying at 90 ℃ for 10 hours.
4. The preparation method according to claim 1 or 2, wherein in the preparation method of the modified mesoporous silica supported Nb/Mo/Cu trimetallic active site catalyst in the step (1), the silicotungstic acid solution has a mass concentration of 3.0%.
5. The preparation method according to claim 1 or 2, wherein in the step (1), the mass ratio of the mixed m-cresol and modified mesoporous silica supported Nb/Mo/Cu trimetallic active center catalyst is 20: 1.
6. The production method according to claim 1 or 2, wherein in the step (1), the temperature of the hot water is 80 ℃ and the pressure in the tank is 0.3 MPa.
7. The production method according to claim 1 or 2, wherein in the step (2), the ultrasonic power is 850W and the ultrasonic frequency is 35 kHz.
8. The preparation method according to claim 1 or 2, wherein in the step (2), the temperature of the alkylation reaction kettle is controlled at 65 ℃ and the alkylation reaction time is 7.5 h.
9. The process according to claim 1 or 2, wherein in the step (2), the conversion of mixed m-cresol and p-cresol is 99.85% or more, and the selectivity of 2, 6-di-t-butyl-p-cresol is 90.32% or more.
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| CN113952965A (en) * | 2021-10-15 | 2022-01-21 | 南京工业大学 | Stable double-active-component solid acid catalyst, preparation method and application thereof |
| CN114956963B (en) * | 2022-06-16 | 2023-10-24 | 河北工业大学 | Method for preparing 2, 6-di-tert-butyl-p-cresol from furan 2, 5-dicarboxaldehyde dioxime |
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