CN113651678A - Method for synthesizing alkylphenol and application thereof - Google Patents

Method for synthesizing alkylphenol and application thereof Download PDF

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Publication number
CN113651678A
CN113651678A CN202010395827.2A CN202010395827A CN113651678A CN 113651678 A CN113651678 A CN 113651678A CN 202010395827 A CN202010395827 A CN 202010395827A CN 113651678 A CN113651678 A CN 113651678A
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Prior art keywords
phenol
resin
lewis acid
modified
decene
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Inventor
任行涛
吴凯
何明阳
陈群
钱俊峰
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Priority to CN202010395827.2A priority Critical patent/CN113651678A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
    • C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
    • C07C37/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/32—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides a method for synthesizing alkylphenol and application thereof. The method for synthesizing alkylphenol provided by the invention comprises the step of contacting a raw material liquid containing olefin and phenol compounds with a modified resin, wherein the modified resin is an acidic cationic resin modified by Lewis acid. The method modifies the resin through Lewis acid modification, has high reaction efficiency, high activity and high selectivity, provides a high value-added utilization method of byproduct olefin, and is an effective way for reasonably utilizing resources.

Description

Method for synthesizing alkylphenol and application thereof
Technical Field
The invention relates to a method for synthesizing alkylphenol and application thereof.
Background
The long-chain alkylphenol is an important fine chemical intermediate, is mainly used for synthesizing phenolic resin, nonionic surfactant, antistatic agent, rubber antioxidant, paint, coating and the like, is also an important chemical raw material for preparing lubricating oil detergent sulfurized alkylphenol salt, and particularly, the long-chain alkylphenol polyoxyethylene ether obtained by reacting alkylphenol and ethylene oxide is an excellent chemical auxiliary agent, has the characteristics of stable property, acid and alkali resistance, low cost and the like, and is mainly used for products such as high-performance detergent, petroleum demulsifier, water-coal-slurry dispersant and the like.
Decyl phenol is synthesized by alkylation reaction with decene and phenol as raw materials and solid acid or liquid acid as a catalyst. The decene mainly comes from a byproduct of a hexene device, is mainly a series of isomer mixtures of alpha-olefin, contains a small amount of low-carbon olefin such as octene, is mainly sold as a fuel at present, and has low additional value, so that the enterprise profit can be greatly improved by realizing the high additional value development of the decene, and the preparation of products such as a nonionic surfactant and the like by using the decene and phenol alkylation reaction synthesized decyl phenol as an intermediate is a reliable way for high additional value utilization. The product mainly contains para-decyl phenol, a small amount of ortho-decyl phenol and dialkyl products, and a small amount of octyl phenol and the like.
Therefore, there is an urgent need for a catalyst for synthesizing alkylphenol having high reactivity and less dialkylated products.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for synthesizing alkylphenol, which takes Lewis acid modified strong acid cation resin as a catalyst, has high conversion rate of reaction olefin, high selectivity of alkylphenol product, low reaction temperature, less dialkylated product, stable product quality, simple device operation and higher reaction efficiency.
In a first aspect, the present invention provides a process for the synthesis of an alkylphenol comprising subjecting a feedstock comprising an olefin and a phenolic compound to a modificationThe resin is contacted, wherein the modified resin is an acidic cationic resin modified by Lewis acid. According to some embodiments of the invention, the lewis acid comprises AlCl3And MnCl2One or two of them.
According to a preferred embodiment of the invention, the lewis acid comprises AlCl3And MnCl2。
According to a preferred embodiment of the present invention, among the Lewis acids, AlCl3And MnCl2The mass ratio of (b) is 0.5:1 to 5:1, and may be, for example, 1:1, 2:1, 3:1, or 4: 1.
According to a further preferred embodiment of the present invention, among the lewis acids, AlCl3And MnCl2The mass ratio of (A) to (B) is 1:1-3.5: 1.
According to some embodiments of the invention, the acidic cation resin is selected from styrenic strongly acidic cation resins.
According to some embodiments of the invention, the contacting is carried out in a fixed bed reactor.
According to some embodiments of the invention, the feed solution has a temperature of 90 to 100 ℃.
According to some embodiments of the invention, the space velocity of the feed liquid is between 0.2 and 2.0h-1For example, it may be 0.4h-1、0.6h-1、0.8h-1、1.0h-1、1.2h-1、1.4h-1、1.6h-1。
According to a preferred embodiment of the invention, the space velocity of the feed liquid is between 0.5 and 1.0h-1。
In the invention, raw material liquid is fed by an injection pump, the loading volume of the fixed catalyst is unchanged, and the airspeed is controlled by adjusting the feeding flow and is 0.2-2.0h-1The contact time of the reaction liquid and the catalyst is determined by the space velocity, and the reaction efficiency, the reaction temperature and the like are influenced. The inventors of the present invention found that when the airspeed is preferably 0.5-1.0h-1Especially 0.6h-1The effect is more ideal.
According to some embodiments of the invention, the fixed bed continuous reactor is a tubular reactor.
According to some embodiments of the invention, the temperature of the contacting is 70-150 ℃, for example 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃.
According to a preferred embodiment of the invention, the temperature of said contacting is between 90 and 110 ℃.
The reaction tube of the invention adopts a three-section type electric heating mode to control the temperature, the temperature is 70-150 ℃, the reaction temperature is increased, the conversion rate of olefin can be improved, but the cracking of olefin and the generation of dialkyl products can be promoted, and the content of byproducts is increased. The inventors of the present invention have found that the effect is more desirable when the reaction temperature is from 90 to 110 c, in particular 100 c.
According to some embodiments of the invention, the molar ratio of olefin to phenolic compound in the feed solution is from 1:2 to 1:10, and may be, for example, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1: 9.
According to a preferred embodiment of the present invention, the molar ratio of the olefin to the phenol compound in the raw material liquid is 1:3 to 1: 5.
According to a preferred embodiment of the present invention, the molar ratio of the olefin to the phenol compound in the raw material liquid is 1:3.5 to 1: 4.5.
In the invention, the phenol alkylation reaction usually reduces the generation of dialkyl products in the product by excessive amount of the phenol compound, and improves the conversion rate of olefin, but the phenol compound is solid at normal temperature, the feed pipeline is easy to solidify and block due to the improvement of the content of the phenol compound, and the separation and purification cost of the product is correspondingly increased. The inventors of the present invention found that the reaction effect is more preferable when the molar ratio of the phenol compound to the olefin is 3.5:1 to 4.5: 1.
According to some embodiments of the invention, the olefin is a C8-C11 olefin.
According to a preferred embodiment of the invention, the olefin is decene, preferably 1-decene.
In the present invention, the term "phenolic compound" refers to benzene substituted with one or more hydroxyl groups, and may further have one or more substituents selected from the group consisting of C1-C6 alkyl, C1-C6 alkoxy and halogen on the benzene ring.
According to some embodiments of the invention, the phenolic compound is phenol (C)6H5OH)。
According to some embodiments of the invention, the method of preparing the modified resin comprises:
step A: contacting the acidic cation resin with the Lewis acid in an organic solvent to obtain Lewis acid modified acidic cation resin; and the number of the first and second groups,
optional step B: and washing and drying the Lewis acid modified acidic cationic resin to obtain the modified resin.
According to some embodiments of the invention, the washing comprises washing with ethanol 1-5 times, preferably 3 times, and then rinsing with deionized water until free of chloride ions, and drying for use.
According to some embodiments of the invention, prior to step a, the acidic cationic resin is swollen in an organic solvent.
According to some embodiments of the invention, the swelling time is 5 to 10 hours.
According to some embodiments of the invention, the organic solvent is selected from C1-C10 alkyl alcohols.
According to a preferred embodiment of the invention, the organic solvent is selected from the group consisting of C1-C6 alkyl alcohols.
According to a further preferred embodiment of the invention, the organic solvent is ethanol.
According to some embodiments of the invention, in step a, the lewis acid is present in an amount of 1 to 30 wt% of the acidic cationic resin.
According to a preferred embodiment of the invention, in step a, the weight of the lewis acid is 5 to 20 wt% of the acidic cationic resin.
According to a preferred embodiment of the invention, in step a, the weight of the lewis acid is 5 to 15 wt% of the acidic cationic resin.
According to some embodiments of the invention, the temperature of the contacting in step a is 70-90 ℃.
According to some embodiments of the invention, in step a, the contacting is for a time of 6 to 8 h.
According to some embodiments, the method comprises: the fixed bed is used as a reactor, the raw materials are decylene and phenol which are melted and mixed according to a proportion, the mixture is electrically heated to be kept at 90-100 ℃, the materials are fed through an injection pump according to a certain flow, all pipelines are kept at 70-90 ℃, a single reaction tube is adopted and vertically placed, the materials are fed from top to bottom, the outside of the reaction tube is heated by an electric heating furnace in a three-stage mode to be controlled at a certain temperature, reaction products enter a storage tank after being cooled, and the gas chromatography is adopted to analyze the composition of the products.
Compared with the synthesis of decyl phenol disclosed by the prior patent, the method adopts aluminum chloride and manganese chloride to modify the cationic resin, carries out coordination complex reaction, generates new acid centers, enhances the activity, can obtain higher reaction activity at lower reaction temperature, and simultaneously reduces the content of dialkylated products.
In a second aspect, the present invention provides the use of a process according to the first aspect of the claims in the production of alkyl phenols.
According to some embodiments of the invention, the alkylphenol is decylphenol, preferably 4-decylphenol (CAS 2985-57-1).
In a third aspect, the present invention provides an alkylphenol wherein the content of dialkylphenol is less than 6.5 wt%.
According to some embodiments of the invention, the content of the dialkylphenol is less than 6.0 wt%, such as less than 5.5 wt%, less than 5.0 wt%, less than 4.5 wt%, less than 4.0 wt%, less than 3.5 wt%.
According to a preferred embodiment of the invention, the content of said dialkylphenols is lower than 3.0 wt.%.
In a fourth aspect, the present invention provides an alkylphenol produced according to the process of the first aspect, wherein the content of dialkylphenol is less than 6.5 wt%.
According to some embodiments of the invention, the content of the dialkylphenol is less than 6.0 wt%, such as less than 5.5 wt%, less than 5.0 wt%, less than 4.5 wt%, less than 4.0 wt%, less than 3.5 wt%.
According to a preferred embodiment of the invention, the content of said dialkylphenols is lower than 3.0 wt.%.
The invention has the beneficial technical effects that: the invention provides a method for synthesizing alkylphenol by continuous reaction, the conversion rate of olefin can reach 99.4%, the selectivity of alkylphenol can reach 95.5%, the reaction efficiency is high, the activity is high, the selectivity is high, a high value-added utilization method of byproduct olefin is provided, and the method is an effective way for reasonably utilizing resources.
Detailed Description
The present invention will be more fully understood by those skilled in the art by describing the present invention in detail with reference to the following examples, which should not be construed as limiting the scope of the present invention in any way.
The resins used in the following examples are all macroporous strongly acidic styrenic cation exchange resins available from DA-330 of Special resins of Dandeng pearl, Inc.
In the examples and comparative examples, decene means 1-decene; decyl phenol refers to 4-decyl phenol.
Preparation example 1
Drying 50g of resin, swelling with ethanol for 6h, and adding 5g of AlCl3Stirring at 70 deg.C, refluxing in water bath for 6 hr, cooling and filtering after modification treatment, washing with ethanol for 3 times, washing with deionized water until no chloride ion exists, and drying.
Preparation example 2
Taking 50g of resin, drying, swelling with ethanol for 6h, and adding 5g of MnCl2Stirring at 70 deg.C, refluxing in water bath for 6 hr, cooling and filtering after modification treatment, washing with ethanol for 3 times, washing with deionized water until no chloride ion exists, and drying.
Preparation example 3
Drying 50g of resin, swelling with ethanol for 6h, and adding 2.5g of AlCl3And 2.5g of MnCl2Stirring at 70 deg.C, refluxing in water bath for 6 hr, cooling and filtering after modification treatment, washing with ethanol for 3 times, washing with deionized water until no chloride ion exists, and drying.
Preparation example 4
Oven drying 50g resin, swelling with ethanol for 6 hr, adding 5.0g AlCl3And 2.5g of MnCl2Stirring at 80 ℃, refluxing in water bath for 7h, cooling and filtering after modification treatment is finished, washing for 3 times by using ethanol, washing by using a large amount of deionized water until no chloride ion exists, and drying for later use.
Preparation example 5
Drying 50g of resin, swelling with ethanol for 6h, and adding 7.5g of AlCl3And 2.5g of MnCl2Stirring at 90 deg.C, refluxing in water bath for 8 hr, cooling and filtering after modification treatment, washing with ethanol for 3 times, washing with deionized water until no chloride ion exists, and drying.
Preparation example 6
Drying 50g of resin, swelling with ethanol for 6h, and adding 1.7g of AlCl3And 3.3g of MnCl2Stirring at 70 deg.C, refluxing in water bath for 6 hr, cooling and filtering after modification treatment, washing with ethanol for 3 times, washing with deionized water until no chloride ion exists, and drying.
Preparation example 7
Oven drying 50g resin, swelling with ethanol for 6 hr, adding 3.75g AlCl3And 1.25g of MnCl2Stirring at 70 deg.C, refluxing in water bath for 6 hr, cooling and filtering after modification treatment, washing with ethanol for 3 times, washing with deionized water until no chloride ion exists, and drying.
Preparation example 8
Drying 50g of resin, swelling with ethanol for 6h, and adding 4.2g of AlCl3And 0.8g of MnCl2Stirring at 70 deg.C, refluxing in water bath for 6 hr, cooling and filtering after modification treatment, washing with ethanol for 3 times, washing with deionized water until no chloride ion exists, and drying.
Preparation example 9
Drying 50g of resin, swelling with ethanol for 6h, and adding 4.5g of AlCl3And 0.5g of MnCl2Stirring at 90 deg.C, refluxing in water bath for 8 hr, cooling and filtering after modification treatment, washing with ethanol for 3 times, washing with deionized water until no chloride ion exists, and drying.
Example 1
The reaction tube was filled with 20mL of the solution of preparation example 1The modified resin is used as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at the temperature of 90-100 ℃, and the flow airspeed of a regulating pump is 0.3h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 96.9%, the selectivity of the decyl phenol is 92.7%, and the content of the dialkyl phenol is 3.9%.
Example 2
20mL of the modified resin in preparation example 2 is filled in a reaction tube as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to a molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.3h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 96.5%, the selectivity of the decyl phenol is 93.2%, and the content of the dialkyl phenol is 3.7%.
Example 3
The reaction tube is filled with 20mL of the modified resin in preparation example 3 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.3h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 97.4%, the selectivity of the decyl phenol is 93.4%, and the content of the dialkyl phenol is 3.5%.
Example 4
The reaction tube is filled with 20mL of the modified resin in preparation example 4 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.3h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 98.1%, the selectivity of the decyl phenol is 93.3%, and the content of the dialkyl phenol is 3.3%.
Example 5
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.3h-1The temperature of the reaction tube is set to be 100 ℃, the product is analyzed by gas chromatography, and the decene conversion rate is increased99.5%, decyl phenol selectivity 94.2%, dialkyl phenol content 2.8%.
Example 6
The reaction tube is filled with 20mL of the modified resin in preparation example 6 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.3h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 97.0%, the decyl phenol selectivity is 94.0%, and the content of dialkyl phenol is 3.1%.
Example 7
The reaction tube is filled with 20mL of the modified resin in preparation example 7 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.3h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 97.6%, the selectivity of the decyl phenol is 92.4%, and the content of the dialkyl phenol is 3.6%.
Example 8
The reaction tube is filled with 20mL of the modified resin in preparation example 8 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.3h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 97.8%, the decyl phenol selectivity is 91.9%, and the content of dialkyl phenol is 3.8%.
Example 9
The reaction tube is filled with 20mL of the modified resin in preparation example 9 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.3h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 98.0%, the decyl phenol selectivity is 91.5%, and the content of dialkyl phenol is 4.0%.
Example 10
The reaction tube was filled with 20mL of the resin modified in preparation example 5 as a catalyst, and phenol and decene were added in a molar ratio of 41, heating, dissolving and stirring uniformly, adding the mixture into a raw material storage tank, keeping the temperature at 90-100 ℃, and adjusting the flow airspeed of a pump to be 0.6h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 99.4%, the decyl phenol selectivity is 95.5%, and the content of dialkyl phenol is 2.0%.
Example 11
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 1.8h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 94.3%, the decyl phenol selectivity is 95.4%, and the content of dialkyl phenol is 1.9%.
Example 12
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.1h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 99.8%, the decyl phenol selectivity is 91.3%, and the content of dialkyl phenol is 5.6%.
Example 13
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 3h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 88.5%, the selectivity of the decyl phenol is 96.0%, and the content of the dialkyl phenol is 1.71%.
Example 14
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.6h-1The temperature of the reaction tube is set to be 90 ℃, the product is analyzed by gas chromatography, the decene conversion rate is 98.9 percent, the selectivity of the decylphenol is 94.6 percent, and the content of the dialkylphenolThe content was found to be 3.2%.
Example 15
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.6h-1The temperature of the reaction tube is set to be 110 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 99.5%, the selectivity of the decyl phenol is 93.3%, and the content of the dialkyl phenol is 2.3%.
Example 16
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.6h-1The temperature of the reaction tube is set to 70 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 97.1%, the decyl phenol selectivity is 94.8%, and the content of dialkyl phenol is 3.2%.
Example 17
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 4:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.6h-1The temperature of the reaction tube is set to be 150 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 99.7%, the selectivity of the decyl phenol is 90.2%, and the content of the dialkyl phenol is 4.5%.
Example 18
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 3:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.6h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 99.2%, the decyl phenol selectivity is 94.3%, and the content of dialkyl phenol is 3.1%.
Example 19
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 5:1, and the mixture is added into a raw material storage tank and is stirred at the temperature of 90-100 DEGKeeping the temperature, and regulating the flow airspeed of the pump to be 0.6h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 99.6%, the decyl phenol selectivity is 95.4%, and the content of dialkyl phenol is 1.7%.
Example 20
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 1:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.6h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 97.6%, the decyl phenol selectivity is 91.3%, and the content of dialkyl phenol is 6.2%.
Example 21
The reaction tube is filled with 20mL of the modified resin in preparation example 5 as a catalyst, phenol and decene are heated, dissolved and stirred uniformly according to the molar ratio of 10:1, the mixture is added into a raw material storage tank and is kept at 90-100 ℃, and the flow space velocity of a regulating pump is 0.6h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 99.8%, the selectivity of the decyl phenol is 96.2%, and the content of the dialkyl phenol is 1.5%.
Comparative example 1
The unmodified strong acid cation resin is used as a catalyst, 20mL of the catalyst is filled in a reaction tube, phenol and decene are heated, dissolved and stirred uniformly according to the mol ratio of 4:1, the mixture is added into a raw material storage tank and is kept at the temperature of 90-100 ℃, and the flow airspeed of a regulating pump is 0.6h-1The temperature of the reaction tube is set to be 100 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 95.6%, the decyl phenol selectivity is 91.3%, and the content of dialkyl phenol is 5.7%.
Comparative example 2
The unmodified strong acid cation resin is used as a catalyst, 20mL of the catalyst is filled in a reaction tube, phenol and decene are heated, dissolved and stirred uniformly according to the mol ratio of 4:1, the mixture is added into a raw material storage tank and is kept at the temperature of 90-100 ℃, and the flow airspeed of a regulating pump is 0.6h-1The temperature of the reaction tube is set to be 120 ℃, and the product is analyzed by gas chromatography, so that the decene conversion rate is 98.9%, the selectivity of the decyl phenol is 89.1%, and the content of the dialkyl phenol is 6.6%.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not set any limit to the present invention. The invention has been described with reference to an exemplary embodiment, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the appended claims, and changes can be made thereto without departing from the spirit and scope of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

Claims (10)

1. The method for synthesizing the alkylphenol comprises the step of contacting a raw material liquid containing olefin and phenol compounds with a modified resin, wherein the modified resin is an acidic cationic resin modified by Lewis acid.
2. The method of claim 1, wherein the Lewis acid comprises AlCl3And MnCl2Preferably, the lewis acid comprises AlCl3And MnCl2(ii) a More preferably, among the Lewis acids, AlCl3And MnCl2The mass ratio of (A) to (B) is 0.5:1-5:1, preferably 1:1-3.5: 1; and/or
The acidic cation resin is selected from styrene strong acid cation resins.
3. The process according to claim 1 or 2, characterized in that the contacting is carried out in a fixed bed reactor, preferably with a space velocity of the feed liquid of 0.2-2.0h-1More preferably 0.5 to 1.0h-1(ii) a And/or
In the fixed bed continuous reactor, the reaction tube is a tubular reactor.
4. A method according to any one of claims 1 to 3, wherein the temperature of the contacting is 70 to 150 ℃, preferably 90 to 110 ℃; and/or the molar ratio of the olefin to the phenolic compound is from 1:2 to 1:10, preferably from 1:3 to 1:5, more preferably from 1:3.5 to 1: 4.5.
5. The process according to any one of claims 1 to 4, characterized in that in the feed liquid the olefin is a C8-C11 olefin, preferably decene; and/or the phenol compound is phenol.
6. The method according to any one of claims 1 to 5, wherein the modified resin is prepared by a method comprising:
step A: contacting the acidic cation resin with the Lewis acid in an organic solvent to obtain Lewis acid modified acidic cation resin; and the number of the first and second groups,
optional step B: washing and drying the Lewis acid modified acidic cationic resin to obtain the modified resin;
preferably, the acidic cationic resin is swollen in an organic solvent prior to step a.
7. The method according to claim 6, wherein the organic solvent is selected from C1-C10 alkyl alcohols, preferably from C1-C6 alkyl alcohols, more preferably ethanol.
8. The process according to claim 6 or 7, characterized in that in step a, the weight of the lewis acid is 1-30 wt%, preferably 5-20 wt% of the acidic cationic resin;
and/or in the step A, the contact temperature is 70-90 ℃ and the contact time is 6-8 h.
9. Use of a method according to any one of claims 1 to 8 in the production of alkyl phenols, such as decyl phenol.
10. An alkylphenol, in particular an alkylphenol prepared according to the process of any of claims 1 to 8, wherein the content of dialkylphenol is lower than 6.5 wt%, preferably lower than 6.0 wt%, more preferably lower than 3.0 wt%.
CN202010395827.2A 2020-05-12 2020-05-12 Method for synthesizing alkylphenol and application thereof Pending CN113651678A (en)

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