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CN117126041A - C (C) 9 H 12 O preparation method - Google Patents

C (C) 9 H 12 O preparation method Download PDF

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Publication number
CN117126041A
CN117126041A CN202311101293.8A CN202311101293A CN117126041A CN 117126041 A CN117126041 A CN 117126041A CN 202311101293 A CN202311101293 A CN 202311101293A CN 117126041 A CN117126041 A CN 117126041A
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China
Prior art keywords
catalyst
phenol
reaction
phosphate
reaction solution
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CN202311101293.8A
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Chinese (zh)
Inventor
汪学广
张利凡
李志闯
邹秀晶
尚兴付
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Priority to CN202311101293.8A priority Critical patent/CN117126041A/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
    • C07C37/16—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 condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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

Abstract

The invention relates to the technical field of organic synthesis, in particular to a C 9 H 12 O is prepared by a method. The method comprises the steps of taking phenol and isopropanol as reaction raw materials, then heating up under a protective atmosphere, and enabling the mixed reaction solution to finish the reaction through the surface of a catalyst to prepare C 9 H 12 O. In the process, when the catalyst is a phosphate catalyst, mainly synthesizing the isopropoxy benzene; when the catalyst is an Al-P-O catalyst, the O-isopropyl phenol and the P-isopropyl phenol are mainly synthesized. The reaction has low preparation cost, is not easy to produce harmful substances, is an environment-friendly reaction path, realizes C 9 H 12 The O production is environment-friendly and low in cost.

Description

C (C) 9 H 12 O preparation method
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a C 9 H 12 O is prepared by a method.
Background
Molecular formula C 9 H 12 The isomers of O comprise isopropoxy benzene and isopropyl phenol.
Wherein, the isopropyl radicalBenzene, also known as 1-isopropoxy benzene, isopropyl phenyl ether, isopropoxy benzene, CAS number 2741-16-4, melting point-33 ℃, boiling point 178.9+ -9.0deg.C at760mmHg, density 0.9+ -0.1 g/cm 3 Is a colorless liquid, and is slightly soluble in water. The isopropoxy benzene is an excellent organic solvent and is widely used in the fields of printing ink, coating, cleaning agent and the like. The isopropoxy benzene is also used as an intermediate for synthesizing organic compounds, and has wide application in the fields of medicines, pesticides and the like.
Isopropyl phenol is an important fine chemical raw material and is divided into ortho, meta and para isomers. Among them, the o-and p-isopropyl phenol is very widely used. Para-isopropyl phenol, also known as 4-isopropyl phenol, is an off-white crystal that can be used as a machine cleaner, wire coating, synthetic resin, surfactant, binder, pharmaceutical intermediate, etc.
O-isopropyl phenol, also known as 2-isopropyl phenol, is a transparent to pale yellow liquid. In addition to the same uses as p-isopropyl phenol, o-isopropyl phenol can also be used to make preservatives, fuel additives, paint fall off resistance agents and as intermediates in the synthesis of pesticide leafhopper powder.
Therefore, the isopropyl phenyl and the o-and p-isopropyl phenol have large market demand in China and high economic value. However, the conventional pot reaction synthesis of isopropoxy benzene uses phenol and 2-chloropropane or 2-bromopropane as raw materials. The 2-chloropropane and the 2-bromopropane are highly toxic chemicals, have high risk, and have the defects of troublesome operation, easy corrosion, serious pollution, difficult separation, high energy consumption, low yield and the like. And the production of the propofol mostly adopts the traditional phenol aluminum catalyst production process. The process has the advantages of complicated operation, serious equipment corrosion, low product selectivity, difficult separation and high production cost.
In view of the shortcomings of the existing methods, the invention needs to provide a green and environment-friendly C with low production cost 9 H 12 O preparation method.
Disclosure of Invention
The invention aims to provide C 9 H 12 O preparation method for improving product selectionAnd the production cost is reduced.
In order to achieve the above object, the present invention provides the following technical solutions:
c (C) 9 H 12 The preparation method of O comprises the following steps:
mixing phenol and isopropanol to obtain a mixed reaction solution, heating the mixed reaction solution in a protective atmosphere, and then enabling the mixed reaction solution to react through the surface of a catalyst to obtain C 9 H 12 O。
Optionally, the molar ratio of the phenol to the isopropanol is 1:1 to 6.
Optionally, the protective atmosphere comprises at least one of nitrogen and hydrogen.
Optionally, the catalyst is phosphate, and the prepared C 9 H 12 O is isopropoxy benzene.
Optionally, the phosphate comprises one or more of aluminum phosphate, lanthanum phosphate, gallium phosphate, titanium phosphate, silicon phosphate, calcium phosphate and magnesium phosphate.
Optionally, when the isopropoxy benzene is prepared, the temperature is increased to 140-200 ℃; the reaction space velocity of the mixed reaction solution passing through the surface of the catalyst is 0.1 to 1.5h -1 。
Optionally, the catalyst is an Al-P-O catalyst, and the prepared C 9 H 12 O is isopropyl phenol.
Optionally, the mole ratio of phosphorus to aluminum in the Al-P-O catalyst is 1:0.25 to 1.25, wherein the isopropyl phenol comprises o-isopropyl phenol and p-isopropyl phenol.
Optionally, when the isopropyl phenol is prepared, the temperature is 200-260 ℃; the reaction space velocity of the mixed reaction solution passing through the surface of the catalyst is 0.3 to 1.2h -1 。
The invention provides a method for producing C in green by gasifying phenol and isopropanol and then carrying out alkylation reaction under the action of a catalyst 9 H 12 O method.
When phenol reacts with isopropanol, the reaction process is as follows:
the catalyst is used in the reaction process of the phenol and the isopropanol, the active center of the reaction is an acid-base active site on the surface of the catalyst, and the proper catalyst is selected, so that the reaction process can be influenced, and the selectivity of a target product is improved.
At a reaction temperature of 140-200 ℃, the phosphate-based catalyst mainly catalyzes the O-alkylation process. When the catalyst is a phosphate catalyst, the gasified phenol and isopropanol react under the action of the phosphate catalyst, and the O-alkylation reaction is easier to occur, so that the phenol and the isopropanol mainly synthesize the isopropoxy benzene.
At a reaction temperature of 200-260 ℃, the Al-P-O catalyst can inhibit the O-alkylation process and strengthen the C-alkylation process. When the catalyst is an Al-P-O catalyst, the gasified phenol and isopropanol react under the action of the Al-P-O catalyst, the O-alkylation reaction is inhibited, and the C-alkylation is easier to occur, so that the main products of the reaction of the phenol and the isopropanol are the O-isopropyl phenol and the P-isopropyl phenol.
The raw materials involved in the preparation method are only phenol and isopropanol, the price is low, the production cost is low, no other solvent is used, the reactant is nontoxic, no waste is discharged, harmful byproducts are hardly produced, equipment is hardly corroded, and the preparation method is an environment-friendly reaction path.
The method adopts a fixed bed reaction device in the generation process, is simple and easy to operate, has low reaction energy consumption, has continuity in production, and has high reaction rate, high reaction efficiency and high reaction conversion rate and product selectivity. Moreover, the preparation method adopts a solid catalyst, the reaction liquid passes through the catalyst in a gas form and is a gas-solid phase catalytic process, and products and the catalyst do not need to be separated after the reaction is completed.
Drawings
FIG. 1 is a diagram of an activity evaluation apparatus for alkylation of phenol with isopropanol; wherein 1 is a gas pipeline valve; 2 is a liquid flow pump; 3 is a mixed reaction liquid of phenol and isopropanol; 4 is a gas mass flowmeter; 5 is a heating furnace; 6 is a reaction tube; 7 is a catalyst bed; 8 is a thermocouple; 9 is a reaction product collection bottle.
Detailed Description
The invention provides a C 9 H 12 The preparation method of O comprises the following steps:
mixing phenol and isopropanol to obtain a mixed reaction solution, heating the mixed reaction solution in a protective atmosphere, and then enabling the mixed reaction solution to react through the surface of a catalyst to obtain C 9 H 12 O。
In the invention, the mole ratio of the phenol to the isopropanol is 1:1 to 6, preferably 1:1.5 to 5, more preferably 2 to 4.5, still more preferably 3 to 4.
In the present invention, the protective atmosphere contains at least one of nitrogen and hydrogen.
In the present invention, the catalyst is phosphate, and the prepared C 9 H 12 O is isopropoxy benzene.
In the invention, the phosphate comprises one or more of aluminum phosphate, lanthanum phosphate, gallium phosphate, titanium phosphate, silicon phosphate, calcium phosphate and magnesium phosphate.
In the present invention, when isopropoxy benzene is produced, the temperature up to which the temperature is raised is 140 to 200 ℃, preferably 150 to 190 ℃, more preferably 160 to 180 ℃, still more preferably 165 to 170 ℃;
the reaction space velocity of the mixed reaction solution passing through the surface of the catalyst is 0.1 to 1.5h -1 Preferably 0.3 to 1.2h -1 More preferably 0.4 to 1.0h -1 More preferably 0.5 to 0.6 hours -1 。
In the invention, the catalyst is an Al-P-O catalyst, and the prepared C 9 H 12 O is isopropyl phenol.
In the invention, the mole ratio of phosphorus to aluminum in the Al-P-O catalyst is 1:0.25 to 1.25, preferably 1:0.35 to 1.1, more preferably 0.5 to 1.0, still more preferably 0.75 to 0.9;
the isopropyl phenol comprises ortho-isopropyl phenol and para-isopropyl phenol.
In the present invention, when isopropyl phenol is produced, the temperature to which the temperature is raised is 200 to 260 ℃, preferably 210 to 250 ℃, more preferably 220 to 240 ℃, still more preferably 225 to 230 ℃;
the reaction space velocity of the mixed reaction solution passing through the surface of the catalyst is 0.3 to 1.2h -1 Preferably 0.4 to 1.0h -1 More preferably 0.5 to 0.9h -1 More preferably 0.6 to 0.8 hours -1 。
The activity evaluation of the alkylation reaction of phenol and isopropanol was carried out on a fixed bed continuous flow apparatus, the schematic diagram of which is shown in FIG. 1 (1. Gas pipeline valve; 2. Liquid flow pump; 3. Reaction liquid mixture of phenol and isopropanol; 4. Gas mass flowmeter; 5. Heating furnace; 6. Reaction tube; 7. Catalyst bed; 8. Thermocouple; 9. Reaction product collecting bottle).
Wherein the reaction tube is glass or quartz reaction tube, the catalyst bed is placed in the reaction tube, the lower end of the catalyst bed is supported by a fine glass tube, and inert filler is added into the upper part of the catalyst bed. The mixed reaction liquid of phenol and isopropanol is pumped into a reaction tube by a liquid flow pump, gasified by a heating furnace, passes through a catalyst bed layer in a gaseous form, reacts under the action of a catalyst to generate a product, and the product is condensed at the bottom of the reaction tube and is collected in a collecting bottle. The reaction product was analyzed for its composition using a chromatograph-mass spectrometer and a gas chromatograph.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Phenol and isopropanol were mixed in a molar ratio of 1:4, mixing to obtain a mixed reaction solution, placing an aluminum phosphate catalyst in a fixed bed reactor, and then heating the fixed bed reactor to 140 ℃ under nitrogen atmosphere for 0.4h -1 The mixed reaction solution passes through an aluminum phosphate catalyst, and the product isopropoxy benzene and other byproducts are collected after the reaction is completed. In this reaction, the conversion of reactant phenol was 55%, with a selectivity to isopropoxy benzene of 70%, and isopropoxy benzeneThe single pass yield was 38%.
Example 2
Phenol and isopropanol were mixed in a molar ratio of 1:2, mixing to obtain a mixed reaction solution, placing a lanthanum phosphate catalyst in a fixed bed reactor, and then heating the fixed bed reactor to 170 ℃ under nitrogen atmosphere for 0.1h -1 The mixed reaction solution passes through lanthanum phosphate catalyst, and the product isopropoxy benzene and other byproducts are collected after the reaction is completed. In this reaction, the conversion of reactant phenol was 67%, with a selectivity of 65% for isopropoxy benzene and a once-through yield of 43% for isopropoxy benzene.
Example 3
Phenol and isopropanol were mixed in a molar ratio of 1:5, mixing to obtain a mixed reaction solution, placing a magnesium phosphate catalyst in a fixed bed reactor, and then heating the fixed bed reactor to 160 ℃ under nitrogen atmosphere for 0.1h -1 The mixed reaction solution passes through a magnesium phosphate catalyst, and the product isopropoxy benzene and other byproducts are collected after the reaction is completed. In this reaction, the conversion of reactant phenol was 65%, with a selectivity to isopropoxy benzene of 70% and a once-through yield of isopropoxy benzene of 45%.
Example 4
Phenol and isopropanol were mixed in a molar ratio of 1:4 preparing a reaction solution, placing an aluminum phosphate catalyst in a fixed bed reactor, and then heating the fixed bed reactor to 150 ℃ under nitrogen atmosphere for 0.6h -1 The mixed reaction solution passes through an aluminum phosphate catalyst, and the product isopropoxy benzene and other byproducts are collected after the reaction is completed. In this reaction, the conversion of reactant phenol was 69%, with a selectivity of 85% for isopropoxy benzene and a one-pass yield of 58% for isopropoxy benzene.
Example 5
Phenol and isopropanol were mixed in a molar ratio of 1:6 preparing a reaction solution, placing a magnesium phosphate catalyst in a fixed bed reactor, and then heating the fixed bed reactor to 180 ℃ under nitrogen atmosphere for 0.4h -1 The mixed reaction liquid passes through a magnesium phosphate catalyst at a space velocity, and the products of isopropoxy benzene and isopropoxy benzene are collected after the reaction is completedOther by-products. In this reaction, the conversion of reactant phenol was 74%, with 45% selectivity to isopropoxy benzene, 33% single pass yield of isopropoxy benzene,
example 6
Phenol and isopropanol were mixed in a molar ratio of 1:4 preparing a reaction solution, placing an Al-P-O catalyst with a phosphorus-aluminum molar ratio of 0.5 in a fixed bed reactor, then heating the fixed bed reactor to 220 ℃ under nitrogen atmosphere, adopting 0.8h -1 The reaction solution passes through the Al-P-O catalyst, and the O-isopropyl phenol, the P-isopropyl phenol and other byproducts are collected after the reaction is completed. In this reaction, the conversion of reactant phenol was 40%, the combined selectivity to o-and p-isopropyl phenol was 75%, and the combined yield of o-and p-isopropyl phenol was 30%.
Example 7
Phenol and isopropanol were mixed in a molar ratio of 1:3 preparing a reaction solution, placing an Al-P-O catalyst with a phosphorus-aluminum molar ratio of 0.75 in a fixed bed reactor, then heating the fixed bed reactor to 240 ℃ under nitrogen atmosphere, adopting 0.8h -1 The reaction solution passes through the Al-P-O catalyst, and the O-isopropyl phenol, the P-isopropyl phenol and other byproducts are collected after the reaction is completed. In this reaction, the conversion of reactant phenol was 45%, the combined selectivity to o-and p-isopropyl phenol was 70%, and the combined yield of o-and p-isopropyl phenol was 31%.
Example 8
Phenol and isopropanol were mixed in a molar ratio of 1:3 preparing a reaction solution, placing an Al-P-O catalyst with a phosphorus-aluminum molar ratio of 1.0 in a fixed bed reactor, then heating the fixed bed reactor to 250 ℃ under the nitrogen atmosphere, adopting 0.5h -1 The reaction solution passes through the Al-P-O catalyst, and the O-isopropyl phenol, the P-isopropyl phenol and other byproducts are collected after the reaction is completed. In this reaction, the conversion of reactant phenol was 65%, the combined selectivity to o-and p-isopropyl phenol was 85%, and the combined yield of o-and p-isopropyl phenol was 55%.
Example 9
Phenol and isopropanol were mixed in a molar ratio of 1:6 is prepared into a reaction solution inThe Al-P-O catalyst with the mole ratio of phosphorus to aluminum of 1.25 is placed in the fixed bed reactor, and then the fixed bed reactor is heated to 260 ℃ under the nitrogen atmosphere, and the temperature is increased for 0.3h -1 The reaction solution passes through the Al-P-O catalyst, and the O-isopropyl phenol, the P-isopropyl phenol and other byproducts are collected after the reaction is completed. In this reaction, the conversion of reactant phenol was 55%, the combined selectivity to o-and p-isopropyl phenol was 70%, and the combined yield of o-and p-isopropyl phenol was 38%.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (9)

1. C (C) 9 H 12 The preparation method of O is characterized by comprising the following steps:
mixing phenol and isopropanol to obtain a mixed reaction solution, heating the mixed reaction solution in a protective atmosphere, and then enabling the mixed reaction solution to react through the surface of a catalyst to obtain C 9 H 12 O。
2. The preparation method according to claim 1, wherein the molar ratio of phenol to isopropanol is 1:1 to 6.
3. The production method according to claim 1 or 2, wherein the protective atmosphere contains at least one of nitrogen and hydrogen.
4. The process of claim 3, wherein the catalyst is a phosphate salt, and the C is 9 H 12 O is isopropoxy benzene.
5. The method according to claim 4, wherein the phosphate comprises one or more of aluminum phosphate, lanthanum phosphate, gallium phosphate, titanium phosphate, silicon phosphate, calcium phosphate, and magnesium phosphate.
6. The method according to claim 4 or 5, wherein the temperature up to which the temperature is raised is 140 to 200 ℃; the reaction space velocity of the mixed reaction solution passing through the surface of the catalyst is 0.1 to 1.5h -1 。
7. The process according to claim 3, wherein the catalyst is an Al-P-O catalyst, C being obtained 9 H 12 O is isopropyl phenol.
8. The preparation method according to claim 7, wherein the molar ratio of phosphorus to aluminum in the Al-P-O catalyst is 1:0.25 to 1.25, wherein the isopropyl phenol comprises o-isopropyl phenol and p-isopropyl phenol.
9. The preparation method according to claim 7 or 8, wherein the temperature up to which the temperature is raised is 200 to 260 ℃; the reaction space velocity of the mixed reaction solution passing through the surface of the catalyst is 0.3 to 1.2h -1 。
CN202311101293.8A 2023-08-29 2023-08-29 C (C) 9 H 12 O preparation method Pending CN117126041A (en)

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