CN112479836B - Method for synthesizing cyclopropane formaldehyde by 1, 4-butanediol - Google Patents

Method for synthesizing cyclopropane formaldehyde by 1, 4-butanediol Download PDF

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CN112479836B
CN112479836B CN202011355446.8A CN202011355446A CN112479836B CN 112479836 B CN112479836 B CN 112479836B CN 202011355446 A CN202011355446 A CN 202011355446A CN 112479836 B CN112479836 B CN 112479836B
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butanediol
cyclopropanecarboxaldehyde
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CN112479836A (en
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牟新东
刘晓然
李慧
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Shanghai Suntian Technology Co ltd
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    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8913—Cobalt and noble metals
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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    • B01J37/18—Reducing with gases containing free hydrogen
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    • C07—ORGANIC CHEMISTRY
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Abstract

The invention relates to a method for synthesizing cyclopropane formaldehyde by 1, 4-butanediol. The method has the advantages of easily available raw materials, low cost, simple process, one-step reaction generation, high efficiency and continuous operation.

Description

Method for synthesizing cyclopropane formaldehyde by 1, 4-butanediol
Technical Field
The invention relates to the field of chemical synthesis, in particular to a method for synthesizing cyclopropane formaldehyde by using 1, 4-butanediol.
Background
Cyclopropylamine is an important pharmaceutical synthesis intermediate, and is used for synthesizing novel antibacterial drugs, namely ciprofloxacin, enrofloxacin, sparfloxacin and other drugs. In addition, cyclopropylamine is also an important intermediate for synthesizing pesticides, chemical book plant protection agents and herbicides. Currently, the synthesis method of cyclopropylamine is mainly obtained by degrading cyclopropylformamide through Hofmann. An important intermediate in the synthesis of cyclopropanecarboxamide is cyclopropanecarboxaldehyde, which is the current greenest synthetic route of cyclopropylamine.
Figure BDA0002802417030000011
CN1181058A and CN1234018A disclose methods for preparing cyclopropane formaldehyde by using 2, 3-dihydrofuran as a raw material through thermal isomerization, and the method can catalyze isomerization of 2, 3-dihydrofuran to prepare cyclopropane formaldehyde by reducing the reaction temperature to about 250 ℃ under the condition of adopting a heat carrier. US5254701A reports that 2, 3-dihydrofuran can be prepared by continuously catalyzing 2, 5-dihydrofuran to isomerize in a reaction rectification mode by adopting Ru and Rh homogeneous catalysts. U.S. Pat. No. 4, 2556325A discloses the preparation of 2, 3-bis (dihydrofuran) by the isomerization of alkali metal alkoxides (sodium, potassium) at 100-260 deg.C A method for hydrogenating furan. CN 1223645A discloses a process for preparing 2, 3-dihydrofuran by catalyzing 2,5-DHF isomerization by Pt and Pd. CN107626310A provides a method for preparing 2, 3-dihydrofuran by catalyzing 1, 4-butanediol, which uses Cu/SiO 2 -Al 2 O 3 The catalyst can realize the continuous preparation of 2, 3-dihydrofuran. Leite et al reported that monometallic Co promoted with Pd, Au, and the like catalyzes the dehydrogenation and dehydration of 1, 4-butanediol to produce 2, 3-dihydrofuran (Catalysis communications 3(2002)341-347, Journal of Molecular Catalysis A: Chemical 215(2004)95-10, Applied Catalysis A: General 362(2009) 147-154). In summary, there is no report that cyclopropane carboxaldehyde is prepared by a one-step reaction directly using 1, 4-butanediol as a raw material.
Disclosure of Invention
The invention aims to provide a method for synthesizing cyclopropane formaldehyde by 1, 4-butanediol.
Accordingly, the present invention provides a process for the synthesis of cyclopropanecarboxaldehyde from 1, 4-butanediol, which process comprises the steps of:
(1) placing the catalyst in a fixed bed reactor, purging with nitrogen at the flow rate of 20-80ml/min, introducing hydrogen, reducing at the temperature of 200-500 ℃ for 10min-20h, switching to an inert atmosphere, purging for 5-20h, switching to carrier gas, and keeping the pressure of 0.1-9MPa in the reactor;
(2) Preheating 1, 4-butanediol at the temperature of 120-500 ℃ through a preheating furnace; feeding the preheated 1, 4-butanediol into a fixed bed reactor for reaction, wherein the height of a bed layer is preferably about 2-3 cm;
(3) the product cyclopropanecarboxaldehyde is received in liquid form through a condenser tube,
wherein the catalyst is a supported catalyst in which a metal active component is supported on a carrier, wherein the metal active component includes: co as the main metal active component; and at least one selected from Cu, Zn, Pd, Au, Pt, Ni, Ru as a second metal component.
In step (1) of the process of the present invention, in the catalyst, preferably, the carrier comprises at least one selected from the group consisting of γ -alumina, silica, niobium pentoxide, tungsten trioxide, zirconium dioxide, molecular sieve, diatomaceous earth, and kaolin; more preferably selected from gamma-alumina, silica, niobium pentoxide, diatomaceous earth, kaolin.
In step (1) of the process of the present invention, the metal Co is preferably contained in the catalyst in an amount of 1 to 60% by weight, more preferably 5 to 40% by weight, based on the total mass of the catalyst.
In step (1) of the process of the present invention, the second metal is preferably contained in the catalyst in an amount of 0.1 to 10 wt%, more preferably 0.5 to 5 wt%, based on the total mass of the catalyst.
In step (1) of the method of the present invention, preferably, the reduction temperature is 300-450 ℃.
In step (1) of the method of the present invention, preferably, the reduction time is 30min to 6 h.
In step (1) of the method of the present invention, preferably, the carrier gas comprises at least one inert gas selected from nitrogen, helium and argon, and may also be a mixed gas of at least one of the above three inert gases and oxygen, and the volume ratio of oxygen in the mixed gas is 0.05-30%.
In step (2) of the method, the preheating temperature of the 1, 4-butanediol is preferably 200-400 ℃.
In step (2) of the process of the present invention, 1, 4-butanediol is preferably added for 0.01 to 30 hours -1 Is fed at a space velocity of (c).
In step (2) of the process of the present invention, the starting material may preferably be pure 1, 4-butanediol or a 1, 4-butanediol solution. When the solution is adopted for feeding, the solvent can be at least one selected from methanol, ethanol, isopropanol, water, tetrahydrofuran and 1, 4-dioxane; preferably methanol, ethanol or water.
In step (3) of the method of the present invention, preferably, the reaction temperature of the reaction is 200-. In step (3) of the process of the present invention, the reaction pressure of the reaction is preferably 0.1 to 8MPa, more preferably 0.3 to 4 MPa.
In step (1) of the process of the present invention, preferably, the catalyst can be obtained by one of the following methods:
dissolving Co metal salt and second metal component metal salt in water to prepare solution (preferably, the concentration of the Co metal salt is 0.1-5mol/L, the concentration of the second metal component metal salt is 0.1-3mol/L), adding a carrier into the solution, stirring for 3-30h (for example, 2h), drying the mixture at 90-120 ℃ for 5-30h (for example, 20h), roasting at 200-500 ℃ for 4-30h (for example, 10h), and then reducing with hydrogen at 200-500 ℃ for 2-6h to obtain the catalyst;
method two, dissolving Co metal salt and second metal component metal salt in water to prepare solution (preferably, Co metal salt concentration is 0.1-5mol/L, second metal component metal salt concentration is 0.1-3mol/L), adding carrier into the above solution and stirring for 3-30h (for example, 2h), adding sodium hydroxide solution (for example, sodium hydroxide solution with concentration of 0.5 mol/L) into the mixture to adjust the pH of the solution to 9-10, heating to 90 deg.C, stirring for 2-10h (e.g., 5h), filtering, drying the obtained solid at 90-120 deg.C for 5-30h (e.g., 20h), roasting at 200-500 ℃ for 4-30h (for example, 10h), and then reducing with hydrogen at 200-500 ℃ for 2-6h to obtain the catalyst.
In the first or second method, preferably, the Co metal salt may be at least one selected from the group consisting of cobalt nitrate, cobalt chloride, cobalt acetate, and cobalt oxalate, the second metal component may be at least one selected from the group consisting of Cu, Zn, Pd, Au, Pt, Ni, and Ru, and the second component metal salt may be at least one selected from the group consisting of nitrate, chloride, acetate, and oxalate of the second metal component.
The invention has the advantages of
The catalyst provided by the invention can be used for synthesizing cyclopropane formaldehyde from 1, 4-butanediol, the method for synthesizing cyclopropane formaldehyde has the advantages of simple process, cheap and easily obtained 1, 4-butanediol as a raw material, only one step for reaction, short steps, lower cost, greener route, high efficiency, continuous operation and easy realization of industrial production.
Detailed Description
The following examples are given by way of illustration of embodiments of the invention and are not to be construed as limiting the invention, as those skilled in the art will appreciate that various modifications may be made without departing from the spirit and scope of the invention.
The raw materials used in the invention are 1, 4-butanediol, cobalt nitrate hexahydrate, copper nitrate, palladium nitrate, chloroauric acid, kaolin and niobium pentoxide purchased from national medicine group chemical reagent limited company, the deionized water is self-made, and the SiO is 2 、γ-Al 2 O 3 Purchased from Qingdao sea wave silica gel desiccant, Inc., and cation exchange resin purchased from Michelin reagent, Inc.; the fixed bed reactor is self-made; the gas chromatograph is Shimazu-GC 2010plus from Shimadzu, and the gas chromatograph is Shimazu-QP-2010Ultra from Shimadzu.
The products obtained in the examples were passed through a 0.22 μm filter and analyzed by Gas Chromatography (GC). Qualitative analysis of the products was performed by gas chromatography-mass spectrometry (GC-MS) and standard GC retention time comparison to determine that the reaction products were predominantly cyclopropanecarboxaldehyde, 2, 3-dihydrofuran, tetrahydrofuran, and γ -butyrolactone. The product was quantified by Varian 450-GC gas chromatography and analyzed quantitatively by comparison to standard retention time and peak area size. The correlation calculation formula is as follows:
conversion (%) of 1, 4-butanediol ═ n BDO-1 /(n BDO-1 -n BDO-2 ))×100％
Yield (%) of cyclopropanecarboxaldehyde ═ n Cyclopropanecarboxaldehyde /n BDO-1 )×100％
Selectivity (%) of cyclopropanecarboxaldehyde/yield of 1, 4-butanediol × 100% conversion of n Cyclopropanecarboxaldehyde Is the molar amount of cyclopropanecarboxaldehyde, n BDO-1 Is the molar weight of the 1, 4-butanediol as the starting material, n BDO-2 Is the molar amount of 1, 4-butanediol in the reaction product.
Preparation examples
Preparation of example 1
10g of cobalt nitrate hexahydrate and 0.12g of palladium nitrate were dissolved in 50ml of water with stirring, 10g of kaolin was added to the above metal salt solution with stirring for 24 hours, and then the above mixture was dried at 110 ℃ for 20 hours, calcined at 450 ℃ in a muffle furnace for 10 hours, and then reduced with hydrogen at 250 ℃ for 5 hours to obtain catalyst 1.
Preparation of example 2
10g of cobalt nitrate hexahydrate and 0.48g of palladium nitrate were dissolved in 50ml of water with stirring, 10g of kaolin was added to the above metal salt solution with stirring for 24 hours, and then the above mixture was dried at 110 ℃ for 20 hours, calcined at 450 ℃ in a muffle furnace for 10 hours, and then reduced with hydrogen at 250 ℃ for 5 hours to obtain catalyst 2.
Preparation of example 3
Dissolving 10g of cobalt nitrate hexahydrate and 0.10g of chloroauric acid in 50ml of water, stirring and dissolving, and dissolving 10g of gamma-Al 2 O 3 The above metal salt solution was added and stirred for 24 hours, and then the above mixture was dried at 110 ℃ for 20 hours, calcined at 450 ℃ in a muffle furnace for 10 hours, and reduced with hydrogen at 250 ℃ for 5 hours to obtain catalyst 3.
Preparation of example 4
Dissolving 10g of cobalt nitrate hexahydrate and 0.42g of chloroauric acid in 50ml of water, stirring and dissolving, and dissolving 10g of gamma-Al 2 O 3 The above metal salt solution was added and stirred for 24h, then the above mixture was dried at 110 ℃ for 20h, calcined in a muffle furnace at 450 ℃ for 10h, and reduced with hydrogen at 250 ℃ for 5h to give catalyst 4.
Preparation of example 5
Dissolving 15g of cobalt nitrate hexahydrate and 3g of copper nitrate in 50ml of water, stirring and dissolving 10g of SiO 2 The above metal salt solution was added and stirred for 24 hours, and then the above mixture was dried at 110 ℃ for 20 hours, calcined at 450 ℃ in a muffle furnace for 10 hours, and reduced with hydrogen at 250 ℃ for 5 hours to obtain catalyst 5.
Preparation of example 6
Dissolving 7g of cobalt nitrate hexahydrate and 6g of copper nitrate in 50ml of water, stirring and dissolving, and adding 10g of Nb 2 O 5 The above metal salt solution was added and stirred for 24h, and then the above mixture was dried at 110 ℃ for 20h, calcined at 450 ℃ in a muffle furnace for 10h, and reduced with hydrogen at 250 ℃ for 5h to obtain catalyst 6.
Comparative preparation example 1
6g of copper nitrate was dissolved in 50ml of water with stirring, 10g of kaolin was added to the above metal salt solution with stirring for 24 hours, and then the above mixture was dried at 110 ℃ for 20 hours, calcined at 450 ℃ in a muffle furnace for 10 hours, and then reduced with hydrogen at 250 ℃ for 5 hours to obtain catalyst 7.
Examples
Example 1
1. Placing 2g of the formed catalyst 1 in a fixed bed reactor, purging with nitrogen at the flow rate of 50ml/min for 30min, heating to 400 ℃ in a hydrogen atmosphere, reducing for 1h, switching to nitrogen purging for 30min, and keeping the pressure of the reactor at 2 MPa.
2. 1, 4-butanediol is pumped by a plunger pump for 0.6h -1 Is preheated at 250 ℃ by a preheating furnace.
3. The preheated 1, 4-butanediol enters a fixed bed reactor to react at 400 ℃.
4. The product was received in liquid form via a condenser tube, and GC detection showed 86% conversion of 1, 4-butanediol, 53% selectivity for cyclopropanecarboxaldehyde, 3% selectivity for cyclopropanemethanol, 13% selectivity for 2, 3-dihydrofuran, 8% selectivity for tetrahydrofuran, and 10% selectivity for γ -butyrolactone.
Example 2
1. Placing 2g of the formed catalyst 2 in a fixed bed reactor, purging with nitrogen at the flow rate of 50ml/min for 30min, heating to 400 ℃ in a hydrogen atmosphere, reducing for 1h, switching to nitrogen purging for 30min, and keeping the pressure of the reactor at 2 MPa.
2. 1, 4-butanediol is pumped by a plunger pump for 0.6h -1 Is preheated at 250 ℃ by a preheating furnace.
3. The preheated 1, 4-butanediol enters a fixed bed reactor to react at 400 ℃.
4. The product was received in liquid form via a condenser tube, and GC detection showed 86% conversion of 1, 4-butanediol, 63% selectivity for cyclopropanecarboxaldehyde, 3% selectivity for cyclopropanemethanol, 18% selectivity for 2, 3-dihydrofuran, 2% selectivity for tetrahydrofuran, and 4% selectivity for γ -butyrolactone.
Example 3
1. 2g of the molded catalyst 3 was placed in a fixed bed reactor, purged with nitrogen at a flow rate of 50ml/min for 30min, reduced at 400 ℃ under a hydrogen atmosphere for 1h, then purged with nitrogen for 30min, and then purged with oxygen/nitrogen (5ml/min) at a volume ratio of 0.1%, and the reactor pressure was maintained at 2 MPa.
2. 1, 4-butanediol is pumped by a plunger pump for 0.6h -1 Is preheated at 250 ℃ by a preheating furnace.
3. The preheated 1, 4-butanediol enters a fixed bed reactor to react at 400 ℃.
4. The product was received in liquid form via a condenser tube, and GC detection showed 100% conversion of 1, 4-butanediol, 55% selectivity for cyclopropanecarboxaldehyde, 1% selectivity for cyclopropanecarboxylic acid, 13% selectivity for 2, 3-dihydrofuran, 7% selectivity for tetrahydrofuran, and 12% selectivity for γ -butyrolactone.
Example 4
1. 2g of the molded catalyst 4 was placed in a fixed bed reactor, purged with nitrogen at a flow rate of 50ml/min for 30min, reduced at 400 ℃ under a hydrogen atmosphere for 1h, then purged with nitrogen for 30min, and then purged with oxygen/nitrogen (5ml/min) at a volume ratio of 0.1%, and the reactor pressure was maintained at 2 MPa.
2. 1, 4-butanediol is pumped by a plunger pump for 0.6h -1 Is preheated at 250 ℃ by passing through a preheating furnace.
3. The preheated 1, 4-butanediol enters a fixed bed reactor to react at 400 ℃.
4. The product was received in liquid form via a condenser tube, and GC detection showed 100% conversion of 1, 4-butanediol, 66% selectivity for cyclopropanecarboxaldehyde, 3% selectivity for cyclopropanecarboxylic acid, 16% selectivity for 2, 3-dihydrofuran, 1% selectivity for tetrahydrofuran, and 3% selectivity for γ -butyrolactone.
Example 5
1. Placing 2g of the formed catalyst 5 in a fixed bed reactor, purging with nitrogen at the flow rate of 50ml/min for 30min, heating to 400 ℃ in a hydrogen atmosphere, reducing for 1h, switching to nitrogen purging for 30min, and keeping the pressure of the reactor at 2 MPa.
2. 1, 4-butanediol is pumped by a plunger pump for 0.6h -1 Is preheated at 250 ℃ by a preheating furnace.
3. The preheated 1, 4-butanediol enters a fixed bed reactor to react at 400 ℃.
4. The product was received in liquid form via a condenser tube, and GC detection showed 100% conversion of 1, 4-butanediol, 47% selectivity for cyclopropanecarboxaldehyde, 2% selectivity for cyclopropanemethanol, 19% selectivity for 2, 3-dihydrofuran, 5% selectivity for tetrahydrofuran, and 12% selectivity for γ -butyrolactone.
Example 6
1. Placing 2g of the formed catalyst 6 in a fixed bed reactor, purging with nitrogen at the flow rate of 50ml/min for 30min, heating to 400 ℃ in a hydrogen atmosphere, reducing for 1h, switching to nitrogen purging for 30min, and keeping the pressure of the reactor at 2 MPa.
2. 1, 4-butanediol is pumped by a plunger pump for 0.6h -1 Is preheated at 250 ℃ by a preheating furnace.
3. The preheated 1, 4-butanediol enters a fixed bed reactor to react at 400 ℃.
4. The product was received in liquid form via a condenser tube, and GC detection showed 100% conversion of 1, 4-butanediol, 11% selectivity for cyclopropanecarboxaldehyde, 1% selectivity for cyclopropanemethanol, 37% selectivity for 2, 3-dihydrofuran, 6% selectivity for tetrahydrofuran, and 36% selectivity for γ -butyrolactone.
Comparative example 1
1. Placing 2g of the formed catalyst 7 in a fixed bed reactor, purging with nitrogen at the flow rate of 50ml/min for 30min, heating to 400 ℃ in a hydrogen atmosphere, reducing for 1h, switching to nitrogen purging for 30min, and keeping the pressure of the reactor at 2 MPa.
2. 1, 4-butanediol is pumped by a plunger pump for 0.6h -1 Is preheated at 250 ℃ by a preheating furnace.
3. The preheated 1, 4-butanediol enters a fixed bed reactor to react at 400 ℃.
4. The product was received in liquid form through a condenser tube, the conversion of 1, 4-butanediol by GC was 100%, cyclopropanecarboxaldehyde and 2, 3-dihydrofuran were not detected in the product, the selectivity for tetrahydrofuran was 3%, and the selectivity for γ -butyrolactone was 93%.
As can be seen from the above examples and comparative examples, 2, 3-dihydrofuran and cyclopropanecarboxaldehyde are not produced by the catalyst not described in the present invention, and γ -butyrolactone is the main product of the reaction.

Claims (13)

1. A process for synthesizing cyclopropanecarboxaldehyde from 1, 4-butanediol, comprising the steps of:
(1) the catalyst is placed in a fixed bed reactor, after being purged by nitrogen at the flow rate of 20-80ml/min, hydrogen is introduced at 200-500- o C, reducing for 10 min-20 h, switching to inert atmosphere, purging for 5-20 h, switching to carrier gas, and keeping the pressure of 0.1-9 MPa in the reactor;
(2) the raw materials are processed at 120-500 o Preheating by a preheating furnace; feeding the preheated raw material into a fixed bed reactor for reaction, wherein the raw material is pure 1, 4-butanediol or a 1, 4-butanediol solution, and the solvent is at least one selected from methanol, ethanol, isopropanol, water, tetrahydrofuran and 1, 4-dioxane when the solution is fed;
(3) The product cyclopropanecarboxaldehyde is received in liquid form via a condenser tube,
wherein the catalyst is a supported catalyst which is prepared by supporting a metal active component on a carrier, wherein the carrier is at least one selected from gamma-alumina, silicon dioxide, niobium pentoxide, tungsten trioxide, zirconium dioxide, a molecular sieve, kieselguhr and kaolin,
wherein the metal active component consists of a main metal active component and a second metal component, and the main metal active component is Co; and the second metal component is at least one selected from Cu, Zn, Pd, Au, Pt, Ni and Ru, wherein the mass content of metal Co in the catalyst is 5-40 wt% based on the total mass of the catalyst.
2. A process for the synthesis of cyclopropanecarboxaldehyde from 1, 4-butanediol as in claim 1, wherein:
in the step (1), in the catalyst, the carrier is selected from gamma-alumina, silica, niobium pentoxide, diatomite and kaolin; and/or
In the step (1), the content of the second metal in the catalyst is 0.1-10 wt% based on the total mass of the catalyst.
3. The process for synthesizing cyclopropanecarboxaldehyde from 1, 4-butanediol as recited in claim 1, wherein in the step (1), the content of the second metal in the catalyst is from 0.5 to 5% by weight based on the total mass of the catalyst.
4. A process for the synthesis of cyclopropanecarboxaldehyde from 1, 4-butanediol as in claim 1, wherein:
in the step (1), the reduction temperature is 300-450- o C; and/or
In the step (1), the reduction time is 30 min-6 h; and/or
In the step (1), the carrier gas includes an inert gas.
5. The method for synthesizing cyclopropanecarboxaldehyde from 1, 4-butanediol as claimed in claim 1, wherein in step (1), the carrier gas is at least one selected from nitrogen, helium and argon, or a mixture of at least one selected from nitrogen, helium and argon and oxygen, and the volume ratio of oxygen in the mixture is 0.05-30%.
6. The process for synthesizing cyclopropanecarboxaldehyde from 1, 4-butanediol as recited in claim 1, wherein, in the step (2), the bed height is 2 to 3 cm.
7. A process for the synthesis of cyclopropanecarboxaldehyde from 1, 4-butanediol as in claim 1, wherein:
in the step (2), the preheating temperature of the 1, 4-butanediol is 200 o C-400 o C; and/or
In the step (2), 1, 4-butanediol is added for 0.01-30 h -1 Is fed at a space velocity of (c).
8. A process for the synthesis of cyclopropanecarboxaldehyde from 1, 4-butanediol as in claim 1, wherein the solvent is methanol, ethanol or water.
9. A process for the synthesis of cyclopropanecarboxaldehyde from 1, 4-butanediol as in claim 1, wherein:
in the step (3), the reaction temperature of the reaction is 200-700- o C; and/or
In the step (3), the reaction pressure of the reaction is 0.1-8 MPa.
10. A process for the synthesis of cyclopropanecarboxaldehyde from 1, 4-butanediol as in claim 1, wherein:
in the step (3), the reaction temperature of the reaction is 350- o C; and/or
In the step (3), the reaction pressure of the reaction is 0.3-4 MPa.
11. The process for synthesizing cyclopropanecarboxaldehyde from 1, 4-butanediol according to claim 1, wherein in step (1), the catalyst is obtainable by one of the following processes:
dissolving Co metal salt and second metal component metal salt in water to prepare solution, adding carrier into the solution and stirring for 3-30 h, and mixing the mixture at 90-120% o Drying for 5-30 h at 200- o Roasting for 4-30 h under C, and then baking for 500 h under 200 DEG C o Reducing for 2-6 h by hydrogen under C to obtain a catalyst;
dissolving Co metal salt and second metal component metal salt in water to prepare solution, adding the carrier into the solution, stirring for 3-30 h, adding sodium hydroxide solution into the mixture to adjust the pH value of the solution to 9-10, and heating to 90 DEG o C, stirring for 2-10 h, filtering to obtain solid of 90-120% o Drying for 5-30 h under the condition of temperature of 200- o Roasting for 4-30 h under C, and then baking for 500-200 DEG C o And (4) reducing for 2-6 h by hydrogen under the condition of C to obtain the catalyst.
12. A method of synthesizing cyclopropanecarboxaldehyde from 1, 4-butanediol as recited in claim 11, wherein in the first method or the second method, the Co metal salt is at least one selected from cobalt nitrate, cobalt chloride, cobalt acetate and cobalt oxalate, and the second metal component metal salt is at least one selected from nitrate, chloride, acetate and oxalate of the second metal component.
13. The method of synthesizing cyclopropanecarboxaldehyde from 1, 4-butanediol as recited in claim 11, wherein in the first method or the second method, the Co metal salt and the second metal component metal salt are dissolved in water to prepare a solution, the concentration of the Co metal salt is 0.1-5 mol/L, and the concentration of the second metal component metal salt is 0.1-3 mol/L.
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GB1334952A (en) * 1971-01-06 1973-10-24 Ici Ltd Cyclopentane derivat-ves and a process for their manufacture
US4275238A (en) * 1980-01-10 1981-06-23 Ciba-Geigy Corporation Process for the preparation of cyclopropylmethyl-n-propylamine
JPS61155382A (en) * 1984-12-28 1986-07-15 Taisho Pharmaceut Co Ltd (-)-(3s)(5r)-5-substituted oxymethyl-3-isoprenyltetrafuran-2-one and preparation thereof
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