CN109400452B - Method for preparing 3-acetyl propanol and 1, 4-pentanediol by acid catalytic hydrogenation of furan derivative - Google Patents

Method for preparing 3-acetyl propanol and 1, 4-pentanediol by acid catalytic hydrogenation of furan derivative Download PDF

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CN109400452B
CN109400452B CN201710710748.4A CN201710710748A CN109400452B CN 109400452 B CN109400452 B CN 109400452B CN 201710710748 A CN201710710748 A CN 201710710748A CN 109400452 B CN109400452 B CN 109400452B
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CN109400452A (en
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刘菲
刘巧云
乔波涛
王爱琴
张涛
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Dalian Institute of Chemical Physics of CAS
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    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
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    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
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    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
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Abstract

The invention relates to a method for preparing 3-acetyl propanol and 1, 4-pentanediol by selective hydrogenation of furan derivatives. Under the action of a bifunctional catalytic system, the furan derivative is subjected to selective hydrogenation/ring opening to prepare 3-acetyl propanol and 1.4 pentanediol in an intermittent stirred tank reactor or a continuous fixed bed at the reaction temperature of 40-200 ℃ and the hydrogen pressure of 0.1-5 MPa by taking water as a solvent. The catalytic system comprises a catalyst A and a catalyst B, wherein the catalyst A is a supported ruthenium-based catalyst, and the catalyst B is an acid catalyst. Wherein the content of Ru is 0.5-5 wt% of the total mass of the catalyst A. The invention has the obvious advantages of cheap and easily obtained raw materials, simple catalyst preparation method, simple and convenient recovery, easy product separation, high reaction activity and selectivity for preparing the 3-acetyl propanol and the 1, 4-pentanediol by selectively hydrogenating the furan derivatives, and the like.

Description

Method for preparing 3-acetyl propanol and 1, 4-pentanediol by acid catalytic hydrogenation of furan derivative
Technical Field
The invention belongs to the field of fine chemical engineering, and relates to a method for preparing 3-acetyl propanol and 1, 4-pentanediol by acid-catalyzed hydrogenation of furan derivatives.
Introduction of background:
furfural (furfuryl alcohol) is one of the important biomass-based platform compounds and is currently the only important industrial raw material that can be completely extracted from agricultural and forestry wastes. Since the chemical property of the furfural is very active, a plurality of high value-added chemicals can be derived through reactions such as oxidation, hydrogenation, chlorination, esterification, condensation and the like. Such as: the C5-alcohol-based compound can be used for producing high molecular polymers such as polyester, polyether and the like, and can also be used as an intermediate of organic synthesis for industrial production. The C5-keto compound is a very important and common organic compound and can be used as a drug synthesis intermediate.
1, 4-pentanediol, the earliest research began in the forty 20 th century, was considered an important precursor for the preparation of pentadienes. The literature reports are limited to processes for the preparation of 1, 4-pentanediol starting from levulinic acid and the reaction is catalyzed by a metal complex system formed by a homogeneous catalyst, trivalent ruthenium metal, and phosphine ligands (angew. chem. int. ed.,2010,49, 5510; j.am. chem. soc.,2011,133,14349). However, homogeneous catalysis has the disadvantages of difficult recovery, difficult recycling and the like, and the subsequent separation and purification of products are also difficult. The supported catalyst can effectively avoid the problems, and the supported bimetallic catalyst has higher activity and selectivity for selective hydrogenation of furfural. Mizugaki et al use Mg-Al hydrotalcite loaded Pt-Mo bimetallic catalyst to catalyze the conversion of levulinic acid to 1, 4-pentanediol, and the selectivity of 1, 4-pentanediol can reach 93% (Green chem.,2015,17, 5136). Considering that the industrial production of levulinic acid is usually carried out in a stronger protic acid, this medium is disadvantageous for the stabilization of 1, 4-pentanediol.
3-acetyl propanol, an important medical intermediate and an organic synthesis intermediate, can be used for synthesizing antimalarial drugs and vitamin B. Currently, the synthesis of 3-acetyl propanol is mainly realized by selective oxidation of dihydric alcohol or alkyne hydration. At present, metal complexes such as gold, ruthenium, platinum and the like are used as catalysts to obtain 3-acetyl propanol (ACS Cat., 2016,6, 7363-.
Therefore, it is important to develop an environmentally friendly synthetic process route for producing C5-alcohol and ketone compounds by using raw materials with wide sources and low price.
Disclosure of Invention
The invention aims to generate 3-acetyl propanol and 1, 4-pentanediol by taking furfural (or furfuryl alcohol) as a reaction raw material and adopting a composite catalyst through acid catalysis-hydrogenation reaction under proper reaction conditions.
In order to achieve the purpose, the invention adopts the following technical scheme:
under the conditions that the reaction temperature is 40-200 ℃, the hydrogen pressure is 0.1-5 Mpa and the reaction time is not less than 1 hour, under the action of a composite catalyst, furan derivatives are taken as reaction raw materials to carry out acid catalysis-hydrogenation reaction in a water solvent to prepare 3-acetyl propanol and 1.4-pentanediol;
wherein the composite catalyst comprises a catalyst A and a catalyst B; the catalyst A is a supported ruthenium-based catalyst, and the catalyst B is an acid catalyst; wherein the content of Ru is 0.5-5 wt% of the total mass of the catalyst A.
The catalyst A is a supported ruthenium-based catalyst, an active component is supported on a carrier, the carrier is a composite carrier of one or two of active carbon and iron oxide, and the loading capacity of the active component Ru is preferably 1.5% -3%;
the catalyst A is prepared by adopting an equal-volume impregnation or coprecipitation method:
the impregnation process is as follows: firstly, adding a certain amount of ruthenium trichloride aqueous solution into a preformed activated carbon or FeOx/C carrier according to a metering ratio, soaking in a medium volume, standing at room temperature for more than 2 hours, then drying, and roasting at the temperature of 300-600 ℃ for 2-5 hours to prepare a roasted catalyst; and then reducing the catalyst in a hydrogen atmosphere for 0.5-2 h to prepare the active catalyst.
The coprecipitation process is as follows: weighing a proper amount of activated carbon carrier treated by nitric acid into a certain amount of aqueous solution, adding a certain amount of anhydrous sodium carbonate to enable the pH of the solution to be larger than 9, uniformly stirring at 80 ℃, uniformly mixing a certain amount of ruthenium trichloride aqueous solution and ferric nitrate aqueous solution, dropwise adding the mixture into the mixed solution, stirring for two hours, standing for two hours, filtering, washing, and drying in a 60 ℃ oven; and then reducing the catalyst in a hydrogen atmosphere for 0.5-2 h to prepare the active catalyst.
The catalyst B is solid acid or liquid acid; the solid acid is one of ZMS-5, HZSM-5, Amberlyst15, Amberlyst36 and Nafion-212; the liquid acid is one of hydrochloric acid, sulfuric acid, formic acid and acetic acid; the solid acid is preferably Amberlyst15 and Amberlyst 36; the liquid acid is preferably formic acid, hydrochloric acid and sulfuric acid.
The furan derivative is furfuryl alcohol or furfural, the mass percentage of the furfuryl alcohol or furfural in the solvent is 1-20wt%, and the mass ratio of the furfuryl alcohol or furfural to the active Ru in the supported ruthenium-based catalyst is 1: 0.001-0.1; the mass ratio of the furfuryl alcohol or the furfural to the acid catalyst is 1: 0.01-1.
The reaction is carried out in a high-pressure reactor, the preferable reaction temperature is 60-120 ℃, the preferable hydrogen pressure is 0.1-1 MPa, and the preferable reaction time is 4-24 h. The method is carried out in a fixed bed reactor, the reaction temperature is preferably 60-120 ℃, and the liquid material/catalyst mass space velocity of the furan derivative in the fixed bed reactor (1 wt% -10 wt%) is preferably 0.15-5 h < -1 >.
The catalyst is a composite catalyst, is a supported catalyst taking Ru as an active component, and has the advantages that: under mild conditions, furfural (or furfuryl alcohol) is directly converted into high value-added chemicals, namely 3-acetyl propanol and 1.4-pentanediol, and the method has the advantages of readily available raw materials, low cost and sustainable development.
The invention has the obvious advantages of cheap and easily obtained raw materials, simple catalyst preparation method, simple and convenient recovery, easy product separation, high reaction activity and selectivity for preparing the 3-acetyl propanol and the 1, 4-pentanediol by selectively hydrogenating the furan derivatives, and the like.
Detailed Description
The following examples will help to understand the present invention, but the scope of the present invention is not limited to these examples.
The present invention will be described in detail with reference to examples
Example 1
0.1g of furfural and 5g of water were added into a 50ml high-pressure reaction kettle, 30mg (2 wt%) of Ru/C and 40mg of acid catalyst (Amberlyst15) were simultaneously added into the reaction kettle, 0.2MPa of hydrogen was introduced, the Parr kettle was sealed, the autoclave was heated to 80 ℃ for 25 minutes to carry out a reaction, the reaction was stopped after 20 hours, and the temperature was lowered to room temperature. The mixture is detected by a gas chromatography internal standard method, the conversion rate of the furfural is 100 percent, and the yields of the 3-acetyl propanol and the 1.4-pentanediol are respectively 64 percent and 2 percent.
Examples 2 to 4
0.1g of furfural and 5g of water were charged in a 50ml high-pressure reaction vessel, and 30mg of ruthenium-based catalyst (1.5 wt% Ru-15 FeO) was simultaneously charged in the reaction vesselx(15 represents the percentage of FeOx by mass15%, x is between 1 and 1.15, the same applies hereinafter)) and 40mg of acid catalyst (Amberlyst15), introducing 0.2MPa hydrogen, sealing the Parr kettle, heating the autoclave to 80 ℃ for 25 minutes for reaction, stopping the reaction after 20 hours of reaction, and cooling to room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in table 1.
Examples 5 to 6
0.1g of furfural and 5g of water were charged into a 50ml high-pressure reaction vessel, and a certain amount of ruthenium-based catalyst (1.5 wt% Ru-15 FeO) was simultaneously charged into the reaction vesselx/C (15 means 15% by mass of FeOx) and 40mg of an acid catalyst (Amberlyst15), introducing 0.2MPa of hydrogen, sealing the Parr kettle, heating the autoclave to 80 ℃ for 25 minutes to perform a reaction, stopping the reaction after the reaction is performed for 20 hours, and cooling to room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in table 1.
Examples 7 to 8
0.1g of furfural and 5g of water were charged in a 50ml high-pressure reaction vessel, and 30mg of ruthenium-based catalyst (1.5 wt% Ru-15 FeO) was simultaneously charged in the reaction vesselx/C (15 represents that the mass content of FeOx is 15 percent)) and a certain amount of acid catalyst (Amberlyst15), introducing 0.2MPa hydrogen, sealing the Parr kettle, heating the autoclave to 80 ℃ for reaction for 25 minutes, stopping the reaction after the reaction is carried out for 20 hours, and cooling to room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in table 1.
Example 9
0.1g of furfural and 5g of water were added into a 50ml high-pressure reaction kettle, at the same time, 40mg of an acid catalyst (Amberlyst15) was added into the reaction kettle, 0.2MPa of hydrogen was introduced, the Parr kettle was closed, the autoclave was heated to 80 ℃ for reaction for 25 minutes, the reaction was stopped after 20 hours, and the temperature was reduced to room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in table 1.
Example 10
0.1g of furfural and 5g of water were charged in a 50ml high-pressure reaction vessel, and 30mg of ruthenium-based catalyst (1.5 wt% Ru-15 FeO) was simultaneously charged in the reaction vesselx/C (15 means 15% of FeOx by mass) and 40mg of an acid catalyst (Amberlyst15), the Parr kettle was closed, the autoclave was heated to 80 ℃ for 25 minutes to carry out a reaction, and after 20 hours of the reaction, the reaction was carried outThe reaction was stopped and cooled to room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in table 1.
Example 11
0.1g of levulinic acid, 5g of water were charged into a 50ml autoclave, to which was simultaneously added 30mg of ruthenium-based catalyst (1.5 wt% Ru-15 FeO)x/C (15 means 15% by mass of FeOx) and 40mg of an acid catalyst (Amberlyst15), introducing 0.2MPa of hydrogen, sealing the Parr kettle, heating the autoclave to 80 ℃ for 25 minutes to perform a reaction, stopping the reaction after the reaction is performed for 20 hours, and cooling to room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in table 1.
Example 12
0.1g of furfuryl alcohol and 5g of water were charged into a 50ml autoclave, to which was simultaneously added 20mg of ruthenium-based catalyst (1.5 wt% Ru-15 FeO)x/C (15 means 15% by mass of FeOx) and 40mg of an acid catalyst (Amberlyst15), introducing 0.2MPa of hydrogen, sealing the Parr kettle, heating the autoclave to 80 ℃ for 25 minutes to perform a reaction, stopping the reaction after the reaction is performed for 20 hours, and cooling to room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in table 1.
Figure BDA0001382602070000041
The table shows that when the ruthenium-based catalyst and solid acid catalyst composite system provided by the invention is used for furfural catalysis, the mass ratio of the active Ru in the furfural to the supported ruthenium-based catalyst is 1:0.09, and when the mass ratio of the furfural to the acid catalyst is 1:0.4, the full conversion of the furfural can be realized by introducing 0.2MPa hydrogen, and the selectivity of 1, 4-pentanediol is up to 86%. And 3-acetyl propanol (72%) can be obtained with high selectivity by improving the mass ratio of the furfural to the active Ru in the supported ruthenium-based catalyst.
Example 13
0.1g of furfural and 5g of water were charged in a 50ml Parr vessel, while 30mg of ruthenium-based catalyst (2 wt% Ru/FeO) was charged in the reactorx(x is between 1 and 1.15) and 40mg of acid catalyst (Amberlyst15) into a closed Parr kettle under 0.2MPa of hydrogenThe autoclave was heated to 80 ℃ for 25 minutes to carry out a reaction, and after 20 hours of the reaction, the reaction was stopped and cooled to room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in the table.
Examples 14 to 17
0.1g of furfural and 5g of water are added into a 50ml Parr kettle, 30mg of ruthenium-based catalyst with different FeOx carrying amounts (the mass carrying amount of Ru is 1.5-2.5%) and 40mg of acid catalyst (Amberlyst15) are simultaneously added into the reaction kettle, 0.2MPa of hydrogen is introduced, the Parr kettle is sealed, the autoclave is heated to 80 ℃ for reaction after 25 minutes, the reaction is stopped after 20 hours of reaction, and the temperature is reduced to the room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in the table.
Figure BDA0001382602070000051
As can be seen from the table, RuFeO proposed by the present invention is usedxthe/AC catalyst has higher activity and selectivity relative to other catalyst contents when the FeOx supporting amount is 15 percent.
Examples 18 to 22
0.1g of furfural and 5g of water were charged in a 50ml Parr vessel, while 30mg of ruthenium-based catalyst (1.5 wt% Ru-15F eO) was added to the reactorxC (15 represents that the mass content of FeOx is 15%)) and 40mg of different solid acid catalysts, introducing 0.2MPa hydrogen, sealing the Parr kettle, heating the autoclave to 80 ℃ for reaction for 25 minutes, stopping the reaction after the reaction is carried out for 20 hours, and cooling to the room temperature. The mixture was checked by gas chromatography internal standard method and the reaction results are shown in the table.
Figure BDA0001382602070000052
As can be seen from the table, RuFeO proposed by the present invention is usedxWhen the/C catalyst is mixed with the solid acid A-15, the catalytic system has better catalytic performance compared with other solid acids.
Example 23
0.5 g of catalyst is filled in a fixed bed reactor, hydrogen flows through a catalyst bed layer from top to bottom under the control of a mass flow meter, a reaction raw material is furfural, and the furfural is pumped into the catalyst bed layer from top to bottom through a high performance liquid chromatography pump. 1.5wt% Ru-15FeOx/AC (15 means the percentage of FeOx mass content is 15%) and Amberlyst15 in a mass ratio of 3:4 are used as composite catalysts. The reaction temperature is 70 ℃, and the hydrogen pressure is 0.1 MPa; the yield of 3-acetylpropanol was 80% at a mass space velocity of 0.36h-1 and a hydrogen flow of 20mL min-1.
Example 24
2 g of catalyst is filled in a fixed bed reactor, hydrogen flows through a catalyst bed layer from top to bottom under the control of a mass flow meter, a reaction raw material is furfural, and the furfural is pumped into the catalyst bed layer from top to bottom through a high performance liquid chromatography pump. 1.5wt% Ru-15FeOx/AC (15 means the percentage of FeOx mass content is 15%) and Amberlyst15 in a mass ratio of 3:4 are used as composite catalysts. The reaction temperature is 70 ℃, and the hydrogen pressure is 0.1 MPa; the yield of 1, 4-pentanediol was 90% at a mass space velocity of 1.2h-1 and a hydrogen flow rate of 30mL min-1.

Claims (4)

1. A method for preparing 1, 4-pentanediol by acid catalytic hydrogenation of furan derivatives is characterized in that: the method comprises the steps of taking furan derivatives as reaction raw materials, carrying out acid catalytic hydrogenation reaction in water in a closed intermittent stirring reaction kettle or a continuous fixed bed, wherein the adopted catalyst is a composite catalyst and comprises a catalyst A and a catalyst B; the catalyst A is a supported ruthenium-based catalyst, and the catalyst B is an acid catalyst;
the hydrogen pressure is 0.2-0.5 Mpa;
the catalyst A is a supported ruthenium-based catalyst, active components are supported on a carrier, and the carrier is an active carbon and iron oxide composite carrier;
the furan derivative is furfural or furfuryl alcohol; the mass percentage of the furan derivative in the solvent water is 1-20 wt%;
when the furan derivative is furfural, the mass ratio of the furfural to the supported ruthenium-based catalyst is 1: 0.3; the mass ratio of the furfural to the acid catalyst is 1: 0.4; the supported ruthenium-based catalyst is 1.5wt% Ru-15FeOxC, 15 represents the percentage of FeOx mass content15% and the acid catalyst is Amberlyst 15;
when the furan derivative is furfuryl alcohol, the mass ratio of the furfuryl alcohol to the supported ruthenium-based catalyst is 1:0.2, the mass ratio of the furfuryl alcohol to the acid catalyst is 1:0.4, and the supported ruthenium-based catalyst is 1.5wt% of Ru-15FeOx15 represents a percentage of FeOx mass content of 15%, the acid catalyst is Amberlyst 15;
wherein x represents that the iron oxide carrier has certain defect sites, and the atomic ratio of oxygen to iron is between 1 and 1.5.
2. The method of claim 1, wherein: the catalyst A is a supported ruthenium-based catalyst, the active component is supported on a carrier, the carrier is an active carbon and iron oxide composite carrier, and the mass of the active carbon in the composite carrier accounts for 5-98% of the total mass of the carrier.
3. The process according to claim 1 or 2, characterized in that catalyst a is prepared by an equal volume impregnation or coprecipitation method:
the impregnation process is as follows: firstly, adding a soluble salt solution of a precursor A into a preformed activated carbon or FeOx/C carrier according to a metering ratio, soaking in a medium volume, wherein the mass content of FeOx in the carrier is 1-30%, standing at room temperature for more than 2 hours, drying, and roasting at 300-600 ℃ for 2-5 hours to prepare a roasted catalyst; then reducing the catalyst in a hydrogen atmosphere for 0.5-2 h to prepare an active catalyst;
the coprecipitation process is as follows: weighing 70% by mass of nitric acid, soaking the dried activated carbon carrier in ultrapure water, adding anhydrous sodium carbonate to enable the pH of the solution to be larger than 9, uniformly stirring at 60-80 ℃, uniformly mixing a ruthenium trichloride aqueous solution and a ferric nitrate aqueous solution, dropwise adding the mixture into the mixed solution, stirring for more than two hours, standing for more than two hours, filtering, washing, and drying in a 50-60 ℃ oven; and then reducing the catalyst in a hydrogen atmosphere for 0.5-2 h to prepare the active catalyst.
4. The method of claim 1, wherein:
the reaction is carried out in a batch type reaction kettle or a fixed bed reactor;
when the reaction is carried out in an intermittent reaction kettle, the reaction temperature is 40-200 ℃, the hydrogen pressure is 0.2-0.5 MPa, and the reaction time is 1-24 hours;
when the catalyst is placed in a fixed bed reactor, the reaction temperature is 40-200 ℃, and the hydrogen pressure is 0.2-0.5 MPa; the mass airspeed of the liquid material/catalyst of the furan derivative in the fluid phase reactor is 0.1-10 h-1The volume space velocity of hydrogen/catalyst is 50-5000 h-1。
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