CN106866360B - Method for preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural - Google Patents

Method for preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural Download PDF

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CN106866360B
CN106866360B CN201510918319.7A CN201510918319A CN106866360B CN 106866360 B CN106866360 B CN 106866360B CN 201510918319 A CN201510918319 A CN 201510918319A CN 106866360 B CN106866360 B CN 106866360B
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hydroxymethylfurfural
hexanediol
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郑明远
萧斌
庞纪峰
孙睿岩
李新生
王爱琴
王晓东
张涛
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention provides a method for preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural. The method takes 5-hydroxymethylfurfural as a raw material, and realizes the preparation of 1, 6-hexanediol from the 5-hydroxymethylfurfural raw material with high efficiency, high selectivity and high yield through a one-step catalytic conversion process on a supported catalyst with a catalyst active component of M-ReOx under the conditions of 50-200 ℃ and 1-13MPa of hydrogen pressure. The reaction provided by the invention has the advantages that the raw material is derived from biomass, and the reaction is renewable, green and the like. Meanwhile, the reaction atom has high economical efficiency. In addition, compared with other technologies for preparing 1, 6-hexanediol by taking biomass as a raw material, the process has the advantages of short reaction time, good 1, 6-hexanediol selectivity, high space-time yield and the like.

Description

Method for preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural
Technical Field
The invention belongs to the technical field of biological energy development, and particularly relates to a method for preparing 1, 6-hexanediol by catalytic conversion of biomass 5-hydroxymethylfurfural under a hydrogenation condition.
Background
1, 6-hexanediol is mainly used in the fields of novel polyesters, polyurethanes, coatings, adhesives, sealants, plasticizers, and the like. The polyester prepared by using the 1, 6-hexanediol is convenient to modify, and is beneficial to the improvement of the mechanical strength, the heat resistance, the water resistance, the oxidation resistance and the like of a subsequent polymer. Meanwhile, the 1, 6-hexanediol has a long carbon chain and relatively high flexibility, and can be used for preparing novel polyester products with special properties. In addition, with the improvement of living standard, the requirement of people on the environmental quality is higher, and the 1, 6-hexanediol is widely applied to the aspects of environment-friendly water-soluble resin coating, polyurethane adhesive and the like.
Currently, 1, 6-hexanediol is mainly prepared by oxidation and hydrogenation, and specifically comprises the following steps: when cyclohexane is oxidized to produce cyclohexanone and/or cyclohexanol, a carboxylic acid mixture containing glutaric acid, adipic acid and 6-hydroxycaproic acid is obtained as a by-product, and this carboxylic acid mixture is esterified and then hydrogenated to produce 1, 6-hexanediol, which is then separated by distillation (US 3,268,588). However, the method has the defects of non-renewable raw materials, low product yield, difficult separation and the like.
The 5-hydroxymethylfurfural has an aldehyde group and a hydroxymethyl group in a molecule, and can be used for synthesizing a plurality of useful compounds and novel high polymer materials through hydrogenation, oxidative dehydrogenation, esterification, halogenation, polymerization, hydrolysis and other chemical reactions. The preparation method of the hydroxymethylfurfural is mainly a biomass hydrolysis method, and the raw material source is rich and the price is low, so the hydroxymethylfurfural is expected to become a novel platform compound based on biomass resources (the research progress of the preparation and application of the 5-hydroxymethylfurfural, the chemical development, 2008,27, 702-707).
Buntara et al prepared 1, 6-hexanediol from 1,2, 6-hexanetriol by catalytic conversion in Rh-ReOx/SiO2The selectivity to the target product was 73% over the catalyst (ref 1, top. cat., 2012,55, 612-. However, the reaction time of the process reaches 20 hours, the efficiency is low, and starting from 1,2, 6-hexanetriol, the problems of raw material shortage, high raw material value and the like exist. Tuteja et al use Pd/ZrP as a catalyst and formic acid as a hydrogen source to realize one-step catalytic conversion of 5-hydroxymethylfurfural to 1, 6-hexanediol, with a hexanediol yield of 43% (reference 2, Chemusshem, 2014,7,96-100.) the reaction is also carried out in a reaction kettle, with a reaction time of 20 hours and a lower product yield, and therefore a catalyst system is urgently needed to be developed to improve product selectivity and reaction efficiency.
The method provided by the invention takes 5-hydroxymethylfurfural as a raw material and directly converts the 5-hydroxymethylfurfural into 1, 6-hexanediol under the action of a catalyst. The method is simple to operate and low in cost, and the catalytic conversion efficiency of the raw materials and the space-time yield of the dihydric alcohol are obviously improved.
Disclosure of Invention
The invention aims to provide a method for efficiently catalytically converting 5-hydroxymethylfurfural raw material into 1, 6-hexanediol, which has the advantages of high space-time yield, less byproducts and easiness in industrial production compared with the conventional 1, 6-hexanediol preparation process.
In order to achieve the purpose, the invention adopts the technical scheme that:
5-hydroxymethylfurfural is used as a reaction raw material, catalytic hydrogenation reaction is carried out in a fixed bed by adopting a double-bed catalyst, the active component of an upper-layer catalyst A is one or more than two of transition metals of groups 8, 9 and 10, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum, the active component of a lower-layer catalyst B is M-ReOx, x is 0-3, M is one or more than two of transition metals of groups 8, 9 and 10, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum, the reaction is carried out in hydrogen, the reaction pressure is more than 1MPa, the reaction temperature is more than or equal to 50 ℃, and the weight space velocity of reactants is 0.1-50h-1To (c) to (d);
the active components of the catalysts A and B are loaded on a carrier, and the carrier is a composite carrier of one or more of active carbon, alumina, silicon oxide, silicon carbide, zirconia, zinc oxide and titanium dioxide; the content of active component metal on the catalyst is 0.1-50 wt%.
The catalyst A is a framework metal catalyst; the M component in the catalyst B is preferably iridium or rhodium.
A preferred support for catalyst B is silica; the weight ratio of catalyst a to catalyst B in the fixed bed reactor is from 1:10 to 10: 1.
The catalyst is used for the reaction of preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural, and the catalyst is reduced for 0.5 to 5 hours by hydrogen at the temperature of 200 ℃ and 450 ℃ before the reaction; in the reaction process, the reaction temperature is preferably 80-200 ℃; the preferred pressure of hydrogen in the reaction is 2-10 MPa; .
The reaction solvent is one or more than two of water, tetrahydrofuran, methanol, methylcyclohexane and octadeca-crown-6, and the mass concentration of the reactant 5-hydroxymethylfurfural is 0.5-50%.
Preferably, the solvent is a mixed solution of water and tetrahydrofuran, and the volume ratio of the water to the tetrahydrofuran is 10:1-1: 10.
The preferred mass space velocity of the reaction mass in the reaction is 1-10h-1。
The 5-hydroxymethylfurfural raw material is prepared by a biomass conversion method, and the impurity content is less than 5%.
The invention has the following advantages:
1. the biomass catalytic conversion product 5-hydroxymethylfurfural is used as a reaction raw material. Compared with the raw materials used in the existing industrial synthesis route of 1, 6-hexanediol, the process has the advantage of renewable raw material resources and meets the requirement of sustainable development.
2. Under the composite catalyst, the conversion efficiency of the 5-hydroxymethylfurfural is high, the selectivity of the 1, 6-hexanediol is good, the space-time yield is high, and the industrial utilization is easier.
The present invention will be described in detail with reference to specific examples, which are not intended to limit the scope of the present invention.
Detailed Description
Example 1
Preparation of the catalyst
M/SiO2The (M ═ Pd, Pt and Rh) catalyst is prepared by an impregnation method, the carrier is silicon oxide, the aqueous solution of the metal salt is impregnated in an equal volume, after 12h of impregnation, the catalyst is dried for 12h under 393K, then the catalyst is roasted for 3h under 773K air atmosphere, and finally 573K hydrogen reduction is carried out for 2 h. When the active carbon is used as a carrier, the air atmosphere is changed into high-purity nitrogen, and other conditions are the same as the above.
M-Re/SiO2The preparation method of the catalyst comprises the step of preparing the prepared M/SiO2Catalyst isovolumetric impregnation of aqueous solution of perrhenic acid, in which M/SiO2The catalyst was prepared in the same manner as before, after 12h of impregnation, dried at 393K for 12h and finally reduced in situ at 573K with hydrogen for 2 h.
Example 2
Catalytic conversion experiments:
the fixed bed reactor is 31cm long, 15mm in outer diameter and 4.5mm in inner diameter, the upper end and the lower end of the catalyst are filled with 60-80-mesh quartz sand, and the loading amount of the catalyst is 1.0 g. Before the reaction, the catalyst is reduced in situ for 2h at a set temperature, and the reaction is carried out after the temperature is reduced to the reaction temperature. The reactant solution was injected into the reaction tube at a constant flow rate using a high pressure liquid chromatography pump (model LC-20A, Shimadzu corporation), the gas phase product was analyzed by on-line chromatography (Agilent 7890B GC), and the liquid phase product was collected by cooling in an ice bath and analyzed by chromatography.
Example 3
The results of the catalytic conversion of 5-hydroxymethylfurfural to 1, 6-hexanediol over different catalysts (Table I) were obtained under the same reaction conditions as in example 2.
TABLE-results of the catalytic conversion of 5-hydroxymethylfurfural to 1, 6-hexanediol over different catalysts (373K,5MPa H)2The solvent is a mixture of water and THF, the volume ratio of the water to the THF is 2:3, the raw material concentration is 1 wt%, and the mass space velocity of the material is 6h-1)
Figure BDA0000873577920000031
Figure BDA0000873577920000041
Note: 1,6-HDO, 1,5-HDO are 1, 6-hexanediol and 1, 5-hexanediol, respectively; the figures following the catalyst are the metals and the Re content.
As can be seen from Table I, the yield of 1, 6-hexanediol on the composite catalyst increased with increasing Re content, and the yields of 1, 6-hexanediol at 2.5% and 5% Re were similar, 46-48%, which is higher than the yield of 43% in reference 2 (Chemusschem, 2014,7, 96-100.).
Example 4
The reaction conditions for preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural in different solvents are the same as those in example 2.
Influence of different solvents on preparation of 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural (catalyst is Pd/SiO)2(0.6%) and Ir-ReOx/SiO2(5% -5%) 373K,3MPa H2The HMF concentration is 1 wt%, and the weight space velocity is 6h-1)
Figure BDA0000873577920000042
As shown in Table II, the solvent has a great influence on the selectivity of the product, wherein the water and THF systems show unique promoting effects, and the yield of 1, 6-hexanediol reaches 36.1% at a water content of 40%, which is much higher than the reaction results in the presence of a solvent of mono-pure water or tetrahydrofuran.
Example 5
The reaction results of the catalytic conversion of 5-hydroxymethylfurfural to 1, 6-hexanediol under different hydrogen pressures (Table III) were as in example 2.
Reaction results of preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural under different apparent pressures (the catalyst is Pd/SiO2(0.6%) and Ir-ReOx/SiO2(5% -5%) 373K,3MPa H2The HMF concentration is 1 wt%, and the weight space velocity is 6h-1)
Figure BDA0000873577920000051
As shown in Table III, the yield of 1,6-HDO was gradually increased with an increase in hydrogen pressure, and the yield of 1,6-HDO was 51.7% at 7 MPa.
Example 6
Stability of the catalyst
TABLE IV reaction results of 5-hydroxymethylfurfural catalytic conversion to 1, 6-hexanediol under different times (catalyst is Pd/SiO)2(0.6%) and Ir-ReOx/SiO2(5% -5%) 373K,3MPa H2The HMF concentration is 1 wt%, and the weight space velocity is 6h-1)
Figure BDA0000873577920000052
Figure BDA0000873577920000061
As shown in Table IV, the catalyst has high stability, and the yield of the 1, 6-hexanediol still exceeds 50% after the reaction for 15 hours.
Comparative example 1
TABLE five different catalysts, reactionsComparison of preparation of 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural in an apparatus (373K,3MPa H)2The concentration of HMF is 1 wt%, the reaction time of the reaction kettle is 5 hours, and the weight space velocity of the fixed bed is 6 hours-1)
Figure BDA0000873577920000062
As can be seen from the comparative examples in Table five, Pd/SiO2(0.6%) and Ir-ReOx/SiO2(5% -5%) of the catalyst system has high reaction activity and selectivity, and the yield of 1, 6-hexanediol is far higher than that of a single-bed catalyst and a reaction kettle.
The composite catalyst system can efficiently convert 5-hydroxymethylfurfural into 1, 6-hexanediol, and has the advantages of high space-time yield, simple catalyst operation and preparation, easiness in industrialization and the like.

Claims (8)

1. A method for preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural is characterized by comprising the following steps: 5-hydroxymethylfurfural is used as a reaction raw material, catalytic hydrogenation reaction is carried out in a fixed bed by adopting a double-bed catalyst, the active component of an upper-layer catalyst A is one of transition metals of 8, 9 and 10 groups, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, iridium and platinum, the active component of a lower-layer catalyst B is M-ReOx, x =0-3, M is one or more of transition metals of 8, 9 and 10 groups, such as ruthenium, rhodium and iridium, the reaction is carried out in hydrogen, the reaction pressure is greater than 1MPa, the reaction temperature is greater than or equal to 50 ℃, and the weight space velocity of reactants is 0.1-50h-1To (c) to (d);
the reaction solvent is one of water, methanol, a mixed solution of water and tetrahydrofuran and a mixed solution of water and methylcyclohexane, and the mass concentration of the reactant 5-hydroxymethylfurfural is 0.5-50%.
2. The method of claim 1, wherein: the active components of the catalysts A and B are loaded on a carrier, and the carrier is a composite carrier of one or more of active carbon, alumina, silicon oxide, silicon carbide, zirconia, zinc oxide and titanium dioxide; the content of active component metal on the catalyst is 0.1-50 wt%.
3. The method of claim 1, wherein: the catalyst A is a framework metal catalyst; the M component in the catalyst B is one or two of iridium and rhodium.
4. The method of claim 1, wherein: the carrier of the catalyst B is silicon dioxide; the weight ratio of catalyst a to catalyst B in the fixed bed reactor is from 1:10 to 10: 1.
5. The method of claim 1, wherein: the catalyst is used for the reaction of preparing 1, 6-hexanediol by catalytic conversion of 5-hydroxymethylfurfural, and the catalyst is reduced for 0.5 to 5 hours by hydrogen at the temperature of 200 ℃ and 450 ℃ before the reaction; in the reaction process, the reaction temperature is 80-200 ℃; the pressure of hydrogen in the reaction is 2-10 MPa.
6. The method of claim 1, wherein: the solvent is a mixed solution of water and tetrahydrofuran, and the volume ratio of the water to the tetrahydrofuran is 10:1-1: 10.
7. The method of claim 1, wherein: the mass space velocity of the reaction materials in the reaction is 1-10h-1。
8. The method of claim 1, wherein: the 5-hydroxymethylfurfural raw material is prepared by a biomass conversion method, and the impurity content is less than 5 wt%.
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CN107011107A (en) * 2017-05-16 2017-08-04 中国科学技术大学 A kind of method that use load type metal catalyst prepares alcohol
CN111253212B (en) * 2018-11-30 2021-05-25 中国科学院大连化学物理研究所 Method for preparing 2, 5-hexanediol
CN112898164B (en) * 2019-12-03 2022-03-04 中国科学院大连化学物理研究所 Method for preparing 1, 6-hexamethylene diamine from 5-hydroxymethylfurfural
CN111233797A (en) * 2020-02-28 2020-06-05 浙江糖能科技有限公司 Preparation method of 2, 5-tetrahydrofuran dimethanol
CN114713236B (en) * 2022-03-30 2023-07-25 郑州大学 Ni-ReO x /TiO 2 Bimetallic catalyst, preparation method thereof and application thereof in selective hydrogenation of biomass aldehyde
CN115779898A (en) * 2022-12-28 2023-03-14 宁波环洋新材料股份有限公司 Catalyst for removing aldehyde from 1, 3-propylene glycol and preparation method and application thereof

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