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CN109678654A - A kind of method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol - Google Patents

A kind of method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol Download PDF

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CN109678654A
CN109678654A CN201910069482.9A CN201910069482A CN109678654A CN 109678654 A CN109678654 A CN 109678654A CN 201910069482 A CN201910069482 A CN 201910069482A CN 109678654 A CN109678654 A CN 109678654A
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hexanetriol
hydrogenation
hydroxymethyl furfural
reaction
salt
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CN109678654B (en
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夏启能
贾红燕
王燕刚
葛志刚
李溪
沈张锋
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Jiaxing University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
    • B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C29/132—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
    • 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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Abstract

本发明涉及一种5‑羟甲基糠醛加氢直接生产1,2,6‑己三醇的方法，该方法包括在溶剂存在下，采用以5‑羟甲基糠醛为原料，以非晶态合金为催化剂，在一定反应温度、氢压条件下进行加氢反应，一步法生成1,2,6‑己三醇。该方法具有己三醇收率高、反应条件温和、催化剂制备成本低和反应后分离简单的优点，具备良好的工业化应用前景。The invention relates to a method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethyl furfural. The method comprises using 5-hydroxymethyl furfural as a raw material in the presence of a solvent, and using amorphous state The alloy is used as a catalyst, and the hydrogenation reaction is carried out under a certain reaction temperature and hydrogen pressure to generate 1,2,6-hexanetriol in one step. The method has the advantages of high hexanetriol yield, mild reaction conditions, low catalyst preparation cost and simple separation after the reaction, and has good industrial application prospects.

Description

A kind of method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Technical field
The invention belongs to hydrogen addition technology fields, and in particular to a kind of 5 hydroxymethyl furfural add hydrogen directly produce 1,2,6- oneself three The method of alcohol.
Background technique
1,2,6- hexanetriol industrially has very important application, is synthesis of polyurethane resin, alkyd resin, plasticising Agent, lubricant important intermediate, while also can be used as the extractant haveing excellent performance, xylose, arabinose, glucose can be made The solvent of equal carbohydrates, is widely used in the extraction of various products, is alternatively arranged as the swelling agent of low toxicity.It is industrial at present to be mainly 1,2,6- hexanetriols are produced based on fossil resource path, is mainly hydrolyzed by acrolein dimer plus hydrogen is made.The process route At high cost with reaction raw materials, non-renewable, process steps are more, discharge the deficiencies of high.
Biomass resource is a kind of reproducible organic carbon source, has the characteristics that widely distributed, cheap and easy to get, neutral carbon, Liquid fuel and fine chemicals are prepared in recent years by the extensive pass of domestic and international chemist by biomass and its derivative Note.The furfuran compound typical case such as 5 hydroxymethyl furfural of biomass derived, obtains after being dehydrated by hexose.5- methylol chaff Aldehyde has been cited as important biomass platform chemicals, can be oriented by means of catalysis and be converted into a variety of chemical products, including (the Chemical such as 1,2,6- hexanetriol, 1,6-HD, 2,5- furan dicarboxylic acid, 2,5- dimethyl furan, levulic acid reviews,2013,113:1499-1597.).Using 5 hydroxymethyl furfural as reaction raw materials directly at produce 1,2,6- hexanetriols, It can overcome that prior art cost of material is high, the disadvantage more than reaction step.
Preparing 1,2,6- hexanetriols by 5 hydroxymethyl furfural plus hydrogen can be by the way that in the case where hydrogenation catalyst acts on, furan nucleus be direct Hydrogenolysis obtains.Document report uses Ni-Co-Al composite oxides (ACS Sustain.Chem.Eng.2014,2:173-180) As catalyst, using methanol as solvent, under the conditions of 120oC, 4.0MPa react 12h obtain highest 64.5% 1,2,6- oneself Triol.107001197 A of patent CN discloses a kind of use multistep continuously hydrogen adding method, under 80-180 DEG C, 50-2000psi, Take water as a solvent and reacted to obtain 1,2,6- hexanetriols, this method first by 5 hydroxymethyl furfural Ni, Co, Cu, Ag, Pt, The effect of Pd, Fe or Ru hydrogenation metal is lower plus hydrogen obtains 2,5- hydroxymethylfurans, then adds hydrogen in Ni, Co, Cu, Ag, Pt, Pd or Ru Continue under metal function plus hydrogen obtains 2,5- hydroxymethyl tetrahydrofuran, is finally answered what added Mo, La, Sm, Y, W or Re were modified It closes under hydrogenation catalyst effect, 2,5- hydroxymethyl tetrahydrofuran hydrogenolysis is obtained into 1,2,6- hexanetriols.
Summary of the invention
The present invention adds hydrogen to prepare in 1,2,6- hexanetriol technical process for existing 5 hydroxymethyl furfural, 1,2,6- hexanetriol The problem that yield is relatively low, reaction step is more, the period is long, provide a kind of new 5 hydroxymethyl furfural add hydrogen directly produce 1,2,6- oneself The method of triol.The method of the present invention is high with target product yield, catalytic reaction condition is mild, catalyst preparation is at low cost, anti- It answers rear catalyst to separate simple advantage, has good industrial applications prospect.
In order to solve the above technical problems, the technical solution adopted by the present invention is as follows: a kind of 5 hydroxymethyl furfural adds hydrogen direct The method for producing 1,2,6- hexanetriol, including be to urge with amorphous alloy using 5 hydroxymethyl furfural as raw material in the presence of solvent Agent, carries out hydrogenation reaction under the conditions of certain reaction temperature, hydrogen pressure, and one-step method generates 1,2,6- hexanetriols.Present invention preparation Amorphous alloy have ferromagnetism, after reaction can pass through Magnetic Isolation quick separating recycle catalyst.
The solvent is at least one of water, ethyl alcohol, normal propyl alcohol, isopropanol, tetrahydrofuran and dioxane.
The reaction temperature is 120~180 DEG C.
The reactive hydrogen pressure is 0.5~2.0MPa.
The reaction carries out in intermittent stainless steel cauldron.
The reaction time be 6~for 24 hours.
The amorphous alloy includes metallic element and nonmetalloid, and the metallic element is in Fe, Co and Ni At least one, the nonmetalloid are at least one of B, P, the metallic element of the amorphous alloy catalyst with it is non- The molar ratio of metallic element is 1:2~4.
The amorphous alloy is prepared using chemical reduction method, and preparation process includes:
A. a certain amount of metal salt is added water and stirred into dissolution, then a certain amount of boron source, phosphorus source is added water and stirred into dissolution for use； The metal salt is one or more of molysite, cobalt salt and nickel salt.
B. under inert gas protection, in ice-water bath by boron source, phosphorus source to be slowly added dropwise above-mentioned metal salt solution It emerges to bubble-free, solid product is obtained by filtration after reaction.
C. it is respectively adopted solid product 3~5 times that distilled water and dehydrated alcohol washing step b are obtained, will finally obtain Solid product is stored in the atmosphere or medium of anhydrous and oxygen-free.
In the preparation process of above-mentioned amorphous alloy, the molysite is in frerrous chloride, ferrous sulfate and ferrous acetate One or more；The cobalt salt is one or more of cobalt chloride, cobaltous sulfate and cobalt acetate；The nickel salt is chlorination One or more of nickel, nickel sulfate and nickel acetate.
The boron source is KBH4And NaBH4At least one of.
Phosphorus source is KH2PO2And NaH2PO2At least one of.
The beneficial effects of the present invention are:
(1) present invention is using 5 hydroxymethyl furfural as raw material, selected from Fe, Co and Ni at least one metallic element and selected from B The amorphous alloy formed at least one of P nonmetalloid is catalyst, and controls metallic element in amorphous alloy It with the molar ratio of nonmetalloid, is reacted in intermittent stainless steel cauldron, the direct step production 1,2,6- of hydrogen can be added Hexanetriol, reaction temperature be 120~180 DEG C, reaction pressure be 0.5~2.0MPa, the reaction time be 6~for 24 hours.
(2) using the substitution fossil feedstock production of 5 hydroxymethyl furfural derived from cheap reproducible biomass resource 1,2,6- oneself Triol, raw material sources are abundant and at low cost；Using amorphous alloy as catalysis material, target product 1,2,6- hexanetriol yield It is high, reaction condition is mild, catalyst low in cost
(3) amorphous alloy that the present invention uses has ferromagnetism, and Magnetic Isolation can be used in post catalyst reaction, easy to be fast Speed and low energy consumption.
Specific embodiment
The present invention is using 5 hydroxymethyl furfural as raw material, selected from least one of Fe, Co and Ni metallic element and selected from B The amorphous alloy formed at least one of P nonmetalloid is catalyst, is carried out in intermittent stainless steel cauldron Reaction, one step of direct hydrogenation produce 1,2,6- hexanetriols, and reaction temperature is 120~180 DEG C, and reaction pressure is 0.5~2.0MPa, Reaction time be 6~for 24 hours.
In the present invention, it first prepared by the amorphous alloy catalyst, the preparation process of the catalyst includes:
A. a certain amount of molysite, cobalt salt, nickel salt are added water and stirred into dissolution, then a certain amount of boron source, phosphorus source is added water and stirred Dissolution is stand-by.
B. under inert gas protection, boron source, phosphorus source are slowly added dropwise with certain speed in ice-water bath above-mentioned Metal salt solution to bubble-free is emerged, and solid product is obtained by filtration after reaction.
C. it is respectively adopted solid product 3~5 times that distilled water and dehydrated alcohol washing step b are obtained, finally protects sample There are in anhydrous and oxygen-free atmosphere or medium.
The present invention is further described by following specific embodiments, and but the scope of the present invention is not limited thereto.
A kind of embodiment one: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Its production method are as follows: 11.9g cobalt chloride hexahydrate and 150mL water are added in 500mL round-bottomed flask stir it is molten Solution is placed in ice-water bath, separately by 6.75g KBH4150mL water is dissolved in be placed in dropping funel, under nitrogen atmosphere protection, It is slowly added dropwise in above-mentioned round-bottomed flask, be swift in response progress, releases bulk gas, generates Co-B precipitating.To no gas When generation, solid product is obtained by filtration, is successively respectively washed solid product 3-5 times with deionized water and dehydrated alcohol, finally by sample Product are stored in spare in dehydrated alcohol.By 0.2g Co-B amorphous alloy catalyst, 0.5g 5 hydroxymethyl furfural, 10.0mL second Alcohol is put into 50mL in the stainless steel cauldron of polytetrafluoroethylene (PTFE), is reacted under the conditions of 140 DEG C of temperature, pressure are 1.5MPa 12h。
A kind of embodiment two: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Its production method are as follows: be added to 5.95g cobalt chloride hexahydrate, 5.95g Nickel dichloride hexahydrate and 150mL water Stirring and dissolving is placed in ice-water bath in 500mL round-bottomed flask, separately by 6.75g KBH4It is dissolved in 150mL water and is placed in dropping funel In, it under nitrogen atmosphere protection, is slowly added dropwise in above-mentioned round-bottomed flask, be swift in response progress, releases bulk gas, raw It is precipitated at Co-Ni-B.When no gas generates, solid product is obtained by filtration, is successively respectively washed with deionized water and dehydrated alcohol Sample is finally stored in spare in dehydrated alcohol by solid product 3-5 times.By 0.2g Co-Ni-B amorphous alloy catalyst, 0.5g 5 hydroxymethyl furfural, 10.0mL ethyl alcohol is put into 50mL in the stainless steel cauldron for having polytetrafluoroethylene (PTFE), in temperature 160 DEG C, pressure be 1.5MPa under the conditions of react 12h.
A kind of embodiment three: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Its production method are as follows: 11.9g cobalt chloride hexahydrate and 150mL water are added in 500mL round-bottomed flask stir it is molten Solution is placed in ice-water bath, separately by 4.73g NaBH4With 2.75g NaH2PO2150mL water is dissolved in be placed in dropping funel, It under nitrogen atmosphere protection, is slowly added dropwise in above-mentioned round-bottomed flask, be swift in response progress, releases bulk gas, generates Co- P-B precipitating.When no gas generates, solid product is obtained by filtration, successively respectively washs solid with deionized water and dehydrated alcohol and produces Sample is finally stored in spare in isopropanol by object 3-5 times.By 0.2g Co-P-B amorphous alloy catalyst, 0.5g 5- hydroxyl Methyl furfural, 10.0mL isopropanol put into 50mL in the stainless steel cauldron of polytetrafluoroethylene (PTFE), in 120 DEG C of temperature, press Power is reacted for 24 hours under the conditions of being 1.0MPa.
A kind of example IV: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Its production method are as follows: by 5.95g cobalt chloride hexahydrate, the anhydrous frerrous chloride of 3.17g and 150mL water are added to Stirring and dissolving is placed in ice-water bath in 500mL round-bottomed flask, separately by 6.75g KBH4It is dissolved in 150mL water and is placed in dropping funel In, it under nitrogen atmosphere protection, is slowly added dropwise in above-mentioned round-bottomed flask, be swift in response progress, releases bulk gas, raw It is precipitated at Fe-Co-B.When no gas generates, solid product is obtained by filtration, is successively respectively washed with deionized water and dehydrated alcohol Sample is finally stored in spare in dehydrated alcohol by solid product 3-5 times.By 0.2g Fe-Co-B amorphous alloy catalyst, 5.0g 5 hydroxymethyl furfural, 10.0mL ethyl alcohol is put into 50mL in the stainless steel cauldron for having polytetrafluoroethylene (PTFE), in temperature 150 DEG C, pressure be 1.2MPa under the conditions of react 20h.
A kind of comparative example one: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Preparation method it is basic as in the first embodiment, with embodiment one the difference is that: reaction temperature is 100 DEG C.
A kind of comparative example two: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Its production method it is basic as in the first embodiment, with embodiment one the difference is that: reaction temperature is 200 DEG C.
A kind of comparative example three: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Its production method it is basic as in the first embodiment, with embodiment one the difference is that: the pressure reacted are as follows: 0.3MPa.
A kind of comparative example four: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Its production method it is basic as in the first embodiment, with embodiment one the difference is that: the pressure reacted is 2.5MPa.
A kind of comparative example five: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Its production method it is basic as in the first embodiment, with embodiment one the difference is that: KBH4Dosage be 2.7g, Co and B Molar ratio be 1:1.
A kind of comparative example six: method that 5 hydroxymethyl furfural adds hydrogen directly to produce 1,2,6- hexanetriol
Its production method it is basic as in the first embodiment, with embodiment one the difference is that: KBH4Dosage be 13.5g, Co and B Molar ratio be 1:5.
Above-described embodiment one~five and comparative example one~six produce obtained 5 hydroxymethyl furfural conversion ratio and 1,2,6- oneself The selectivity of triol is as shown in the table:
As can be seen from the above experimental data, 5 hydroxymethyl furfural provided by the invention add hydrogen directly produce 1,2,6- oneself three In the method for alcohol, not only 5 hydroxymethyl furfural high conversion rate, and 1, the selectivity of 2,6- hexanetriols is also high, is higher than comparative example one ~six.

Claims (10)

1.一种5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，包括在溶剂存在下，采用5-羟甲基糠醛为原料，以非晶态合金为催化剂，在一定反应温度、氢压条件下进行加氢反应，一步法生成1,2,6-己三醇。1. a method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethyl furfural, comprising in the presence of a solvent, using 5-hydroxymethyl furfural as a raw material, and using an amorphous alloy as a catalyst, Under certain reaction temperature and hydrogen pressure, hydrogenation reaction is carried out to generate 1,2,6-hexanetriol in one step. 2.根据权利要求1所述的5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，其特征在于：所述溶剂为水、乙醇、正丙醇、异丙醇、四氢呋喃和二氧六环中的至少一种。2. the method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethyl furfural according to claim 1, is characterized in that: described solvent is water, ethanol, n-propanol, isopropanol , at least one of tetrahydrofuran and dioxane. 3.根据权利要求1所述的5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，其特征在于：所述反应温度为120～180℃。3 . The method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural according to claim 1 , wherein the reaction temperature is 120-180° C. 4 . 4.根据权利要求1所述的5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，其特征在于：所述反应氢压为0.5～2.0MPa。4. The method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural according to claim 1, wherein the reaction hydrogen pressure is 0.5-2.0 MPa. 5.根据权利要求1所述的5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，其特征在于：所述反应时间为6～24h。5. The method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural according to claim 1, wherein the reaction time is 6-24h. 6.根据权利要求1所述的5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，其特征在于：所述非晶态合金包含金属元素和非金属元素，所述的金属元素为Fe、Co和Ni中的至少一种，所述的非金属元素为B和P中的至少一种。6. the method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethyl furfural according to claim 1, is characterized in that: described amorphous alloy comprises metal element and non-metal element, so The metal element is at least one of Fe, Co and Ni, and the non-metal element is at least one of B and P. 7.根据权利要求1所述的5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，其特征在于：所述非晶态合金的金属元素与非金属元素的摩尔比为1:2～4。7. the method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethyl furfural according to claim 1, is characterized in that: the mole of metal element and non-metal element of described amorphous alloy The ratio is 1:2 to 4. 8.根据权利要求1所述的5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，其特征在于：所述非晶态合金催化剂采用化学还原法制备，制备过程包括以下步骤：8. The method for directly producing 1,2,6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural according to claim 1, wherein the amorphous alloy catalyst is prepared by chemical reduction method, and the preparation process Include the following steps: a.将一定量的金属盐加水搅拌溶解，再将一定量的硼源、磷源加水搅拌溶解待用，所述的金属盐为铁盐、钴盐和镍盐中的一种或几种。a. A certain amount of metal salt is added with water to stir and dissolve, and then a certain amount of boron source and phosphorus source are added with water to stir and dissolve for use. The metal salt is one or more of iron salt, cobalt salt and nickel salt. b.在惰性气体保护下，在冰水浴中将硼源、磷源以一定的速度缓慢逐滴加入上述金属盐溶液至无气泡冒出，反应后过滤得到固体产物。b. Under the protection of inert gas, the boron source and the phosphorus source are slowly added dropwise to the above metal salt solution in an ice-water bath at a certain speed until no bubbles emerge, and the solid product is obtained by filtration after the reaction. c.分别采用蒸馏水和无水乙醇洗涤步骤b得到的固体产物3～5次，最后将样品保存在无水无氧气氛或介质中。c. Wash the solid product obtained in step b with distilled water and anhydrous ethanol for 3 to 5 times, and finally store the sample in an anhydrous and oxygen-free atmosphere or medium. 9.根据权利要求8所述的5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，其特征在于：所述的铁盐为氯化亚铁，硫酸亚铁和醋酸亚铁中的一种或几种；所述的钴盐为氯化钴、硫酸钴和醋酸钴中的一种或几种；所述的镍盐为氯化镍、硫酸镍和醋酸镍中的一种或几种。9. 5-Hydroxymethylfurfural hydrogenation according to claim 8 directly produces the method for 1,2,6-hexanetriol, it is characterized in that: described iron salt is ferrous chloride, ferrous sulfate and One or more in ferrous acetate; Described cobalt salt is one or more in cobalt chloride, cobalt sulfate and cobalt acetate; Described nickel salt is in nickel chloride, nickel sulfate and nickel acetate one or more of them. 10.根据权利要求8所述的5-羟甲基糠醛加氢直接生产1,2,6-己三醇的方法，其特征在于：所述硼源为KBH4和NaBH4中的至少一种，所述磷源为KH2PO2和NaH2PO2中的至少一种。10. 5-Hydroxymethylfurfural hydrogenation according to claim 8 directly produces the method for 1,2,6-hexanetriol, it is characterized in that: described boron source is at least one in KBH 4 and NaBH 4 , the phosphorus source is at least one of KH 2 PO 2 and NaH 2 PO 2 .
CN201910069482.9A 2019-01-24 2019-01-24 Method for directly producing 1,2, 6-hexanetriol by hydrogenation of 5-hydroxymethylfurfural Active CN109678654B (en)

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