CN109748777B - Method for preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol - Google Patents
Method for preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol Download PDFInfo
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Abstract
The invention provides a method for preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol. The method takes 1,2, 6-hexanetriol as a raw material, and realizes the preparation of the 1, 6-hexanediol with high conversion rate and high yield of the 1,2, 6-hexanetriol through a one-step catalytic hydrogenolysis process in the presence of a catalyst and a solid acid. The technical route provided by the invention has the characteristics of short reaction time, high raw material conversion rate and high yield of the 1, 6-hexanediol, and the raw materials can be obtained from renewable biomass resources, so that the method has the advantage of being independent of fossil resources.
Description
Technical Field
The invention belongs to the field of biomass conversion and utilization and preparation of fine chemicals, and particularly relates to a method for preparing 1, 6-hexanediol by catalytic hydrogenolysis of biomass-derived 1,2, 6-hexanetriol.
Background
1, 6-hexanediol is an important fine chemical material and has important application in the fields of polyester, coil coating, light curing agent and the like.
The existing mature method for preparing 1, 6-hexanediol uses 1, 6-adipic acid as raw material, and makes esterification reaction with methanol to produce dimethyl adipate, then makes hydrogenation reaction to obtain 1, 6-hexanediol. For example, U.S. Pat. No. 4,3268588 discloses the esterification of a mixture of carboxylic acids such as glutaric acid, adipic acid, 6-hydroxycaproic acid, followed by hydrogenation to give 1, 6-hexanediol, which is then separated by distillation. Chinese patent CN1594252A discloses a method for preparing dimethyl adipate by using adipic acid as raw material through high pressure esterification and separation. Then taking dimethyl adipate as a raw material, and taking noble metals such as Pt, Pd, Ru and the like as catalysts to perform catalytic hydrogenation to prepare the 1, 6-hexanediol. Meanwhile, in Chinese patent CN101113128A, 1, 6-hexanediol is prepared by directly hydrogenating dimethyl adipate. Reaction ofThe pressure is 7MPa, the temperature is 300 ℃, and the space velocity is 0.2h-1. However, the above methods have the disadvantages of non-renewable raw materials, low product yield, more by-products and difficult separation, etc.
An important source of 1,2, 6-hexanetriol is obtained by the biomass-based catalytic hydrogenolysis of 5-Hydroxymethylfurfural (HMF). Catalytic conversion of HMF to 1,2, 6-hexanetriol was accomplished by lanovaya, usa in published patent CN 201580067986.7; patent CN201180036114.6 reports the conversion of 5-hydroxymethylfurfural to tetrahydropyran-2-methanol, followed by the conversion of tetrahydropyran-2-methanol to 1,2, 6-hexanetriol. The 1,2, 6-hexanetriol and the 1, 6-hexanediol have similar chemical structures and similar element compositions, if secondary hydroxyl in the 1,2, 6-hexanetriol molecule can be selectively removed, the 1, 6-hexanediol can be obtained, and a brand new technical route for preparing the 1, 6-hexanediol by taking biomass resources as final raw materials is established.
Disclosure of Invention
The invention aims to provide a method for preparing 1, 6-hexanediol by using 1,2, 6-hexanetriol as a raw material, which is simple to operate, high in conversion rate of the raw material and yield of the 1, 6-hexanediol and less in by-products.
The technical scheme of the invention is as follows:
a method for preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol comprises the steps of carrying out catalytic hydrogenolysis reaction on 1,2, 6-hexanetriol serving as a reaction raw material in a high-pressure reaction kettle; the active component of the catalyst in the reaction is one or more than two of nickel, ruthenium, rhodium, palladium, iridium and platinum, and the loading capacity of the active component in the catalyst on the carrier is 1-10 wt%; the dosage of the catalyst is 1-50% of the mass of the 1,2, 6-hexanetriol; the reaction is carried out in the presence of hydrogen, the pressure of the hydrogen is 0.5-8MPa, the reaction temperature is 60-240 ℃, and the reaction time is 0.5-12 h.
Adding solid acid into the reaction system, wherein the solid acid is one or more than two of tungstic acid, silicotungstic acid, phosphotungstic acid and phosphomolybdic acid; the dosage of the solid acid is less than 50% of the mass of the 1,2, 6-hexanetriol.
The catalyst also comprises a cocatalyst, wherein the cocatalyst and the active component are loaded on the carrier, and the molar ratio of the cocatalyst to the active component is less than 1.0; the catalyst promoter is one or more than two of zinc, magnesium, vanadium, manganese, molybdenum, tungsten and rhenium.
Before the catalyst is used for the reaction of preparing 1, 6-hexanediol by the catalytic hydrogenolysis of 1,2, 6-hexanetriol, the catalyst is pretreated: reducing for 0.5-6h at 200-500 ℃ in a hydrogen atmosphere.
Further, the carrier is Al in metal oxide2O3、TiO2、ZrO2、SiO2、Nb2O5、SnO2Or activated carbon.
Further, the reaction solvent of the catalytic hydrogenolysis reaction is one or more than two of water, propanol, methanol, ethanol and isopropanol; the mass concentration of the 1,2, 6-hexanetriol in the reaction system is 5-20%.
More preferably, the catalytic hydrogenolysis reaction is carried out under the conditions of 1-6MPa, 80-180 ℃ and 1-8 h.
The invention has the following advantages:
1. compared with the prior art, the process has the advantages that the raw material resources are renewable, the requirements of green chemistry and sustainable development are met, and the like.
2. Under the composite catalyst, the conversion rate of the 1,2, 6-hexanetriol is high, the yield of the 1, 6-hexanediol is high, the reaction time is short, and the reaction condition is mild.
Detailed Description
Example 1
Preparation of catalyst and catalytic hydrogenolysis experiment
The catalyst is prepared by adopting an impregnation method, wherein a carrier is nano zirconium dioxide, an aqueous solution of metal salt is subjected to isovolumetric impregnation, the nano zirconium dioxide is dried for 12 hours at 110 ℃ after impregnation, then the nano zirconium dioxide is roasted for 3 hours at 350 ℃ in an air atmosphere, and finally the nano zirconium dioxide is reduced for 2 hours at 300 ℃ in a hydrogen atmosphere. 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. Then, a certain amount of 1,2, 6-hexanetriol, a reaction solvent, a catalyst and solid acid are taken to be put into a 25mL stainless steel reaction kettle, and hydrogen with a certain pressure is introduced to repeatedly replace the air in the kettle. Raising the temperature to the designated temperature and reacting for a certain time. And after the reaction is finished, cooling the reaction kettle to room temperature, and finally carrying out suction filtration and chromatographic analysis on the reaction liquid.
Example 2
TABLE the results of the catalytic hydrogenolysis of 1,2, 6-hexanetriol on different active metal catalysts to 1, 6-hexanediol (160 ℃ C., 1MPa H)2The solvent is 2mL of water, the dosage of 1,2, 6-hexanetriol is 5mmol, the loading capacity of the active component is 5 wt%, and the cocatalyst is as follows: the active component is 1, the dosage of the catalyst is 5 weight percent, the dosage of the phosphotungstic acid is 5 weight percent, and the reaction time is 2h)
It can be seen from table one that the most preferred active component is Ru and the most preferred co-catalyst is Re. With Ru-ReOx/ZrO2The yield of 1, 6-hexanediol was 97 for complete conversion of the substrate by the catalyst. Secondly when using Ru/ZrO2The substrate was also completely converted in the case of the catalyst, and the yield of 1, 6-hexanediol was 95%. In view of economic problems the catalyst used in the following experiments was Ru/ZrO2。
Example 3
TABLE results of the catalytic hydrogenolysis of 1,2, 6-hexanetriol on different catalyst supports to 1, 6-hexanediol (160 ℃ C., 1 MPaH)2The solvent is 2mL of water, the dosage of 1,2, 6-hexanetriol is 5mmol, the loading capacity of Ru is 5 wt%, the dosage of the catalyst is 5 wt%, the dosage of phosphotungstic acid is 5 wt%, and the reaction time is 2h)
From Table two, it can be seen that the optimum carrier for the active component under the same reaction conditions is ZrO2At this time, 1,2, 6-hexanetriol was completely converted, and the selective yield of 1, 6-hexanediol was 98%.
Example 4
TABLE 3 on Ru/SiO2Addition of different solids to the catalystThe influence of the acid on the results of the catalytic hydrogenolysis of 1,2, 6-hexanetriol to 1, 6-hexanediol (160 ℃,1Mpa, 2h, 2mL of water as solvent, 5mmol of 1,2, 6-hexanetriol, 5 wt% of Ru loading, 5 wt% of catalyst and 5 wt% of solid acid).
It can be seen from Table 3 that the addition of both phosphotungstic acid and Amberlyst-15 can completely convert 1,2, 6-hexanetriol and can give high yields of 1, 6-hexanediol, although Amberlyst-15 has poor high temperature resistance, and we prefer phosphotungstic acid here.
Example 5
TABLE IV in Ru/Al2O3The results of the catalytic hydrogenolysis of 1,2, 6-hexanetriol to 1, 6-hexanediol at different reaction times on a catalyst (160 ℃,1MPa H)2The solvent is 2mL of water, the dosage of 1,2, 6-hexanetriol is 5mmol, the loading of Ru is 5 wt%, the dosage of the catalyst is 5 wt%, and the dosage of phosphotungstic acid is 5 wt%).
It can be seen from Table four that2O3The optimal reaction time on the catalyst is 4 hours, the 1,2, 6-hexanetriol is completely converted, and the yield of the 1, 6-hexanediol reaches 97 percent. The yield of 1, 6-hexanediol stabilized first and then decreased with increasing reaction time, and the yield of n-hexanol gradually increased.
Example 6
TABLE V results of the catalytic hydrogenolysis of 1,2, 6-hexanetriol to 1, 6-hexanediol over Ru/ZSM-5 catalyst at various reaction pressures (160 ℃ C., 2h, 2mL water as solvent, 5mmol of 1,2, 6-hexanetriol, 5 wt% Ru, 5 wt% catalyst, and 5 wt% phosphotungstic acid).
From Table V, it can be seen that the optimum reaction pressure was 1MPa, the conversion of 1,2, 6-hexanetriol was 92% and the yield of 1, 6-hexanediol was 94%. It can also be seen that the change in pressure does not have a great effect on the reaction, here we prefer the reaction pressure to be 1 MPa.
Example 7
TABLE VI Rh-Re/ZrO2Results of 1, 6-hexanediol production by catalytic hydrogenolysis of 1,2, 6-hexanetriol over a catalyst at different reaction temperatures (1MPa, 2h, 2mL of water as solvent, 5mmol of 1,2, 6-hexanetriol, 5 wt% of Ru-loading, 5 wt% of catalyst, and 5 wt% of phosphotungstic acid)
It can be seen from Table VI that the conversion of 1,2, 6-hexanetriol gradually increases with increasing temperature and the conversion is complete at 160 ℃ with a yield of 1, 6-hexanediol of 98%. The yield of 1, 6-hexanediol at the temperature was increased further to a maximum at 180 ℃ and then gradually decreased. The optimum reaction temperature is 160 ℃ in view of energy consumption.
Example 8
TABLE VII Ru/SnO2Influence of different solvents on the catalyst on the results of the catalytic hydrogenolysis of 1,2, 6-hexanetriol to 1, 6-hexanediol (160 ℃,1Mpa, 2h, 2mL of water as solvent, 5mmol of 1,2, 6-hexanetriol, 5 wt% of Ru loading, 5 wt% of catalyst and 5 wt% of phosphotungstic acid).
From table 7 we can see that water + tetrahydrofuran as solvent gave the best reaction results.
Example 9
TABLE 8 Ru/ZrO2Influence of different catalyst dosages on the catalyst on the result of preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol (160 ℃,1Mpa, 2h, 2mL of water as solvent, 5mmol of 1,2, 6-hexanetriol, 5 wt% of Ru loading and 5 wt% of phosphotungstic acid).
It can be seen from table eight that the yield of 1, 6-hexanediol shows a tendency of stabilizing and then decreasing with the increase of the catalyst amount, and the yield of n-hexanol starts to increase and finally becomes stable when the catalyst amount is more than 20 wt%. Thus an optimum catalyst loading of 5 wt% can be obtained.
Example 10
TABLE ninth in Ru-ReOx/ZrO2Influence of different solid acid dosages on the catalyst on the result of preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol (160 ℃,1Mpa, 2h, 2mL of water as solvent, 5mmol of 1,2, 6-hexanetriol, 5 wt% of Ru loading and 5 wt% of catalyst).
It can be seen from Table nine that the selectivity of 1, 6-hexanediol increases first and then decreases with increasing solid acid amount, and tetrahydropyran-2-methanol starts to appear when the solid acid amount is 10 wt% and gradually increases with increasing solid acid amount. It can thus be seen that the optimum amount of solid acid is 5% by weight.
Example 11
TABLE in Ru/ZrO2Influence of different substrate concentrations on the catalyst on the results of the catalytic hydrogenolysis of 1,2, 6-hexanetriol to 1, 6-hexanediol (160 ℃,1Mpa, 2h, 2mL water as solvent, 5 wt% Ru loading, 5 wt% catalyst, 5 wt% solid acid).
It can be seen from Table ten that the yield of 1, 6-hexanediol first increases and finally becomes stable as the conversion of 1,2, 6-hexanetriol gradually decreases with the increase of the substrate concentration. Thus, an optimum concentration of 10 wt% of substrate can be obtained.
Those skilled in the art of the present invention can easily conceive of changes or substitutions within the technical scope of the present invention, and all of them are included in the scope of the present invention. Therefore, the protection scope of the present invention is not limited to the above embodiments, and the protection scope of the claims should be subject to.
Claims (3)
1. A method for preparing 1, 6-hexanediol by catalytic hydrogenolysis of 1,2, 6-hexanetriol is characterized by comprising the following steps: carrying out catalytic hydrogenolysis reaction on 1,2, 6-hexanetriol serving as a reaction raw material in a high-pressure reaction kettle; the active component of the catalyst in the reaction is ruthenium, the catalyst also comprises a cocatalyst, the cocatalyst and the active component are loaded on the carrier, and the molar ratio of the cocatalyst to the active component is less than 1.0; the promoter is rhenium; the loading amount of the active component in the catalyst on the carrier is 1-10 wt%; the carrier is Al in metal oxide2O3、ZrO2、SiO2、Nb2O5One of (1); the dosage of the catalyst is 1-50% of the mass of the 1,2, 6-hexanetriol; solid acid is also added into the reaction system, and the solid acid is phosphotungstic acid; the dosage of the solid acid is less than 50 percent of the mass of the 1,2, 6-hexanetriol; the reaction solvent for the catalytic hydrogenolysis reaction is one or more than two of water, propanol, methanol, ethanol and isopropanol; the mass concentration of the 1,2, 6-hexanetriol in the reaction system is 5-20%; the reaction is carried out in the presence of hydrogen, the pressure of the hydrogen is 1-8MPa, the reaction temperature is 140-220 ℃, and the reaction time is 0.5-12 h.
2. The method of claim 1, wherein: the catalyst is used for pretreatment before the 1,2, 6-hexanetriol catalytic hydrogenolysis reaction for preparing the 1, 6-hexanediol: reducing for 0.5-6h at 200-500 ℃ in a hydrogen atmosphere.
3. The method according to claim 1 or 2, characterized in that: the reaction pressure of the catalytic hydrogenolysis reaction is 1-6MPa, the temperature is 140-.
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| CN101767006A (en) * | 2008-12-30 | 2010-07-07 | 拜耳技术工程（上海）有限公司 | Catalyst for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method thereof |
| CN104024197A (en) * | 2011-12-30 | 2014-09-03 | 纳幕尔杜邦公司 | Process for the production of hexanediols |
| JP2014185112A (en) * | 2013-03-25 | 2014-10-02 | Osaka Univ | Method of producing monool or diol |
| CN105344357A (en) * | 2015-09-30 | 2016-02-24 | 东南大学 | Catalyst for preparing 1,3-propanediol through glycerine hydrogenolysis |
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| CN101767006A (en) * | 2008-12-30 | 2010-07-07 | 拜耳技术工程（上海）有限公司 | Catalyst for preparing fatty alcohol with low carbon number by catalyzing and hydrolyzing glycerol and preparation method thereof |
| CN104024197A (en) * | 2011-12-30 | 2014-09-03 | 纳幕尔杜邦公司 | Process for the production of hexanediols |
| JP2014185112A (en) * | 2013-03-25 | 2014-10-02 | Osaka Univ | Method of producing monool or diol |
| CN105344357A (en) * | 2015-09-30 | 2016-02-24 | 东南大学 | Catalyst for preparing 1,3-propanediol through glycerine hydrogenolysis |
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