CN107473936B - A kind of method for preparing lower alkanol from diol compound - Google Patents
A kind of method for preparing lower alkanol from diol compound Download PDFInfo
- Publication number
- CN107473936B CN107473936B CN201710691071.4A CN201710691071A CN107473936B CN 107473936 B CN107473936 B CN 107473936B CN 201710691071 A CN201710691071 A CN 201710691071A CN 107473936 B CN107473936 B CN 107473936B
- Authority
- CN
- China
- Prior art keywords
- diol compound
- lower alkanol
- reaction
- corresponds
- ethanol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- -1 diol compound Chemical class 0.000 title claims description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 64
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 48
- 239000007864 aqueous solution Substances 0.000 claims description 27
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 24
- 238000006722 reduction reaction Methods 0.000 claims description 23
- 239000012279 sodium borohydride Substances 0.000 claims description 23
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 23
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 21
- 235000013772 propylene glycol Nutrition 0.000 claims description 21
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 18
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 14
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical compound OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 9
- WCVRQHFDJLLWFE-UHFFFAOYSA-N pentane-1,2-diol Chemical compound CCCC(O)CO WCVRQHFDJLLWFE-UHFFFAOYSA-N 0.000 claims description 7
- 229940015975 1,2-hexanediol Drugs 0.000 claims description 6
- ZMDUDEDTIDQZHT-UHFFFAOYSA-N buta-1,2-dien-1-ol Chemical compound CC=C=CO ZMDUDEDTIDQZHT-UHFFFAOYSA-N 0.000 claims description 6
- FHKSXSQHXQEMOK-UHFFFAOYSA-N hexane-1,2-diol Chemical compound CCCCC(O)CO FHKSXSQHXQEMOK-UHFFFAOYSA-N 0.000 claims description 6
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 5
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims 3
- 229940083957 1,2-butanediol Drugs 0.000 claims 2
- 229960004063 propylene glycol Drugs 0.000 claims 2
- 229940035437 1,3-propanediol Drugs 0.000 claims 1
- 238000001035 drying Methods 0.000 claims 1
- 238000001914 filtration Methods 0.000 claims 1
- 238000003756 stirring Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 150000002334 glycols Chemical class 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 40
- 230000009467 reduction Effects 0.000 description 20
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 11
- 238000001819 mass spectrum Methods 0.000 description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 150000001298 alcohols Chemical class 0.000 description 6
- 150000002009 diols Chemical class 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010504 bond cleavage reaction Methods 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000006053 organic reaction Methods 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 229940051250 hexylene glycol Drugs 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Images
Classifications
-
- 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
- C07C29/60—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by elimination of -OH groups, e.g. by dehydration
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
本发明属于有机物制备技术领域,公开了一种由二醇类化合物制备低级烷醇的方法,方法为:二醇类化合物和水,在纳米镍催化剂的作用下,发生水热反应,在反应温度160~220℃下反应6~24h可制得低级烷醇。本发明所用催化剂为纳米镍催化剂,原料易得,成本低廉;所述催化剂制备简单,可重复使用;该反应体系以水为溶剂,并不需要引入氢气。本发明的反应条件温和,对设备要求低,只需要密封的反应釜即可,设备简单,操作容易,且对相应低级烷醇的产率(1,2‑丙二醇制备乙醇)最高可达65%,具有良好的工业化前景。
The invention belongs to the technical field of organic compound preparation, and discloses a method for preparing lower alkanols from glycol compounds. Lower alkanols can be obtained by reacting at 160~220℃ for 6~24h. The catalyst used in the invention is a nano-nickel catalyst, the raw materials are readily available, and the cost is low; the catalyst is simple to prepare and can be reused; the reaction system uses water as a solvent, and does not need to introduce hydrogen. The reaction conditions of the invention are mild, the equipment requirements are low, only a sealed reaction kettle is needed, the equipment is simple, the operation is easy, and the yield of the corresponding lower alkanol (1,2-propylene glycol to prepare ethanol) can reach up to 65% , with good industrialization prospects.
Description
技术领域technical field
本发明属于有机物制备技术领域,尤其涉及一种由二醇类化合物制备低级烷醇的方法。The invention belongs to the technical field of organic preparation, and in particular relates to a method for preparing lower alkanols from diol compounds.
背景技术Background technique
近年来,在世界范围内人们广泛研究和发展利用化学或生物等方法将生物质衍生物二醇类化合物(乙二醇,1,2-丙二醇,1,2-丁二醇等)转化为燃料和其他高附加值的化学品。其中将二醇类化合物转化为低级醇类(甲醇,乙醇,丁醇)是该类化合物转化和利用的又一趋势,备受关注。由于低级醇类(甲醇,乙醇,丁醇)可以直接应用于动力燃料,该合成路径既可以提高生物质衍生物的可燃性,又可以提高生物质衍生物的应用范围。二醇类化合物含有碳氧和碳碳,其中碳氧键更容易断裂,但是选择性实现碳碳键断裂制备低级烷醇存在一定的困难。因为在有机化学领域,非极性碳碳键在热力学上非常稳定,它们的HOMO能量太低,LUMO能量太高很难与催化剂相结合,因此在很多有机反应中碳碳键会保持稳定,因此二醇类化合物制备低级烷醇。目前,碳碳键断裂主要存在的问题是:反应底物的复杂性,不具有普适性。催化剂合成复杂,反应条件苛刻,对于低级醇类的选择性低。同样还存在的一个重要的问题是二醇类化合物转化为低级醇类需要引入大量的氢气和有毒的化学溶剂。In recent years, the use of chemical or biological methods to convert biomass derivatives glycol compounds (ethylene glycol, 1,2-propanediol, 1,2-butanediol, etc.) into fuels has been widely studied and developed worldwide. and other high value-added chemicals. Among them, the conversion of glycol compounds into lower alcohols (methanol, ethanol, butanol) is another trend in the conversion and utilization of such compounds, which has attracted much attention. Since lower alcohols (methanol, ethanol, butanol) can be directly applied to power fuels, this synthesis route can not only improve the flammability of biomass derivatives, but also improve the application range of biomass derivatives. Diols contain carbon-oxygen and carbon-carbon, in which the carbon-oxygen bond is easier to break, but it is difficult to selectively realize the cleavage of carbon-carbon bond to prepare lower alkanols. Because in the field of organic chemistry, non-polar carbon-carbon bonds are very thermodynamically stable, their HOMO energy is too low, and their LUMO energy is too high to combine with catalysts, so carbon-carbon bonds will remain stable in many organic reactions, so Diols are used to prepare lower alkanols. At present, the main problem of carbon-carbon bond cleavage is: the complexity of the reaction substrate, which is not universal. The catalyst has complex synthesis, harsh reaction conditions and low selectivity to lower alcohols. There is also an important problem that the conversion of diols into lower alcohols requires the introduction of a large amount of hydrogen and toxic chemical solvents.
综上所述,现有技术存在的问题是:在二醇类化合物制备低级烷醇的过程中,所使用的催化剂制备复杂,通入高压氢气具有一定的危险性并使用了有毒有机溶剂;在合成低级烷醇的过程中选择性较低,存在着易于形成醚类化合物,操作过程困难,成本高等问题。To sum up, the problems existing in the prior art are: in the process of preparing lower alkanols from diol compounds, the catalyst used is complicated to prepare, and the introduction of high-pressure hydrogen is dangerous and toxic organic solvents are used; In the process of synthesizing lower alkanols, the selectivity is low, and there are problems such as easy formation of ether compounds, difficult operation process and high cost.
发明内容SUMMARY OF THE INVENTION
针对现有技术存在的问题,本发明提供了一种由二醇类化合物制备低级烷醇的方法。In view of the problems existing in the prior art, the present invention provides a method for preparing lower alkanols from diol compounds.
本发明是这样实现的,一种由二醇类化合物制备低级烷醇的方法,所述由二醇类化合物制备低级烷醇的方法,在不引入氢气的条件下,以二醇类化合物和水为原料,以纳米镍为催化剂,将所述二醇类化合物、水、纳米镍装入高压反应釜后密封在水的饱和蒸汽压下(0.6-2.3Mpa)发生水热反应,在160℃~220℃下反应6h~30h,冷却后过滤得到低级烷醇溶液。The present invention is achieved in this way, a method for preparing lower alkanols from glycol compounds, the method for preparing lower alkanols from glycol compounds, without introducing hydrogen, with glycol compounds and water As raw material, with nano-nickel as catalyst, the glycol compound, water and nano-nickel are put into the autoclave and sealed under the saturated steam pressure of water (0.6-2.3Mpa) to undergo hydrothermal reaction, and the reaction is carried out at 160 ℃~ The reaction was carried out at 220°C for 6h-30h, and after cooling, the solution was filtered to obtain a lower alkanol solution.
进一步,所述由二醇类化合物制备低级烷醇的方法化学反应式为:Further, the chemical reaction formula of the method for preparing lower alkanol by diol compound is:
进一步,所述二醇类化合物为1,2-丙二醇、1,2-丁二醇、1,2-戊二醇、1,2-己二醇、1,3-丙二醇及1,2-丁二烯醇中的一种。Further, the diol compounds are 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,3-propanediol and 1,2-butanediol One of the dienols.
进一步,反应后的低级烷醇为:1,2-丙二醇对应的是乙醇;1,2-丁二醇对应的是正丙醇;1,2-戊二醇对应的是正丁醇;1,2-己二醇对应的是正戊醇;1,3-丙二醇对应的是乙醇;1,2-丁二烯醇对应的是正丙醇。Further, the lower alkanols after the reaction are: 1,2-propanediol corresponds to ethanol; 1,2-butanediol corresponds to n-propanol; 1,2-pentanediol corresponds to n-butanol; Hexylene glycol corresponds to n-pentanol; 1,3-propanediol corresponds to ethanol; 1,2-butadienol corresponds to n-propanol.
进一步,所述二醇类化合物和水为原料中,二醇类化合物的水溶液为:25ml,0.05mol/L的二醇类化合物水溶液;纳米镍为:0.05g~0.5g。Further, in the diol compound and water as raw materials, the aqueous solution of the diol compound is: 25ml, 0.05mol/L of the diol compound aqueous solution; the nano nickel is: 0.05g~0.5g.
进一步,所述的纳米镍催化剂采用湿化学还原法制得,具体方法包括:Further, the nano-nickel catalyst is prepared by wet chemical reduction method, and the specific method includes:
4.27g的氯化镍溶于300ml水中,在氮气氛围下,逐滴加入100ml的1mol的硼氢化钠水溶液,剧烈搅拌3h~5h,反应结束后用水洗涤数次,在真空干燥箱干燥12h后,得到纳米镍催化剂。4.27g of nickel chloride was dissolved in 300ml of water, under nitrogen atmosphere, 100ml of 1mol sodium borohydride aqueous solution was added dropwise, vigorously stirred for 3h to 5h, washed with water several times after the reaction, and dried in a vacuum drying box for 12h, A nano-nickel catalyst is obtained.
本发明的另一目的在于提供一种利用上述由二醇类化合物制备低级烷醇的方法制备的低级烷醇。Another object of the present invention is to provide a lower alkanol prepared by utilizing the above-mentioned method for preparing lower alkanol from a diol compound.
本发明的另一目的在于提供一种利用上述低级烷醇制备的动力燃料。Another object of the present invention is to provide a power fuel prepared by utilizing the above-mentioned lower alkanol.
本发明的优点及积极效果为:The advantages and positive effects of the present invention are:
本发明发展了一种新的方法,在不使用高压氢气的条件下,通过水热反应,使用简单的非晶镍基催化剂,有效的将二醇类化合物通过选择性碳碳键的断裂转化为低级醇类。为有机反应中碳碳键的活化,特别是碳碳键断裂提供了新的思路。The present invention develops a new method, which can efficiently convert diols into diols through selective carbon-carbon bond cleavage through hydrothermal reaction without using high-pressure hydrogen using a simple amorphous nickel-based catalyst. lower alcohols. It provides a new idea for the activation of carbon-carbon bonds in organic reactions, especially the cleavage of carbon-carbon bonds.
与本发明最接近的现有技术发表在ACS Catal.2012,2,1285-1289上的论文,题目是《Partial Deoxygenation of 1,2-Propanediol Catalyzed by Iridium PincerComplexes》。与此方法相比,本发明的优点在于:The closest prior art to the present invention is a paper published in ACS Catal. 2012, 2, 1285-1289, entitled "Partial Deoxygenation of 1,2-Propanediol Catalyzed by Iridium PincerComplexes". Compared with this method, the advantages of the present invention are:
本发明所用催化剂为纳米镍催化剂,原料易得,成本低廉;所述催化剂制备简单,可重复使用;该反应体系以水为溶剂,并不需要引入氢气。本发明的反应条件温和,对设备要求低,只需要密封的反应釜即可,设备简单,操作容易,且对相应低级烷醇的产率(1,2-丙二醇制备乙醇)最高可达65%,具有良好的工业化前景。The catalyst used in the invention is a nano-nickel catalyst, the raw materials are readily available, and the cost is low; the catalyst is simple to prepare and can be reused; the reaction system uses water as a solvent, and does not need to introduce hydrogen. The reaction conditions of the invention are mild, the equipment requirements are low, only a sealed reaction kettle is needed, the equipment is simple, the operation is easy, and the yield of the corresponding lower alkanol (1,2-propanediol to prepare ethanol) can reach up to 65% , with good industrialization prospects.
附图说明Description of drawings
图1是本发明实施例提供的由二醇类化合物制备低级烷醇的方法流程图。1 is a flow chart of a method for preparing lower alkanols from diol compounds provided in an embodiment of the present invention.
图2是本发明实施例提供的实施例1和18中产物乙醇的质谱图。FIG. 2 is a mass spectrum of the product ethanol in Examples 1 and 18 provided in the embodiment of the present invention.
图3是本发明实施例提供的实施例14和17中产物正丙醇的质谱图。Fig. 3 is the mass spectrum of the product n-propanol in Examples 14 and 17 provided by the embodiment of the present invention.
图4是本发明实施例提供的实施例15中产物正丁醇的质谱图。Fig. 4 is the mass spectrum of the product n-butanol in Example 15 provided by the embodiment of the present invention.
图5是本发明实施例提供的实施例16中产物正戊醇的质谱图。Fig. 5 is the mass spectrum of the product n-amyl alcohol in Example 16 provided by the embodiment of the present invention.
具体实施方式Detailed ways
为了使本发明的目的、技术方案及优点更加清楚明白,以下结合实施例,对本发明进行进一步详细说明。应当理解,此处所描述的具体实施例仅仅用以解释本发明,并不用于限定本发明。In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention, but not to limit the present invention.
现有技术,所使用的催化剂制备复杂,通入高压氢气具有一定的危险性并使用了有毒性的二氧六环为溶剂;合成的正丙醇,存在着易于形成醚类化合物,操作过程困难,成本高等问题。In the prior art, the catalyst used is complicated to prepare, and the introduction of high-pressure hydrogen has certain dangers and toxic dioxane is used as a solvent; the synthetic n-propanol is easy to form ether compounds, and the operation process is difficult , the problem of high cost.
基于此理论,本发明发展了一种新的方法,在水热条件下,使用简单的非晶镍基催化剂有效的将二醇类化合物通过选择性碳碳键的断裂转化为低级醇类。为有机反应中碳碳键的活化,特别是碳碳键断裂提供了新的思路。Based on this theory, the present invention develops a new method to efficiently convert diols into lower alcohols through selective carbon-carbon bond cleavage using a simple amorphous nickel-based catalyst under hydrothermal conditions. It provides a new idea for the activation of carbon-carbon bonds in organic reactions, especially the cleavage of carbon-carbon bonds.
下面结合附图对本发明的应用原理作详细描述。The application principle of the present invention will be described in detail below with reference to the accompanying drawings.
如图1所示,本发明实施例提供的由二醇类化合物制备低级烷醇的方法,包括:As shown in Figure 1, the method for preparing lower alkanol from diol compounds provided in the embodiment of the present invention comprises:
S101:将一定量的二醇类化合物,一定量的水和纳米镍装入高压反应釜中,混合均匀。S101: put a certain amount of glycol compounds, a certain amount of water and nano-nickel into the autoclave, and mix them uniformly.
S102:密封后在160~220℃下反应6~24小时,冷却后得到低级烷醇溶液。S102: After sealing, react at 160-220° C. for 6-24 hours, and obtain a lower alkanol solution after cooling.
作为本发明实施例的优选方案,所述的二醇类化合物为1,2-丙二醇,1,2-丁二醇,1,2-戊二醇,1,2-己二醇,1,3-丙二醇,1,2-丁二烯醇。As a preferred solution in the embodiment of the present invention, the diol compounds are 1,2-propanediol, 1,2-butanediol, 1,2-pentanediol, 1,2-hexanediol, 1,3 - Propylene glycol, 1,2-butadienol.
反应后的主产物是1,2-丙二醇对应的是乙醇,1,2-丁二醇对应的是正丙醇,1,2-戊二醇对应的是正丁醇,1,2-己二醇对应的是正戊醇,1,3-丙二醇对应的是乙醇,1,2-丁二烯醇对应的是正丙醇。The main product after the reaction is that 1,2-propanediol corresponds to ethanol, 1,2-butanediol corresponds to n-propanol, 1,2-pentanediol corresponds to n-butanol, and 1,2-hexanediol corresponds to is n-pentanol, 1,3-propanediol corresponds to ethanol, and 1,2-butadienol corresponds to n-propanol.
所述的纳米镍催化剂采用湿化学还原法制得,具体方法如下:Described nanometer nickel catalyst adopts wet chemical reduction method to make, and concrete method is as follows:
4.27g的氯化镍溶于300ml水中,在氮气氛围下,逐滴加入100ml的1mol的硼氢化钠水溶液,剧烈搅拌3h~5h,反应结束后用水洗涤数次,在真空干燥箱干燥12h后,得到纳米镍催化剂。4.27g of nickel chloride was dissolved in 300ml of water, under nitrogen atmosphere, 100ml of 1mol sodium borohydride aqueous solution was added dropwise, vigorously stirred for 3h to 5h, washed with water several times after the reaction, and dried in a vacuum drying box for 12h, A nano-nickel catalyst is obtained.
作为本发明实施例的优选方案,优选的条件为160~220℃下反应6~30h。As a preferred solution of the embodiment of the present invention, the preferred condition is that the reaction is carried out at 160-220° C. for 6-30 hours.
作为本发明实施例的优选方案,优选的催化剂的量为0.05-0.5g。As a preferred solution of the embodiment of the present invention, the preferred amount of the catalyst is 0.05-0.5 g.
下面结合具体实施例对本发明的应用原理作进一步描述。The application principle of the present invention will be further described below with reference to specific embodiments.
实施例1Example 1
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.2g of nano-nickel prepared by reduction of sodium borohydride into a 30mL autoclave, and after sealing the reactor, react at 200°C for 24h, After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为48%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). From the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 48%.
实施例2Example 2
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在220℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.2g of nano-nickel prepared by sodium borohydride reduction into a 30mL autoclave, and after sealing the reactor, react at 220°C for 24h, After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为43%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). From the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 43%.
实施例3Example 3
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在180℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.2g of nano-nickel prepared by reduction of sodium borohydride into a 30mL autoclave, and after sealing the reactor, react at 180°C for 24h, After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为46%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). Based on the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 46%.
实施例4Example 4
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在160℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.2g of nano-nickel prepared by sodium borohydride reduction into an autoclave with a volume of 30mL. After sealing the reactor, react at 160°C for 24h. After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为35%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product can be calculated to be 35%.
实施例5Example 5
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.05g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.05g of nano-nickel prepared by reduction of sodium borohydride into an autoclave with a volume of 30mL. After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为15%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). From the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 15%.
实施例6Example 6
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.05g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应30h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.05g of nano-nickel prepared by reduction of sodium borohydride into an autoclave with a volume of 30mL. After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为20%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product can be calculated to be 20%.
实施例7Example 7
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.1g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.1g of nano-nickel prepared by reduction of sodium borohydride into a 30mL autoclave, and after sealing the reactor, react at 200°C for 24h, After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为42%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). From the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 42%.
实施例8Example 8
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.3g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.3g of nano-nickel prepared by reduction of sodium borohydride into an autoclave with a volume of 30mL, after sealing the reactor, react at 200°C for 24h, After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为47%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). From the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 47%.
实施例9Example 9
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.4g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.4g of nano-nickel prepared by reduction of sodium borohydride into an autoclave with a volume of 30mL. After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为46%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). Based on the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 46%.
实施例10Example 10
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.5g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.5g of nano-nickel prepared by reduction of sodium borohydride into an autoclave with a volume of 30mL. After sealing the reactor, react at 200°C for 24h. After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为45%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). Based on the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 45%.
实施例11Example 11
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.5g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应30h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L 1,2-propanediol aqueous solution and 0.5g of nano-nickel prepared by reduction of sodium borohydride into a 30mL autoclave, and after sealing the reactor, react at 200°C for 30h, After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为47%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). From the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 47%.
实施例12Example 12
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应6h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.2g of nano-nickel prepared by reduction of sodium borohydride into an autoclave with a volume of 30mL. After sealing the reactor, react at 200°C for 6h. After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为5%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). From the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product can be calculated to be 5%.
实施例13Example 13
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应12h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.2g of nano-nickel prepared by reduction of sodium borohydride into a 30mL autoclave, and after sealing the reactor, react at 200°C for 12h, After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为31%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). From the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 31%.
实施例14Example 14
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.5g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应18h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,2-propanediol and 0.5g of nano-nickel prepared by sodium borohydride reduction into an autoclave with a volume of 30mL. After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为43%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). From the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 43%.
实施例15Example 15
将25ml的0.05mol/L的1,2-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.5g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应30h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L 1,2-propanediol aqueous solution and 0.5g of nano-nickel prepared by reduction of sodium borohydride into a 30mL autoclave, and after sealing the reactor, react at 200°C for 30h, After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为46%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). Based on the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 46%.
实施例16Example 16
将25ml的0.05mol/L的1,2-丁二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。The aqueous solution of the 1,2-butanediol of 0.05mol/L of 25ml and the nano-nickel 0.2g prepared by the reduction of sodium borohydride are put into the autoclave with a volume of 30mL, and after the closed reactor, react at 200°C 24h, after the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中正丙醇的摩尔产率为为42%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the product peak area, the molar yield of n-propanol in the product can be calculated to be 42%.
实施例17Example 17
将25ml的0.05mol/L的1,2-戊二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。The aqueous solution of the 1,2-pentanediol of 0.05mol/L of 25ml and the nano-nickel 0.2g prepared by the reduction of sodium borohydride are put into the autoclave with a volume of 30mL, and after the closed reactor, react at 200°C 24h, after the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中正丁醇的摩尔产率为为50%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the product peak area, the molar yield of n-butanol in the product can be calculated to be 50%.
实施例18Example 18
将25ml的0.05mol/L的1,2-己二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。The aqueous solution of the 1,2-hexanediol of 0.05mol/L of 25ml and the nano-nickel 0.2g prepared by the reduction of sodium borohydride are put into the autoclave with a volume of 30mL, after sealing the reactor, react at 200°C 24h, after the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中正戊醇的摩尔产率为为50%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the product peak area, the molar yield of n-amyl alcohol in the product can be calculated to be 50%.
实施例19Example 19
将25ml的0.05mol/L的1,2-丁二烯醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。The aqueous solution of 25ml of 0.05mol/L 1,2-butadienol and 0.2g of nano-nickel prepared by sodium borohydride reduction were put into the autoclave with a volume of 30mL, after the closed reaction kettle, at 200°C The reaction was carried out for 24h, and after the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中正丙醇的摩尔产率为为32%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). According to the concentration-peak area standard curve and the product peak area, the molar yield of n-propanol in the product can be calculated to be 32%.
实施例20Example 20
将25ml的0.05mol/L的1,3-丙二醇的水溶液和由硼氢化钠还原制备的纳米镍0.2g放入容积为30mL的高压反应釜中,密闭反应釜后,在200℃下反应24h,待反应釜冷却后,反应溶液待测。Put 25ml of 0.05mol/L aqueous solution of 1,3-propanediol and 0.2g of nano-nickel prepared by reduction of sodium borohydride into an autoclave with a volume of 30mL. After the reaction kettle was cooled, the reaction solution was tested.
利用气相色谱-质谱联用仪(TRACE DSQ GC-MS)对所得溶液进行检测。根据浓度-峰面积标准曲线和产物峰面积,可计算出产物中乙醇的摩尔产率为25%。The resulting solution was detected by gas chromatography-mass spectrometry (TRACE DSQ GC-MS). Based on the concentration-peak area standard curve and the product peak area, the molar yield of ethanol in the product was calculated to be 25%.
图2是本发明实施例提供的实施例1和18中产物乙醇的质谱图。FIG. 2 is a mass spectrum of the product ethanol in Examples 1 and 18 provided in the embodiment of the present invention.
图3是本发明实施例提供的实施例14和17中产物正丙醇的质谱图。Fig. 3 is the mass spectrum of the product n-propanol in Examples 14 and 17 provided by the embodiment of the present invention.
图4是本发明实施例提供的实施例15中产物正丁醇的质谱图。Fig. 4 is the mass spectrum of the product n-butanol in Example 15 provided by the embodiment of the present invention.
图5是本发明实施例提供的实施例16中产物正戊醇的质谱图。Fig. 5 is the mass spectrum of the product n-amyl alcohol in Example 16 provided by the embodiment of the present invention.
以上所述仅为本发明的较佳实施例而已,并不用以限制本发明,凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等,均应包含在本发明的保护范围之内。The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention shall be included in the protection of the present invention. within the range.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710691071.4A CN107473936B (en) | 2017-08-14 | 2017-08-14 | A kind of method for preparing lower alkanol from diol compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710691071.4A CN107473936B (en) | 2017-08-14 | 2017-08-14 | A kind of method for preparing lower alkanol from diol compound |
Publications (2)
Publication Number | Publication Date |
---|---|
CN107473936A CN107473936A (en) | 2017-12-15 |
CN107473936B true CN107473936B (en) | 2020-12-11 |
Family
ID=60600226
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710691071.4A Active CN107473936B (en) | 2017-08-14 | 2017-08-14 | A kind of method for preparing lower alkanol from diol compound |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107473936B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103193593A (en) * | 2013-03-08 | 2013-07-10 | 吉林大学 | Method for preparing n-butanol from ethanol by using hydrothermal technique |
CN103288596A (en) * | 2012-02-27 | 2013-09-11 | 中国科学院大连化学物理研究所 | Method for preparing monohydric alcohol or dihydric alcohol through organic acid hydrogenation |
CN103962570A (en) * | 2013-02-03 | 2014-08-06 | 宇辰新能源材料科技无锡有限公司 | Preparation method of nickel nanopowder |
CN106866364A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of method that 1,3- ring pentanediols are prepared by furfuryl alcohol |
CN108187674A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Tantalum base catalyst and its application in the reaction of tetrahydrofurfuryl alcohol 1,5- pentanediols |
-
2017
- 2017-08-14 CN CN201710691071.4A patent/CN107473936B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103288596A (en) * | 2012-02-27 | 2013-09-11 | 中国科学院大连化学物理研究所 | Method for preparing monohydric alcohol or dihydric alcohol through organic acid hydrogenation |
CN103962570A (en) * | 2013-02-03 | 2014-08-06 | 宇辰新能源材料科技无锡有限公司 | Preparation method of nickel nanopowder |
CN103193593A (en) * | 2013-03-08 | 2013-07-10 | 吉林大学 | Method for preparing n-butanol from ethanol by using hydrothermal technique |
CN106866364A (en) * | 2015-12-12 | 2017-06-20 | 中国科学院大连化学物理研究所 | A kind of method that 1,3- ring pentanediols are prepared by furfuryl alcohol |
CN108187674A (en) * | 2016-12-08 | 2018-06-22 | 中国科学院大连化学物理研究所 | Tantalum base catalyst and its application in the reaction of tetrahydrofurfuryl alcohol 1,5- pentanediols |
Also Published As
Publication number | Publication date |
---|---|
CN107473936A (en) | 2017-12-15 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104998659B (en) | It is a kind of to be used to be catalyzed furfural or furfuryl alcohol rearrangement Hydrogenation for the catalyst of cyclopentanol and its preparation method and application method | |
CN105013509B (en) | A kind of furfural or furfuryl alcohol aqueous phase Hydrogenation is for the catalyst of cyclopentanone and its preparation method and application method | |
CN102126957B (en) | Method for preparing carbonic ester and ethylene alcohol by ionic liquid catalysis | |
CN110437184B (en) | A kind of method that furfural lower alkanol transfer hydrogenation prepares furfuryl alcohol | |
CN106824188A (en) | A kind of preparation of tungsten-based catalyst of carrying transition metal and application process | |
CN101455976A (en) | Effective catalyst used in hydrogenation of dimethyl oxalate to synthesizing ethylene glycol and production method thereof | |
CN102516222B (en) | Method for preparing cyclohexyl crown ether by catalytic hydrogenation of carbon-supported ruthenium catalyst | |
CN104437453B (en) | A kind of platinum/carbon aerogel catalyst and its production and use | |
CN109942517A (en) | A kind of method that metal hydroxide catalyzes furfural transfer hydrogenation to prepare furfuryl alcohol | |
CN103922931A (en) | Method for one-step catalytic synthesis of ethylene glycol ethyl ether acetate | |
CN110872254B (en) | Pyrazole salt diionic liquid and method for catalyzing synthesis of cyclic carbonate by utilizing the same | |
CN103204840B (en) | Method for preparing cyclic carbonate by using functional guanidinium ionic liquid | |
CN107473936B (en) | A kind of method for preparing lower alkanol from diol compound | |
CN103157513B (en) | Aluminum complexing conjugated micropore polymer catalyst, preparation thereof and application | |
CN106010627B (en) | A kind of method for being catalyzed aliphatic acid or fatty acid ester hydrogenation deoxidation and preparing long chain alkane fuel | |
CN107253904A (en) | A kind of method of lignin degradation | |
CN111961015A (en) | Method for preparing 2, 5-furandimethanol by catalyzing 5-hydroxymethylfurfural | |
CN112125781A (en) | A kind of method that furfural is converted into 1,2,5-pentanetriol by hydrogenation and hydrolysis | |
CN111393402B (en) | N & lt/EN & gt acid/quaternary ammonium salt composite catalytic CO 2 Method for preparing cyclic carbonate by cycloaddition with epoxide | |
CN115108887A (en) | A kind of preparation method of ethylene glycol | |
CN107417494A (en) | The method that a kind of aliphatic acid original position hydrogenation prepares fatty alcohol | |
CN104324748A (en) | Catalyst for conversion of fructose to 5-hydroxymethylfurfural | |
CN111233942B (en) | Method for converting photocatalytic lignin model compound | |
CN102452911B (en) | Method for converting C-N bond to C-C bond by allyl substitution reaction based on palladium catalysis | |
CN108607553A (en) | A kind of hydrogenolysis of glycerin prepares catalyst and preparation and the application of 1,3- propylene glycol |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |