CN106866364A - Method for preparing 1,3-cyclopentanediol from furfuryl alcohol - Google Patents

Method for preparing 1,3-cyclopentanediol from furfuryl alcohol Download PDF

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CN106866364A
CN106866364A CN 201510923635 CN201510923635A CN106866364A CN 106866364 A CN106866364 A CN 106866364A CN 201510923635 CN201510923635 CN 201510923635 CN 201510923635 A CN201510923635 A CN 201510923635A CN 106866364 A CN106866364 A CN 106866364A
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catalyst
reaction
step
cyclopentenone
alcohol
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CN 201510923635
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李宁
李广亿
张涛
王爱琴
王晓东
丛昱
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中国科学院大连化学物理研究所
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132Preparation 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
    • C07C29/136Preparation 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
    • C07C29/143Preparation 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 ketones
    • C07C29/145Preparation 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 ketones with hydrogen or hydrogen-containing gases
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/17Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/56Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds
    • C07C45/57Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom
    • C07C45/59Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds from heterocyclic compounds with oxygen as the only heteroatom in five-membered rings

Abstract

The invention relates to a method for preparing 1,3-cyclopentanediol from furfuryl alcohol. According to the method, furfuryl alcohol is used as a raw material, and 1,3-cyclopentanediol is prepared through two steps of reactions. The method comprises a first step of subjecting a furfuryl alcohol solution to a rearrangement reaction in the presence of an alkaline catalyst or in the absence of any catalyst so as to prepare hydroxycyclopentenone and a second step of reacting hydroxycyclopentenone with hydrogen under the catalysis of a hydrogenation catalyst so as to prepare 1,3-cyclopentanediol. The catalysts and raw materials used in the invention are cheap and easily available; the preparation method is simple in process; and high activity and selectivity are obtained in the rearrangement reaction of furfuryl alcohol and the hydrogenation reaction of hydroxycyclopentenone. The method provided by the invention is high-efficiency synthetic method for preparing 1,3-cyclopentanediol from a lignocelluloses-based platform compound, i.e., furfuryl alcohol.

Description

一种由糠醇制备1 ,3-环戊二醇的方法 A method of 1, 3-cyclopentane diol prepared from furfuryl alcohol

技术领域 FIELD

[0001] 本发明涉及一种由糠醇制备1,3_环戊二醇的方法。 [0001] The present invention relates to a 1,3_ cyclopentane diol prepared by the method of furfuryl alcohol. 具体包括两步反应:第一步为糠醇溶液在碱催化剂或不添加催化剂的条件下,经重排反应制备羟基环戊烯酮,第二步为羟基环戊烯酮在加氢催化剂催化下与氢气反应制备1,3_环戊二醇。 It comprises two steps: the first step is a solution in alcohol or a base catalyst without the addition of a catalyst, prepared by the rearrangement reaction of a hydroxyl group of the cyclopentenone, cyclopentenone and the second step is a hydroxyl group in the catalytic hydrogenation catalyst preparation 1,3_ cyclopentane diol reacted with hydrogen. 与目前已有报道的制备1,3_环戊二醇的方法相比,本发明催化剂廉价易得,制备工艺简单,反应的活性和选择性高。 Compared with the method of preparing 1,3_ cyclopentane diol currently been reported, the catalyst of the present invention is inexpensive, readily available, simple preparation process, high activity and selectivity of the reaction. 本发明提供了一种由木质纤维素基平台化合物合糠醇合成1,3_环戊二醇的一种廉价高效合成方法。 The present invention provides an inexpensive and efficient method of synthesizing a bonded lignocellulosic internet compound of furfuryl alcohol synthesis 1,3_ cyclopentane diol.

背景技术 Background technique

[0002] 化石资源的日益减少以及由化石能源燃烧引起的温室气体的大量排等环境问题日益突出,加之能源的社会需求量还在持续增加,石油价格不断上涨,可替代化石资源的新能源的开发势在必行。 [0002] dwindling fossil resources and a large number of greenhouse gas emissions caused by burning fossil fuels and other environmental issues have become increasingly prominent, coupled with the social demand for energy continues to increase, rising oil prices, new alternative energy resource of fossil development imperative. 生物质作为一种可再生的有机碳源应用于碳材料、燃料及化学品的生产中成为目前的热点研究。 Biomass as a renewable carbon source is applied to the carbon material, the production of fuels and chemicals become the hot research.

[0003] 1,3_环戊二醇是重要的化工原料之一,广泛应用于合成聚酯、聚氨酯、农药以及其它有机合成中间体(CN 103642005 A,US 20130244170 Al,TO 2013138161 Al)。 [0003] 1,3_ cyclopentane diol is an important chemical raw material, widely used in synthesis of polyesters, polyurethanes, and other organic synthetic intermediate of pesticides (CN 103642005 A, US 20130244170 Al, TO 2013138161 Al). 1,3-环戊二醇的合成方法主要是通过石化路线中的产物环戊二烯经硼烷还原,再通过双氧水氧化合成(J.Am.Chem.Soc.,1963,85(14) :2066)。 Synthesis of 1,3-cyclopentane diol mainly via borane reduction by the product of the petrochemical route cyclopentadiene, and then synthesized by oxidation of hydrogen peroxide (J.Am.Chem.Soc, 1963,85 (14).: 2066). 该路线需要消耗计量比的剧毒的硼烷和双氧水, 是非常不绿色环保的合成方法。 The route of consuming toxic stoichiometric borane and hydrogen peroxide, is not green synthetic methods. 另一方面,该方法的原料来源于化石能源的产品,具有不可再生性。 On the other hand, the process from raw materials of fossil fuels products, having non-renewable. 糠醇是农林废弃物生物质中半纤维素部分通过水解和脱水反应获得的一种重要的平台化合物,目前已经有几十年的工业化生产历史。 Alcohol is an important platform chemical agricultural and forestry waste biomass hemicellulose fraction obtained by hydrolysis and dehydration reaction, there are already several decades of industrial production history. 以糠醛及其衍生物为原料合成1,3_环戊二醇国际上鲜有报道。 Furfural and its derivatives synthesized 1,3_ cyclopentane diol international rarely reported. 最近,Huber等人(J.Catal. ,2015,330:19-27)报道了通过一步法加氢生物质平台化合物糠醇制备1,5_戊二醇,其中副产少量的1,3_环戊二醇(产率小于7%)〇 Recently, Huber et al (J.Catal, 2015,330:. 19-27) reported the preparation of a compound of furfuryl alcohol by one-step hydrogenation 1,5_-pentanediol biomass platform, wherein the amount of by-produced cyclic 1,3_ pentanediol (less than 7% yield) square

[0004] 在本课题组长期从事生物质催化转化制备油品和化学品的工作(中国专利:申请号:201110346501·1和ChemSusChem.2012,5,1958-1966;Bioresource Technology·2013, 134,66-72;Chem.Commun. ,2013,49,5727-5729)。 [0004] In the present research group engaged in preparation of the catalytic conversion of oil and for the chemicals (Biomass Chinese patent: application number: 201 110 346 501 * 1 and ChemSusChem.2012,5,1958-1966; Bioresource Technology · 2013, 134,66 -72; Chem.Commun, 2013,49,5727-5729).. 开发了一系列生物质及其平台化合物高效利用的路线。 We developed a series of route internet biomass and efficient use of the compound. 本专利描述的由糠醛选择性加氢产物一糠醇制备1,3_环戊二醇的制备方法,所用催化剂简单易得,价格低廉;制备工艺中,除了氢气外,无需消耗其它计量比的试剂。 Preparation process, in addition to hydrogen, without consuming additional reagent stoichiometry; prepared by the selective hydrogenation of furfural alcohol product prepared 1,3_ a cyclopentane diol described in this patent, the catalyst is simple and readily available, inexpensive with . 整个路线绿色环保,利用可再生的生物质平台化合物糠醇高效的制备出了1,3_环戊二醇。 Green entire route, the use of biomass renewable internet furfuryl alcohol compounds prepared in an efficient 1,3_ cyclopentane diol.

发明内容 SUMMARY

[0005] 本发明目的在于提供一种由糠醇制备1,3_环戊二醇的方法。 [0005] The object of the present invention to provide a method 1,3_ cyclopentane diol prepared from furfuryl alcohol.

[0006] 本发明是通过以下技术方案实现的: [0006] The present invention is achieved by the following technical solutions:

[0007] 以糠醇为原料制备1,3_环戊二醇共分为两步反应: [0007] In the preparation of alcohol as a raw material 1,3_ cyclopentane diol is divided into two steps:

[0008] 第一步为糠醇溶液在碱催化剂或不添加催化剂的条件下,经重排反应制备羟基环戊烯酮,第二步为羟基环戊烯酮在加氢催化剂催化下与氢气反应制备I,3-环戊二醇。 [0008] The first step in the alcohol solution of an alkali catalyst or without addition of a catalyst, prepared by the rearrangement reaction of the cyclopentenone hydroxy, second stage production of hydrogen by reaction with a hydroxyl group in the cyclopentenone Hydrogenation Catalyst I, 3- cyclopentane diol.

[0009] 与文献(J.Catal. ,2015,330:19-27)相比,本专利采用两步法合成1,3-环戊二醇, 首先在第一步合成出羟基环戊烯酮这一中间化合物,再进行加氢反应,才能高收率获得1, 3-环戊二醇,而对比文献中采用一步法加氢,其产物多达十数种,其中,1,3-环戊二醇的收率不到7%。 [0009] with the literature (J.Catal, 2015,330:. 19-27) compared to two-step method of the present patent Synthesis of 1,3-cyclopentane diol, in a first step the synthesis of the first-hydroxy cyclopentenone this intermediate compound, and then subjected to hydrogenation reaction in order to obtain a high yield 1, 3-cyclopentane diol, while the comparative literature by one-step hydrogenation, which is up to ten several products, wherein the 1,3- yield pentanediol less than 7%. 而本专利中1,3_环戊二醇的收率可以轻松达到50%以上,在一些特定的反应条件下甚至可达90 %以上,这正是本专利的创新之处。 And in this patent yield 1,3_ cyclopentane diol can easily reach more than 50%, in certain reaction conditions or even up to 90%, which is the innovation of this patent.

[0010] 其中第一步糠醇溶液制备羟基环戊烯酮反应的碱催化剂为下述催化剂中的一种或二种以上混合: [0010] The first step in preparing the catalyst wherein the alkali-hydroxy cyclopentenone furfuryl alcohol solution following the reaction the catalyst is one or a mixture of two or more:

[0011 ] NaOH、KOH、Na2CO3、NaHCO3、氨水、Ca (OH) 2、Mg (0H) 2、CaO、MgO、镁错水滑石、镍错水滑石、Ce〇2; [0011] NaOH, KOH, Na2CO3, NaHCO3, ammonia, Ca (OH) 2, Mg (0H) 2, CaO, MgO, magnesium hydrotalcite wrong, the wrong Ni hydrotalcite, Ce〇2;

[0012] 其中,加入催化剂的质量与反应底物溶液质量的比值在0-0.05之间。 [0012] wherein the ratio between the mass and the mass of the reaction substrate solution was added catalyst 0-0.05.

[0013] 第二步羟基环戊烯酮加氢催化剂为下述催化剂中的一种或二种以上混合: [0013] Step hydroxy cyclopentenone hydrogenation catalyst as a mixture of two or more of the following catalysts:

[0014] 以活性炭(AC)、介孔碳(MC)、氧化硅(SiO2)、氧化铝(Al2O3)、氧化铈(CeO2)、氧化钛(11〇2)中的一种或二种以上混合物为载体,负载金属?1:、? [0014] In the activated carbon (AC), mesoporous carbon (MC), silicon oxide (SiO2), alumina (Al2O3), cerium oxide (CeO2), titanium oxide (11〇2) of one or a mixture of two or more as a carrier, supported metal 1:?,? (1、1?11、11'、附、&3、(]11中的一种或二种以上的负载型金属催化剂、过渡金属碳化物或氮化物催化剂、雷尼镍催化剂、非晶态合金催化剂; ? (1, 11, 11 ', attached, & amp; 3, in a medium (] 11 or two or more of the supported metal catalyst, a transition metal carbide or nitride catalysts, Raney nickel catalysts, amorphous alloy catalyst;

[0015] 负载型金属催化剂采用等体积浸渍的方法制备:配制质量浓度0.1-10%的金属前躯体溶液,按照计量比加入上述载体中等体积浸渍,催化剂中金属的质量含量占〇. 〇1 -30%,静置2h后在80-120°C下干燥6-24h,再在200-600°C下用氢气还原l-10h,待温度降低至室温后通入含体积浓度1 % O2的氮气钝化4h以上; Method [0015] The supported metal catalyst prepared by impregnation of: formulating a concentration of 0.1 to 10% by mass of the metal precursor solution, was added according to stoichiometric ratio of the carrier medium volume impregnation, the metal content in the catalyst mass accounted square 〇1 -. 30%, dried 6-24h 2h after standing at 80-120 ° C, then l-10h reduction with hydrogen at 200-600 ° C, until the temperature drops to room temperature, nitrogen gas having passed through a volume concentration of 1% O2 The passivation than 4h;

[0016] 其中,加入催化剂的质量与反应底物溶液质量的比值在0.01%-20%之间。 [0016] wherein the mass ratio of the mass of the reaction substrate solution was added catalyst is between 0.01% to 20%.

[0017] 第一步糠醇溶液制备羟基环戊烯酮反应的溶剂为水或水与下述溶剂中的一种或二种以上混合:甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、四氢呋喃(THF)、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF); [0017] The first step in alcohol solvent hydroxy cyclopentenone was prepared as a reaction of water or water with the following solvent mixture of two or more of: methanol, ethanol, propanol, isopropanol, butanol, isobutanol butanol, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), N, N- dimethylformamide (of DMF);

[0018] 其中糠醇的质量浓度为0.01%-99%,优选浓度范围为0.1%-10%。 [0018] wherein the alcohol concentration is 0.01% to 99%, preferably in a concentration range of 0.1% to 10%.

[0019] 第二步羟基环戊烯酮加氢反应的可不采用溶剂,也可采用下述溶剂中的一种或二种以上混合:水、甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、四氢呋喃(THF)、二甲基亚砜(DMSO)、N,N-二甲基甲酰胺(DMF); [0019] Step-hydroxy cyclopentenone of the hydrogenation reaction may use a solvent, may also be one of the following solvent mixture of two or more of: water, methanol, ethanol, propanol, isopropanol, butanol, , isobutanol, tetrahydrofuran (THF), dimethylsulfoxide (DMSO), N, N- dimethylformamide (of DMF);

[0020] 其中羟基环戊烯酮的质量浓度为0.01 %-100%,优选浓度范围为0.1 %-10%。 [0020] wherein the concentration of hydroxyl groups of cyclopentenone is 0.01% -100%, preferably in a concentration range of 0.1% to 10%.

[0021] 第一步糠醇溶液制备羟基环戊烯酮反应可在釜式反应器中进行,也可以在固定床反应器中进行,其反应温度在50°C_300°C之间,优选反应温度在160°C_250°C间; [0021] The first step was the preparation of alcohol hydroxy cyclopentenone in the reaction may be carried out in a tank reactor, may be performed in a fixed bed reactor in which the reaction temperature is between 50 ° C_300 ° C, the preferred reaction temperature between 160 ° C_250 ° C;

[0022] 采用釜式反应器时,反应时间在0. OOlh-IOh之间,优选反应时间在0. Olh-O. 5h之间;采用固定床反应器时,其质量空速在Ο.ΟΐΡ-ΙΟΟΙΓ1之间;优选空速在IOr1-IOOr1之间; [0022] When using a tank reactor, the reaction time is between 0. OOlh-IOh, the reaction time is preferably in Olh-O between 0. 5h;. When using a fixed bed reactor, in which WHSV Ο.ΟΐΡ between -ΙΟΟΙΓ1; space velocity preferably between IOr1-IOOr1;

[0023] 第二步羟基环戊烯酮加氢反应可在釜式反应器中进行,也可以在固定床反应器中进行,其反应温度在0°c-300°c之间,优选反应温度在15°c-160°c间;其氢气压力在0. IMPa-IOMPa之间,优选压力在lMPa_5MPa之间; [0023] Step hydroxy cyclopentenone hydrogenation reaction may be performed in autoclave reactor, may be performed in a fixed bed reactor in which the reaction temperature is between 0 ° c-300 ° c, preferably the reaction temperature between 15 ° c-160 ° c; between 0. IMPa-IOMPa, preferably a pressure between hydrogen pressure lMPa_5MPa;

[0024] 采用釜式反应器时,反应时间在0.OOlh-IOh之间,优选反应时间在0.1h_2h之间; 采用固定床反应器时,其质量空速在〇.Olir1-IOOir1之间;优选空速在Iir1-IOir1之间;氢气与反应原料的摩尔比为20-1500。 [0024] When using a tank reactor, the reaction time between 0.OOlh-IOh, the reaction time is preferably between 0.1h_2h; When using a fixed bed reactor, which WHSV between 〇.Olir1-IOOir1; a space velocity preferably between Iir1-IOir1; molar ratio of hydrogen to feedstock of the reaction 20-1500.

[0025] 本发明具有如下优点: [0025] The present invention has the following advantages:

[0026] 本发明所提供的方法合成1,3-环戊二醇,其原料来自于可再生的木质纤维素平台化合物糠醇。 Method [0026] The present invention provides the synthesis of 1,3-cyclopentane diol, which is derived from a lignocellulosic raw material alcohol compound renewable internet. 其重排反应和加氢反应均采用常见的碱催化剂与加氢催化剂,简单易得,催化剂成本较低。 And rearrangement reactions which are in most of the hydrogenation reaction base catalyst with a hydrogenation catalyst, simple and easy to obtain, low catalyst cost. 相比于文献中报道的糠醇加氢制1,3-环戊二醇,收率有着明显的提高。 Reported in the literature compared to furfuryl alcohol hydrogenation of 1,3-cyclopentane diol, has significantly improved the yield. 因此本专利的方法是一种非常实用的合成1,3_环戊二醇的方法。 The method of this patent is therefore a very useful method for the synthesis of cyclopentane diol 1,3_.

附图说明 BRIEF DESCRIPTION

[0027] 图1.糠醇重排反应产物羟基环戊烯酮的1H-NMR谱图; [0027] FIG. 1. The rearrangement reaction product of furfuryl alcohol hydroxy cyclopentenone 1H-NMR of spectra;

[0028] 图2.糠醇重排反应产物羟基环戊烯酮的13C-NMR谱图; 13C-NMR [0028] Figure 2. rearrangement reaction product of furfuryl alcohol hydroxy cyclopentenone spectrum;

[0029] 图3.羟基环戊烯酮加氢产物1,3-环戊二醇的1H-NMR谱图; [0029] 3. FIG hydroxy cyclopentenone hydrogenation product 1,3-cyclopentane diol 1H-NMR of spectra;

[0030] 图4.羟基环戊烯酮加氢产物1,3-环戊二醇的13C-NMR谱图; [0030] Figure 4-hydroxy cyclopentenone of the hydrogenation product 1,3-cyclopentane diol 13C-NMR spectrum;

具体实施方式 detailed description

[0031] 下面将以具体的实施例来对本发明加以说明,但本发明的保护范围不局限于这些实例。 [0031] The following embodiment will be illustrated by specific examples of the present invention, but the scope of the present invention is not limited to these examples.

[0032] 1.由糠醇制备羟基环戊烯酮的实验(催化剂的影响,釜式反应器) [0032] 1. The experimentally prepared hydroxy cyclopentenone alcohol (influence of the catalyst, a tank reactor)

[0033] 在IOOmL反应釜中,加入50mL质量浓度为2%的糠醇水溶液,加入一定量的碱催化剂,在一定温度下反应特定的时间。 [0033] In IOOmL autoclave, was added 50mL of 2% concentration of furfuryl alcohol aqueous solution, a certain amount of the alkali catalyst, the reaction time and at a specific temperature.

[0034] 表1.不同碱催化剂的重排反应活性 [0034] reactivity rearrangement Table 1. Different base catalyst

[0035] [0035]

Figure CN106866364AD00061

[0036] 表I.不同碱催化剂的重排反应活性(续表) [0036] Table I. Rearrangement different active base catalyst (Continued)

[0037] [0037]

Figure CN106866364AD00062

[0038] 由表1结果可以看出,不同碱催化剂均可有效的催化糠醇重排反应的发生,获得高收率的羟基环戊烯酮,其中碱性较弱的CeO2效果较差。 [0038] As can be seen from the results in Table 1, the base catalyst can be different effective catalytic rearrangement reaction of furfuryl alcohol, hydroxy cyclopentenone obtained in high yield, wherein the less basic CeO2 poor effect. 但是即使是不加任何催化剂,在较优的反应条件下仍然可以获得60%的羟基环戊烯酮的收率。 But even without any catalyst, the reaction conditions in the superior still obtain a yield of 60% of the hydroxyl groups of cyclopentenone. 催化剂用量对反应活性的影响比较显著,其中在5mg左右的NaOH可以获得较优的收率,大于或小于该数值,均会使得羟基环戊烯酮的收率减低。 Effect of amount of catalyst on the reactivity of the more significant, which can be obtained about 5mg NaOH superior yields, greater or less than this value, so that the yield will reduce hydroxy cyclopentenone. 而反应时间的影响与催化剂量类似,在〇.〇2h的时候有最佳的收率,时间过长,会导目标产物进一步发生副反应,降低产物收率;过短,则会有部分原料未完全转化,造成产率偏低。 Effects similar to the amount of the catalyst and the reaction time, the best yields have 〇.〇2h time, long time, will lead to further side reactions desired product, reducing the product yield; too short, there will be some material incomplete conversion, resulting in low yield. 反应温度同样也有最优值,在240°C时,羟基环戊烯酮的收率达到最大, 过高或过低的温度均导致产率小幅度下降。 The reaction temperature also has an optimum value, at 240 ° C, the yield maximized hydroxy cyclopentenone, high or low temperatures are led to a small decrease in the yield.

[0039] 2.由糠醇制备羟基环戊烯酮的实验(溶剂的影响,爸式反应器) [0039] 2. Preparation of Experimental hydroxy cyclopentenone alcohol (influence of the solvent, dad reactor)

[0040] 在IOOmL反应釜中,加入50mL—定浓度的糠醇水溶液或者水与其它溶剂的混合溶液,以NaOH为催化剂,在240°C下反应0.02h。 [0040] In IOOmL reaction kettle was added an aqueous solution or a mixed solution of furfuryl alcohol 50mL- given concentration of water with other solvents, NaOH as a catalyst, the reaction 0.02h at 240 ° C.

[0041 ]表2.不同溶剂对重排反应活性的影响 [0041] Table 2. Effects of different solvents on the activity of the rearrangement reaction

[0042] [0042]

Figure CN106866364AD00071

[0043] 表2.不同溶剂对反应活性的影响(续表) [0043] Table 2. Effects of different solvents on the reactivity (Continued)

[0044] [0044]

Figure CN106866364AD00072

[0045] 由表2结果可以看出,随着反应底物糠醇浓度的增加,羟基环戊烯酮的收率有了显著的降低,但是仍保持在一个较高的水平。 [0045] As can be seen from the results in Table 2, with the increase of alcohol concentration in the reaction substrate, the yield hydroxy cyclopentenone been significantly decreased, but remained at a high level. 这在实际生产过程中,需要综合考虑产率收率与能量效率来获得最佳浓度。 This is the actual production process, the need to consider yield and the yield of energy efficiency to get the best concentration. 采用混合溶剂对目标产物的产率影响不大,即使是混合溶剂与水的比例在较大范围内浮动,仍可获得较高的羟基环戊烯酮的收率。 Mixed solvent yields the desired product of little effect, even if the ratio of a mixed solvent with water in a wide range of floating, still obtain high yields of hydroxy cyclopentenone.

[0046] 3.由糠醇制备羟基环戊烯酮的实验(固定床反应器) [0046] 3. Preparation experimentally hydroxy cyclopentenone alcohol (fixed bed reactor)

[0047] 在固定床反应器中,用液相色谱栗以一定的速率栗入固定床反应器中不同浓度的糠醇水溶液,以镁铝水滑石为催化剂,在不同的温度下进行反应。 [0047] In a fixed bed reactor, liquid chromatography Li Li at a rate different concentrations of the aqueous alcohol fixed bed reactor, to Hydrotalcite catalyst, reaction was carried out at different temperatures.

[0048] 表3.固定床反应器中糠醇重排反应活性 [0048] Table 3. furfuryl alcohol in a fixed bed reactor rearrangement reaction activity

Figure CN106866364AD00081

[0050] 从表3可以看出,在固定床反应器中,相同的糠醇浓度条件下,可以获得更高的羟基环戊烯酮的收率。 [0050] As can be seen from Table 3, in a fixed bed reactor under the same conditions the alcohol concentration, the yield can be higher hydroxy cyclopentenone. 固定床的空速太大或太小均会使得羟基环戊烯酮的收率降低,这与釜式反应器中反应时间影响产率的道理类似。 Too much or too bed airspeed such that the yield will decrease hydroxy cyclopentenone, which affect similar to the tank reactor to yield truth time. 温度对羟基环戊烯酮的生成有较大的影响,温度太低不利于目标产物的生成,240°C为最优的反应温度。 Temperature has a great influence on the generation of hydroxy cyclopentenone, too low temperature is not conducive to the formation of the desired product, 240 ° C for the optimum reaction temperature.

[0051] 4.羟基环戊烯酮加氢的实验(催化剂的影响,釜式反应器) [0051] 4-hydroxy-cyclopentenone hydrogenation experiments (effect of the catalyst, the tank reactors)

[0052] 在IOOmL反应釜中,加入50mL质量浓度2%的羟基环戊烯酮溶液,溶剂为四氢呋喃(THF),加入0. Ig的加氢催化剂,在一定温度下反应特定的时间。 [0052] In IOOmL autoclave, was added 50mL of a hydroxyl group concentration of 2% by mass solution of the cyclopentenone, the solvent is tetrahydrofuran (THF), 0. Ig of the hydrogenation catalyst was added, the reaction time and at a specific temperature.

[0053] 表4.不同催化剂的加氢反应活性 Hydrogenation activity [0053] Table 4. different catalysts

[0054] [0054]

Figure CN106866364AD00082

[0055] [0055]

Figure CN106866364AD00091

[0056] 表4.不同催化剂的加氢反应活性(续表) [0056] Table 4. hydrogenation reactivity of different catalysts (Continued)

[0057] [0057]

Figure CN106866364AD00092

[0058] 从表4中的数据可以看出,几乎所有常见的加氢催化剂对羟基环戊烯酮的加氢反应均有很好的效果,其中,以金属Ni和Ru表现的活性为最佳。 [0058] As can be seen from the data in Table 4, almost all common hydrogenation catalysts Hydrogenation hydroxy cyclopentenone had very good results, wherein the active metal Ni and Ru best performance . 金属负载量和反应时间对1,3_ 环戊二醇的产率略有影响,但是不是很明显。 Effect of metal loading and reaction time on the yield 1,3_ cyclopentane diol slightly, but not obvious. 反应温度相对来说影响较大,160°C为最佳的反应温度。 The reaction temperature is relatively greater impact, 160 ° C for the optimum reaction temperature.

[0059] 5.羟基环戊烯酮加氢的实验(溶剂的影响,釜式反应器) [0059] The hydrogenation experiments hydroxy cyclopentenone (influence of the solvent, a tank reactor)

[0000] 在IOOmL反应爸中,加入50mL—定浓度的的轻基环戊稀酮溶液,以Ru/AC或者Raney Ni为催化剂,催化剂加入量为O.lg,在160°C下反应lh。 [0000] In the reaction IOOmL Dad was added a dilute solution of ketone 50mL- given concentration of light cyclopentyl, to Ru / AC catalyst or Raney Ni catalyst was added in an amount of O.lg, lh the reaction at 160 ° C.

[0061 ]表5.不同溶剂对加氢反应活性的影响 Activity [0061] Table 5. hydrogenation reactions of different solvents

Figure CN106866364AD00093

[0063]表5.不同溶剂对加氢反应活性的影响(续表) [0063] Activity (Continued) Table 5. Different solvents hydrogenation reaction

Figure CN106866364AD00101

[0066] 从表5中的数据可以看出,溶剂对加氢反应的影响很大,在非质子型溶剂如THF、 DMF、DMS0等可以获得很高的1,3-环戊二醇收率。 [0066] As can be seen from the data in Table 5, a great influence on the hydrogenation reaction solvent, an aprotic solvent such as 1,3-cyclopentadiene available high diol THF, DMF, DMS0 the like yields . 而在水、醇等体系中1,3-环戊二醇收率相对较低。 In the system of water, alcohol and the like 1,3-cyclopentane diol yields are relatively low. 其混合溶剂效果介于两者之间。 A mixed solvent results in between. 底物浓度对1,3-环戊二醇收率影响较大,浓度越小,收率越高。 Effect of substrate concentration on the yield of 1,3-cyclopentane diol larger, the smaller the concentration, the higher the yield.

[0067] 6.羟基环戊烯酮加氢的实验(固定床反应器) [0067] 6. hydroxy cyclopentenone hydrogenation experiments (fixed bed reactor)

[0068] 在固定床反应器中,用液相色谱栗以一定的速率栗入固定床反应器中不同浓度的的羟基环戊烯酮THF溶液,以Ru/AC为催化剂,在不同的温度下进行反应。 [0068] In a fixed bed reactor, liquid chromatography Li Li at a rate into a fixed bed reactor hydroxy cyclopentenone of THF solutions of different concentrations to Ru / AC catalyst, at different temperatures reaction.

[0069] 表6.固定床反应器中加氢反应活性 [0069] Table 6. hydrogenation reaction in a fixed bed reactor activity

Figure CN106866364AD00102

[0071]表6.固定床反应器中加氢反应活性(续表) [0071] Table 6. Hydrogenation in a fixed bed reactor reactivity (Continued)

Figure CN106866364AD00103

[0073]从表6中的数据可以看出,底物浓度对加氢反应的影响很大,过高的底物浓度将导致1,3_环戊二醇收率明显减低。 [0073] As can be seen from the data in Table 6, a large substrate concentration on the hydrogenation reaction, the substrate concentration is too high will result in significantly reduced yield 1,3_ cyclopentane diol. 空速对1,3_环戊二醇收率影响相对较小。 Effect of space velocity on the yield 1,3_ cyclopentane diol is relatively small. 反应温度在高温段160°C_300°C对I,3-环戊二醇收率影响不大,当温度低于100°C时,I,3-环戊二醇收率显著降低。 The reaction temperature is in the high-temperature stage of 160 ° C_300 ° C I, 3-cyclopentyl-diol yields little effect when the temperature is below 100 ° C, I, 3- cyclopentane diol yield is significantly reduced.

[0074]从上述实施例可以看出,通过两步法,完全可以实现从糠醇高收率的制备出1,3_ 环戊二醇。 [0074] As can be seen from the above examples, the two-step process, can achieve an 1,3_ cyclopentane diol prepared from the alcohol in high yield. 且该过程中采用的催化剂为常见、廉价的碱催化剂和加氢催化剂。 And the catalyst employed in the process are common and inexpensive base catalyst and a hydrogenation catalyst. 该过程中除了氢气外,不需加入其它额外消耗品,整个过程绿色环保,是非常高效的1,3-环戊二醇的合成方法。 The hydrogen addition process, without adding other additional consumables, green whole process is very efficient synthesis of 1,3-cyclopentane diol.

Claims (4)

  1. 1. 一种由糠醇制备I,3-环戊二醇的方法,其特征在于: 以糠醇为原料制备1,3-环戊二醇共分为两步反应: 第一步为糠醇溶液在碱催化剂或不添加催化剂的条件下,经重排反应制备羟基环戊烯酮,第二步为羟基环戊烯酮在加氢催化剂催化下与氢气反应制备1,3-环戊二醇。 An alcohol of preparation I, 3-cyclopentyl glycol method, wherein: furfuryl alcohol starting material to prepare 1,3-cyclopentane diol is divided into two steps: the first step of a base to a solution of furfuryl alcohol catalyst under the conditions with or without a catalyst, prepared by the rearrangement reaction of a hydroxyl group of the cyclopentenone, cyclopentenone second step is a hydroxyl-diol prepared by reacting 1,3-cyclopentadiene with hydrogen in the hydrogenation catalyst.
  2. 2. 根据权利要求1所述的制备方法,其特征在于: 第一步糠醇溶液制备羟基环戊烯酮反应的碱催化剂为下述催化剂中的一种或二种以上混合: NaOH、KOH、Na2CO3、NaHCO3、氨水、Ca (OH) 2、Mg (OH) 2、CaO、MgO、镁铝水滑石、镍铝水滑石、 CeO2; 其中,加入催化剂的质量与反应底物溶液质量的比值在〇-〇.05之间; 第二步羟基环戊烯酮加氢催化剂为下述催化剂中的一种或二种以上混合: 以活性炭、介孔碳、氧化硅、氧化铝、氧化铈、氧化钛中的一种或二种以上混合物为载体,负载金属?1?(1、1?11、1^附、(:〇、〇1中的一种或二种以上种的负载型金属催化剂、过渡金属碳化物或氮化物催化剂、雷尼镍催化剂、非晶态合金催化剂; 负载型金属催化剂采用等体积浸渍的方法制备:配制质量浓度〇. 1-10 %的金属前躯体溶液,按照计量比加入上述载体中等体积浸渍,催化剂中 2. The production method according to claim 1, wherein: the alkali catalyst solution prepared in the first step alcohol hydroxy cyclopentenone represented by the following reaction catalyst in one or two or more mixed: NaOH, KOH, Na2CO3 , NaHCO3, ammonia, Ca (OH) 2, Mg (OH) 2, CaO, MgO, Mg-Al hydrotalcite, Ni-Al hydrotalcite, of CeO2; wherein the mass ratio of the mass of the reaction substrate solution was added catalyst 〇- between 〇.05; hydroxy cyclopentenone second step following the hydrogenation catalyst is a catalyst mixture of one or two or more kinds: activated carbon, mesoporous carbon, silicon oxide, aluminum oxide, cerium oxide, titanium oxide one or a mixture of two or more of the carrier, the supported metal 1 (1,1 11,1 ^ is attached, (:??? billion a 〇1 or two or more kinds of supported metal catalyst, a transition metal carbide or nitride catalyst, Raney nickel catalyst, the amorphous alloy catalyst; supported metal catalyst using the incipient wetness impregnation method and the like prepared: formulation concentration of 1-10% square metal precursor solution, in accordance with the stoichiometry described above was added. carrier medium volume impregnation, the catalyst 金属的质量含量占0.01 -30 %,静置2h后在80-120°C下干燥6-24h,再在200-600°C下用氢气还原l-10h,待温度降低至室温后通入含体积浓度1 % 〇2的氮气钝化4h以上; 其中,加入催化剂的质量与反应底物溶液质量的比值在0.01 %-20 %之间。 The metal mass content of from 0.01 to 30%, after drying left 6-24h 2h at 80-120 ° C, then l-10h reduction with hydrogen at 200-600 ° C, until the temperature drops to room temperature aereated 〇2 nitrogen volume concentration of 1% or more passivating 4h; wherein the mass ratio of the mass of the reaction substrate solution was added catalyst is between 0.01% to 20%.
  3. 3. 根据权利要求1所述的制备方法,其特征在于: 第一步糠醇溶液制备羟基环戊烯酮反应的溶剂为水或水与下述溶剂中的一种或二种以上混合:甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺; 其中糠醇的质量浓度为〇.01 %_99%,优选浓度范围为0.1 %-10% ; 第二步羟基环戊烯酮加氢反应的可不用溶剂,也可采用下述溶剂中的一种或二种以上混合:水、甲醇、乙醇、丙醇、异丙醇、丁醇、异丁醇、四氢呋喃、二甲基亚砜、N,N-二甲基甲酰胺; 其中羟基环戊烯酮的质量浓度为0.01 %-1〇〇%,优选浓度范围为0.1 %-1〇%。 3. The production method according to claim 1, wherein: the first step alcohol solvent solution of hydroxy cyclopentenone prepared reaction is water or water mixed with one of the following solvent mixture of two or more of: methanol, ethanol, propanol, isopropanol, butanol, isobutanol, tetrahydrofuran, dimethylsulfoxide, N, N- dimethylformamide; wherein the alcohol concentration is 〇.01% - 99%, preferably a concentration range of 0.1% to 10%; the second step without a solvent may be hydroxy cyclopentenone hydrogenation, it may also be one of the following solvent mixture of two or more of: water, methanol, ethanol, propanol, isopropanol, alcohol, butanol, isobutanol, tetrahydrofuran, dimethylsulfoxide, N, N- dimethylformamide; wherein the concentration of hydroxyl groups of cyclopentenone 0.01% -1〇〇%, preferably in a concentration range of 0.1 % -1〇%.
  4. 4. 根据权利要求1所述的制备方法,其特征在于: 第一步糠醇溶液制备羟基环戊烯酮反应可在釜式反应器中进行,也可以在固定床反应器中进行,其反应温度在50°C_300°C之间,优选反应温度在160°C_250°C间; 采用釜式反应器时,反应时间在0.00Ih-IOh之间,优选反应时间在0. Olh-0.5h之间;采用固定床反应器时,其质量空速在〇. OlP-lOOlT1之间;优选空速在ΙΟΡ-ΙΟΟΙΓ1之间; 第二步羟基环戊烯酮加氢反应可在釜式反应器中进行,也可以在固定床反应器中进行,其反应温度在0°c-300°c之间,优选反应温度在15°c-160°c间;其氢气压力在0 . IMPa-IOMPa之间,优选压力在lMPa_5MPa之间; 采用釜式反应器时,反应时间在0.OOlh-IOh之间,优选反应时间在0.1h-2h之间;采用固定床反应器时,其质量空速在0. Olir1-IOOir1之间;优选空速在Iir1-IOir1之间;氢气与反应原料的摩尔比为20-150 4. The production method according to claim 1, wherein: the first step in preparing a solution of alcohol hydroxy cyclopentenone in the reaction may be carried out in a tank reactor, may be performed in a fixed bed reactor, the reaction temperature between 50 ° C_300 ° C, the reaction temperature is preferably between 160 ° C_250 ° C; when using a tank reactor, the reaction time between 0.00Ih-IOh, the reaction time is preferably between 0. Olh-0.5h; when using a fixed bed reactor, which WHSV between square OlP-lOOlT1; space velocity preferably between ΙΟΡ-ΙΟΟΙΓ1; hydroxy cyclopentenone second step the hydrogenation reaction may be carried out in the reactor tank. may be carried out in a fixed bed reactor in which the reaction temperature is between 0 ° c-300 ° c, the reaction temperature is preferably between 15 ° c-160 ° c;. which hydrogen pressure between 0 IMPa-IOMPa, preferably a pressure between lMPa_5MPa; when using a tank reactor, the reaction time between 0.OOlh-IOh, the reaction time is preferably between 0.1h-2h; when using a fixed bed reactor, in which WHSV 0. Olir1 between -IOOir1; space velocity preferably between Iir1-IOir1; molar ratio of hydrogen to the reaction feed 20 to 150 0。 0.
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