WO2016180000A1 - 一种纤维素两步法制备乙二醇和1,2-丙二醇的方法 - Google Patents

一种纤维素两步法制备乙二醇和1,2-丙二醇的方法 Download PDF

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WO2016180000A1
WO2016180000A1 PCT/CN2015/095076 CN2015095076W WO2016180000A1 WO 2016180000 A1 WO2016180000 A1 WO 2016180000A1 CN 2015095076 W CN2015095076 W CN 2015095076W WO 2016180000 A1 WO2016180000 A1 WO 2016180000A1
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cellulose
catalyst
tungsten
ethylene glycol
reaction
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王爱琴
徐刚
张涛
郑明远
庞纪峰
王�华
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Dalian Institute of Chemical Physics of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
    • C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C31/00—Saturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C31/18—Polyhydroxylic acyclic alcohols
    • C07C31/20—Dihydroxylic alcohols
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters

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  • the invention relates to the field of cellulose production, in particular to a method for preparing ethylene glycol, 1,2-propanediol by a two-step cellulose method.
  • Biomass is the only renewable organic carbon resource that is ideal for replacing petroleum to produce fuels and chemicals. Therefore, the development of new routes and new methods for biomass conversion to fuels and chemicals is an important goal for the future development of sustainable energy systems.
  • the main part of biomass is cellulose, so the effective use of cellulose has become the focus of research.
  • Polyols such as ethylene glycol and 1,2-propanediol are important energy liquid fuels, and are also very important polyester raw materials.
  • the industry mainly adopts the petroleum route, that is, ethylene and propylene are epoxidized to obtain ethylene glycol, 1,2- Propylene Glycol [Document 1: He Li, Research Progress in Ethylene Glycol Synthesis Technology, Industrial Catalysis, 2010, 14(6), 11-15.
  • Literature 2 Zheng Jun, 1,2-Propanediol Production Status and Development Prospects at Home and Abroad, Thermosetting Resin, 2009, 24(1), 58-62]
  • the method is technically difficult, low in efficiency, high in energy consumption and serious in pollution.
  • the object of the present invention is to provide a method for preparing ethylene glycol, 1,2-propanediol from cellulose, firstly converting cellulose into glycolate, lactate, and then hydrogenating to obtain ethylene glycol, 1, 2 - Propylene glycol.
  • cellulose is used as a raw material, and reacted with an alcohol at 180-300 ° C for 0.5-3 h under the action of the first catalyst to form a glycolate, a lactate; and a second catalyst is added to the obtained liquid mixed product, and 0.5 is introduced.
  • Hydrogenation of -7 MPa of hydrogen at 140-220 ° C for 0.1-3 h gives a mixture of ethylene glycol and 1,2-propanediol.
  • the alcohol solvent is at least one of methanol, ethanol, n-propanol or isopropanol.
  • the first catalyst is tungsten oxide, tungsten sulfide, tungsten chloride, tungsten carbide, tungsten hydroxide, tungsten bronze, tungstic acid, tungstate, metatungstic acid, metatungstate, secondary At least one of tungstic acid, paratungstate, peroxo-tungstic acid, peroxytungstate, tungsten-containing heteropolyacid or tungsten-containing heteropolyacid salt.
  • the glycolic acid ester is at least one of methyl glycolate, ethyl glycolate, propyl glycolate or isopropyl glycolate, and the lactate is methyl lactate, ethyl lactate, propyl lactate or isopropyl lactate. At least one of them.
  • the second catalyst uses silica as a carrier, Cu as an active component or a main active component, and contains Ag, Mg, Ca, Ba, Zn, Zr, Co, Cr, Ni, Mn, Sn, Au, Pt, One or more of Pd, Ru or Re as an auxiliary agent, wherein the mass fraction of Cu is 0.5-40%.
  • the additive mass fraction is 0-5%, and the rest is the carrier.
  • the alcohol solvent is used in an amount of 10 to 200 times the mass of the cellulose
  • the first catalyst is used in an amount of 5% to 50% by mass of the cellulose
  • the second catalyst is used in an amount of 10 to 40% by mass of the cellulose.
  • the two-step preparation process of the invention enables the intermediate product to be fixed, and has better stability and controllability.
  • the main active center of the catalyst of the step (2) according to the present invention is Cu, and the catalyst cost is lower than that of the existing noble metals such as Ru and Ni.
  • the alcohol solvent of the present invention has a lower boiling point than the aqueous solvent in the existing hydrolyzed hydrogenation technology, and has lower cost for subsequent product separation and solvent recovery.
  • the heating rate of /min was raised to 550 ° C, and then the temperature was raised to 900 ° C at a heating rate of 1 ° C / min for 1 h, and the hydrogen flow rate was 120 mL / min.
  • the theoretical loading of W in the prepared catalyst was 30% by weight.
  • SBA-15 0.3 g of SBA-15 was dispersed in 30 mL of ethanol, 0.13 g of phosphotungstic acid was dissolved in 10 mL of ethanol, and then added dropwise to the above suspension, and the mixture was stirred for 24 hours, and the solvent was evaporated to dryness to prepare a loading amount of 30%. Supported catalyst.
  • the preparation process of SBA-15 is as follows: 2.0 g of P123 is dissolved in 15 mL of water, then 55 mL of hydrochloric acid is added dropwise, the temperature is raised to 40 ° C and stirred for at least 2-3 h, 4.24 g of tetraethyl orthosilicate is added dropwise, and the reaction is carried out at 40 ° C for 24 h.
  • the mixture was transferred to a hydrothermal reaction kettle, allowed to stand at 100 ° C for 24 h, filtered with a sand core funnel, washed with water until neutral, and the remaining solid was first dried at 60 ° C and then placed at 500 ° C for 6 h.
  • Catalytic conversion experiment 0.5 g of cellulose, 0.2 g of the first catalyst H 2 WO 4 , and 50 ml of methanol were placed in a 100 ml reaction vessel, stirred at a speed of 800 rpm, and simultaneously heated to 260 ° C for 2 h. After the reaction was completed, the liquid product and the catalyst were separated by dropping to room temperature and centrifuging at 5000 rpm for 10 minutes. 0.2 g of the second catalyst 20% Cu/SiO 2 was added to the liquid product, passed through 3 MPa H 2 , and heated to 200 ° C for 2 h. After the reaction was completed, the mixture was cooled to room temperature and centrifuged at 5000 rpm for 10 min to separate the liquid product and the catalyst.
  • the liquid product was analyzed using an Agilent 7890B gas chromatograph equipped with a hydrogen flame (FID) detector and an autosampler.
  • HP-INNOWAX capillary column (30m ⁇ 250 ⁇ m ⁇ 0.5 ⁇ m.), the carrier gas is nitrogen, temperature programmed: stay at 45 ° C for 3 min, then rise to 100 ° C at 5 ° C / min, then rise to 250 ° C / 12 °C stay for 3min.
  • the detector temperature was 270 ° C
  • the hydrogen flow rate was 30 ml/min
  • the air flow rate was 400 ml/min
  • the N 2 flow rate was 35 ml/min.
  • the inlet temperature was 220 ° C
  • the injection volume was 1 ⁇ l
  • the split ratio was 20:1.
  • the cellulose conversion rate is calculated by:
  • cellulose can be converted into ethylene glycol, 1,2-propanediol in high yield on various tungsten-containing and copper-containing catalysts involved in the present invention.
  • W 2 C / AC 5% Fe-15% Cu / SiO 2 can make ethylene glycol, 1,2-propanediol yield of 64.3% and 8.6%.
  • cellulose can be efficiently converted into ethylene glycol, 1,2-propanediol in various alcohol solvents of the present invention.
  • the cellulose was catalyzed by H 2 WO 4 to have excellent ethylene glycol, 1,2-propanediol yield in a certain temperature range.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明提供了一种纤维素两步法制备乙二醇，1,2-丙二醇的方法。包括如下步骤：(1)醇溶剂体系中以纤维素为原料，在第一催化剂作用下与醇反应生成乙醇酸酯，乳酸酯；(2)向步骤(1)得到的液体混合产物加入第二催化剂，通入氢气进行加氢得到乙二醇、1,2-丙二醇。本发明通过醇中酯化和加氢两步反应，纤维素转化率可达到100％，乙二醇、1,2-丙二醇产率可达70％以上，同时降低了分离成本，为高效综合利用纤维素提供了一条新途径。

Description

一种纤维素两步法制备乙二醇和1,2-丙二醇的方法 技术领域
本发明涉及纤维素生产领域，特别是涉及一种纤维素两步法制备乙二醇，1,2-丙二醇的方法。
背景技术
生物质是唯一可再生的有机碳资源，是替代石油生产燃料和化学品的理想选择。因此发展生物质转化制燃料和化学品的新路线和新方法，是未来可持续能源体系发展的重要目标。生物质中主要一部分是纤维素，因此纤维素的有效利用成为研究重点。
多元醇如乙二醇，1,2-丙二醇是重要的能源液体燃料，也是非常重要的聚酯原料，工业主要采用石油路线，即乙烯、丙烯环氧后水合得到乙二醇、1,2-丙二醇【文献1：何立，乙二醇合成技术研究进展，工业催化，2010,14(6),11-15.文献2：郑军，1,2-丙二醇国内外生产现状及发展前景，热固性树脂，2009,24(1),58-62】，该方法技术难度大，效率低，能耗高且污染严重。目前从生物质出发水解加氢制备乙二醇，1,2-丙二醇被视为纤维素转化的新型利用途径，【文献:3：一种纤维素制乙二醇的方法，CN101723802A.文献4：一种生产乙二醇和1，2-丙二醇的方法，CN101768050A.文献5：碳化钨催化剂及其制备和在纤维素制乙二醇反应中的应用，CN101648140】，此方法不仅可以开辟新的合成路径，实现由廉价纤维素得到高经济价值的产品，而且在转化过程中纤维素中葡萄糖单元的羟基得到大量保留，整个过程原子经济性较高，显示了较强的工业利用前景。然而在另一面，纤维素水解加氢时的中间产物极不稳定，不利于串联反应的综合优化及催化体系调节，同时反应在水中进行，产物分离及溶剂回收成本较高。本发明所设计的纤维素两步法制备乙二醇，1,2-丙二醇的方法使得过程分步可控，催化剂可分别回收，且产物回收溶剂回收成本较低。
发明内容
本发明的目的在于提供一种纤维素制备乙二醇，1,2-丙二醇的方法，首先将纤维素催化转化为乙醇酸酯，乳酸酯，然后进行加氢得到乙二醇、1,2-丙二醇。
为实现上述目的，本发明采取的技术方案为：
醇溶剂体系中以纤维素为原料，在第一催化剂作用下与醇在180-300℃反应0.5-3h生成乙醇酸酯，乳酸酯；向得到的液体混合产物加入第二催化剂，通入0.5-7MPa氢气于140-220℃下进行加氢0.1-3h得到乙二醇和1,2-丙二醇的混合物。
醇溶剂为甲醇，乙醇，正丙醇或异丙醇中的至少一种。第一催化剂为钨的氧化物，钨的硫化物，钨的氯化物，钨的碳化物，钨的氢氧化物，钨青铜，钨酸，钨酸盐，偏钨酸，偏钨酸盐，仲钨酸，仲钨酸盐，过氧钨酸，过氧钨酸盐，含钨杂多酸或含钨杂多酸盐中的至少一种。乙醇酸酯为乙醇酸甲酯、乙醇酸乙酯、乙醇酸丙酯或乙醇酸异丙酯中的至少一种，乳酸酯为乳酸甲酯，乳酸乙酯，乳酸丙酯或乳酸异丙酯中的至少一种。
第二催化剂采用二氧化硅为载体，以Cu为活性组分或主要活性组分，同时含有Ag,Mg,Ca,Ba,Zn,Zr,Co,Cr,Ni,Mn,Sn,Au,Pt,Pd,Ru或Re中的一种或多种作为助剂，其中Cu的质量分数为0.5-40％。助剂质量分数为0-5％，其余为载体。
所述醇溶剂用量为纤维素质量的10-200倍，所述第一催化剂用量为纤维素质量的5％-50％，所述第二催化剂用量为纤维素质量的10-40％。
本发明具有如下优点：
1.相对于已有的纤维素制备乙二醇，1,2-丙二醇技术，本发明所涉及的两步法制备工艺使得中间产物得以固定，有更好的稳定性和可控性。
2.本发明所涉及的步骤(2)的催化剂主要活性中心为Cu,相对于已有的Ru,Ni等贵金属相比，催化剂成本更低。
3.本发明涉及的醇溶剂相对于已有的水解加氢技术中的水溶剂沸点更低，对于后续的产物分离及溶剂回收成本更低。
下面通过具体实施例对本发明进行详细说明，但这些实施例并不对本发明的内容构成限制。
具体实施方式
实施例1
Cs2.5H0.5PW12O40催化剂的制备
分别把2.5g CS2CO3和18.12g预处理得到的H3PW12O406H20配成0.1mol·L-1和0.08mol·L-1的溶液，0.1·mol·L-1的Cs2CO3溶液以1mL·min-1的速率在室温下滴加到0.08mol·L-1H3PW12040溶液中。滴加完毕，继续搅拌0.5h后，于室温下静置20h。然后在323K下缓慢蒸发水分，得白色固体，然后在110℃左右烘干，用前在300℃焙烧2h，比表面积为108m2g-1。
实施例2
W2C/AC的制备：称50g活性炭(AC),250mL 33wt％HNO3，置于500mL三口烧瓶中，80℃水浴处理24h,洗涤至中性，120℃烘干24h。将1g预处理过的AC倒入含0.588g偏钨酸铵的水溶液中，经120℃烘箱干燥后，将此催化剂前体于氢气中进行程序升温还原，具体反应过程为：由室温以8.8℃/min的升温速率升至550℃，然后以1℃/min的升温速率升温至900℃并保持1h，氢气流速为120mL/min。所制备的催化剂中W的理论担载量为30wt％。
实施例3
取0.3g SBA-15分散在30mL乙醇中，将0.13g磷钨酸溶解在10mL乙醇中，然后滴加至上述悬浮液，搅拌浸渍24h，蒸干溶剂，干燥，制备成负载量为30％的固载催化剂。其中SBA-15制备过程为：取2.0g P123溶解在15mL水中，然后滴加55mL盐酸，升温至40℃至少搅拌2-3h，滴加4.24g正硅酸乙酯,在40℃下反应24h，然后转移至水热反应釜中，在100℃静置24h，用砂芯漏斗抽滤，水洗至中性，剩余固体先在60℃下烘干后再置于500℃下灼烧6h。
实施例4
在室温下将7.56g Cu(NO3)2·3H2O溶于100mL去离子水中,加入浓氨水调节pH值至9.0,再加入8.0g SiO2。搅拌20min后,将混合物转移至冰水浴中,在搅拌下以15mL·min-1的速度加入去离子水,稀释至2L后过滤。用去离子水洗涤3次后,在120℃下干燥过夜,然后在450℃下焙烧4h。反应前在350℃下还原3h.得到20％Cu/SiO2。
实施例5
将1.90g Cu(NO3)2·3H2O溶解于100mL去离子水中,向溶液中缓慢滴加11mL 28wt.％的氨水后室温下搅拌30min,向上述铜氨络合物溶液中加入含4.0g不同氧化铁(氧化镁，氧化钴)与二氧化硅比例的载体后,再剧烈搅拌2h,溶液初始pH＝11-12,然后升温至90℃蒸发过量的氨水和溶剂，使得铜物种在此过程中沉积到氧化铁和氧化硅载体上，至溶液呈中性时停止蒸发，离心，洗涤后在120℃下干燥12h,然后在450℃下焙烧4h。反应前在350℃下还原3h。如此制得5％Fe-15％Cu/SiO2，5％Mg-15％Cu/SiO2，5％Co-15％Cu/SiO2。
实施例6
催化转化实验：将0.5g纤维素，0.2g第一催化剂H2WO4,和50ml甲醇加入到100ml反应釜中，以800转/min的速度进行搅拌，同时升温到260℃，反应2h。反应结束后，降至室温、5000rpm离心10min分离液体产物与催化剂。取0.2g第二催化剂20％Cu/SiO2加入到液体产物中，通入3MPa H2,升温至200℃反应2h，反应结束后，降至室温、5000rpm离心10min分离液体产物与催化剂。液体产物采用Agilent公司7890B气相色谱仪分析，配有氢火焰(FID)检测器，自动进样器。HP-INNOWAX毛细管柱(30m×250μm×0.5μm.)，载气为氮气，程序升温：45℃下停留3min，然后以5℃/min速率升至100℃，随后以12℃/min升至250℃停留3min。检测器温度270℃，氢气流量30ml/min，空气流量400ml/min，N2流量35ml/min。进样口温度220℃，进样量1μl，分流比20:1。
纤维素转化率由下式计算：
Figure PCTCN2015095076-appb-000001
乙醇、正丙醇收率计算公式如下(其中反应物中纤维素含碳量由元素分析仪确定)：
Figure PCTCN2015095076-appb-000002
Figure PCTCN2015095076-appb-000003
其它液体产物及气体产物(CO，CO2，CH4等)未计算其收率。
实施例7
替换第一催化剂及第二催化剂的种类，其他反应条件同实施例6,比较各类含钨催化剂H2WO4，WO3，Na2WO4,AMT,W2C/AC,HPW/SBA-15,Cs2.5H0.5PW12O40及含铜催化剂20％Cu/SiO2，5％Fe-15％Cu/SiO2，5％Mg-15％Cu/SiO2，5％Co-15％Cu/SiO2催化下纤维素的催化转化结果，见表1。
表1各种催化剂上纤维素催化转化性能的比较
Figure PCTCN2015095076-appb-000004
如表所示，纤维素能够在本发明中所涉及的各种含钨及含铜催化剂上高收率地转化为乙二醇，1,2-丙二醇。其中，W2C/AC 5％Fe-15％Cu/SiO2上能使乙二醇，1,2-丙二醇收率达64.3％和8.6％。
实施例8
替换溶剂种类，其他反应条件同实施例6，比较甲醇，乙醇，正丙醇体系中纤维素催化转化结果，见表2。
表2各种醇溶剂中纤维素催化转化性能的比较
Figure PCTCN2015095076-appb-000005
Figure PCTCN2015095076-appb-000006
如表所示，纤维素能在本发明所涉及的各类醇溶剂中有效转化为乙二醇，1,2-丙二醇。
实施例9
不同反应温度下纤维素催化转化性能的比较。见表3，除反应温度不同外，其他反应条件同实施例6。
表3不同反应温度下纤维素催化转化性能的比较
Figure PCTCN2015095076-appb-000007
从表中可以看出，在一定的温度范围内，用H2WO4催化纤维素均有优良的乙二醇，1,2-丙二醇收率。
实施例10
不同反应时间下纤维素催化转化性能的比较。见表4，除反应时间不同外，其他反应条件同实施例6。
表4不同反应时间下H2WO4催化剂上纤维素催化转化性能的比较
Figure PCTCN2015095076-appb-000008
从表中可以看出，在一定的时间范围内，纤维素均有优良的乙二醇，1,2-丙二醇收率。

Claims (7)

  1. 一种纤维素两步法制备乙二醇和1,2-丙二醇的方法，其特征在于，包括如下步骤：
    (1)醇溶剂中加入纤维素，在第一催化剂作用下发生反应；
    (2)向步骤(1)得到的混合产物加入第二催化剂，通入氢气进行反应得到乙二醇、1,2-丙二醇的混合物。
  2. 如权利要求1所述的方法，其特征在于：步骤(1)中所述的醇溶剂为甲醇、乙醇、正丙醇或异丙醇中的一种或二种以上。
  3. 如权利要求1所述的方法，其特征在于：步骤(1)中所述的第一催化剂为钨的氧化物、钨的硫化物、钨的氯化物、钨的碳化物、钨的氢氧化物、钨青铜、钨酸、钨酸盐、偏钨酸、偏钨酸盐、仲钨酸、仲钨酸盐、过氧钨酸、过氧钨酸盐、含钨杂多酸或含钨杂多酸盐中的一种或二种以上。
  4. 如权利要求1所述的方法，其特征在于：步骤(2)中所述的第二催化剂以二氧化硅为载体，以Cu为活性组分，同时含有Ag、Mg、Ca、Ba、Zn、Zr、Co、Cr、Ni、Mn、Sn、Au、Pt、Pd、Ru或Re中的一种或二种以上作为助剂，其中Cu的质量分数为0.5-40％；助剂质量分数为0-5％，其余为载体。
  5. 如权利要求1所述的方法，其特征在于：步骤(1)中所述醇溶剂质量为纤维素质量的10-200倍，所述第一催化剂质量为纤维素质量的5％-50％，步骤(2)中所述第二催化剂用量为步骤(1)中纤维素质量的10-40％。
  6. 如权利要求1所述的方法，其特征在于：步骤(1)中所述的反应，反应温度为180-300℃，反应时间为0.5-3h。
  7. 如权利要求1所述的方法，其特征在于：步骤(2)中所述的反应，反应温度为140-220℃，反应时间为0.5-3h,氢气压力为0.5-7MPa。
PCT/CN2015/095076 2015-05-13 2015-11-20 一种纤维素两步法制备乙二醇和1,2-丙二醇的方法 Ceased WO2016180000A1 (zh)

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