WO2023078361A1 - 一种制备5-羟甲基糠醛的方法 - Google Patents

一种制备5-羟甲基糠醛的方法 Download PDF

Info

Publication number
WO2023078361A1
WO2023078361A1 PCT/CN2022/129612 CN2022129612W WO2023078361A1 WO 2023078361 A1 WO2023078361 A1 WO 2023078361A1 CN 2022129612 W CN2022129612 W CN 2022129612W WO 2023078361 A1 WO2023078361 A1 WO 2023078361A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
pressure
salt
chloride
sodium
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.)
Ceased
Application number
PCT/CN2022/129612
Other languages
English (en)
French (fr)
Inventor
张建
杨勇
金海涛
陈晨
方乾全
卢国文
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Sugar Energy Technologyco Ltd
Original Assignee
Zhejiang Sugar Energy Technologyco Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Zhejiang Sugar Energy Technologyco Ltd filed Critical Zhejiang Sugar Energy Technologyco Ltd
Priority to EP22889382.2A priority Critical patent/EP4393911A4/en
Publication of WO2023078361A1 publication Critical patent/WO2023078361A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/40—Radicals substituted by oxygen atoms
    • C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the invention relates to a method for preparing 5-hydroxymethylfurfural, which belongs to the field of chemical materials.
  • HMF that is, 5-hydroxymethylfurfural, as a platform compound
  • DMF dihydroxymethylfurfural
  • BHMF a large number of derivatives can be obtained, such as DMF, BHMF, etc.
  • DMF dihydroxymethylfurfural
  • BHMF a large number of derivatives can be obtained, such as DMF, BHMF, etc.
  • HMF is produced by dehydration of biomass.
  • the molecule contains a hydroxymethyl group, an aldehyde group and a furan ring. Its chemical properties are relatively active, and various derivatives can be prepared through condensation, hydrogenation and oxidation reactions.
  • HMF is considered as a versatile chemical intermediate that can be used to synthesize plastics, pharmaceuticals, fine chemicals and liquid fuels.
  • the main way to prepare HMF is to use a catalyst to catalyze the dehydration of sugars under normal pressure. It is commonly used in water systems, organic solvent systems, or water/organic solvent dual-phase systems and ionic liquid systems. The reactions are basically carried out at higher temperatures. , this way will obtain a higher possible conversion rate of fructose to HMF, but inevitably leads to the increase of unwanted substances (including humin) and the complexity and expense of the method.
  • WO2015113060A2 discloses a method of reacting fructose, water, an acid catalyst and at least one other solvent at 80-180° C. within 60 minutes so that the yield of HMF does not exceed 80%.
  • the process disclosed in this document has a step in which a relatively low yield of a given HMF is obtained at the end of partial conversion, and thereafter quenches the conversion of fructose to HMF at the end of partial conversion, adding operational complexity to this process, except
  • the object of the present invention is to provide a kind of simple and convenient method for preparing HMF by the pressure of carbohydrate containing six-carbon sugar basic structural unit. High, severe coking, many by-products, poor HMF selectivity, low yield and other shortcomings.
  • a method for preparing 5-hydroxymethylfurfural is provided, mixing materials containing a salt solution, a carbohydrate compound and a catalyst, and reacting I to obtain the 5-hydroxymethylfurfural;
  • the pressure of reaction I is -0.1 ⁇ -0.015Mpa, and the reaction time is 0.5 ⁇ 8h.
  • the pressure of reaction I is -0.08 ⁇ -0.04Mpa, and the reaction time is 1.5 ⁇ 5h.
  • said reaction I includes reaction II-1 and reaction II-2;
  • the pressure of the reaction II-1 is -0.045 ⁇ -0.015Mpa, and the reaction time is 0 ⁇ 1.5h;
  • the pressure of the reaction II-2 is -0.1 ⁇ -0.045Mpa, and the reaction time is 0.5 ⁇ 6.5h.
  • the pressure of reaction II-1 is -0.04 ⁇ -0.025Mpa, and the reaction time is 0.5 ⁇ 1.5h;
  • the pressure of the reaction II-2 is -0.08 ⁇ -0.065Mpa, and the reaction time is 1 ⁇ 3.5h.
  • Salt solution as a green solvent and phase transfer catalyst, has been widely studied and applied due to its high boiling point, easy extraction, and easy recovery.
  • the application of the reaction of biomass to HMF to quaternary ammonium salt liquid solvents has become a hot research topic in recent years.
  • the normal pressure reaction temperature is high and the coking is serious. Therefore, the present invention controls the material reaction in the system through the negative pressure condition in the reaction process, and prevents coking by-products produced by excessive temperature; and optimizes the process to reduce pressure in stages, which improves the reaction efficiency and the selectivity of the target product; This step is of great significance for the simplification of the process route in the actual production process, the reduction of cost, and the sustainable cycle of production.
  • the salt of the saline solution includes one or more of inorganic salts and organic salts.
  • the salt solution of the reaction I is an inorganic salt solution.
  • the inorganic salt is a metal salt.
  • the metal includes at least one of sodium, potassium, lithium, magnesium, zinc, and calcium.
  • the metal salt includes at least one of metal chlorides, carbonates, bicarbonates, sulfates, and bisulfates.
  • the metal salt is a metal chloride salt.
  • the metal chloride salt includes at least one of sodium chloride, potassium chloride, lithium chloride, calcium chloride, magnesium chloride, and zinc chloride.
  • the metal salt includes at least one of sodium bromide, sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, potassium bromide, potassium chloride, potassium carbonate, lithium bromide, and magnesium sulfate.
  • the salt solution of the reaction II is selected from inorganic salt solutions;
  • the organic salt includes at least one of imidazole-based ionic liquids, pyridine-based ionic liquids, and quaternary ammonium-based ionic liquids.
  • the organic salt includes at least one of alkylammonium halide salts, short-chain alkylimidazole ionic liquids and alkylpyridine ionic liquids.
  • the salt solution includes a solvent; the solvent includes at least one of water and an organic solvent.
  • the organic solvent includes at least one of alcohol compounds, ketone compounds, sulfone compounds, ester compounds, halogenated alkyl compounds and amide compounds.
  • the organic solvent includes 2,5-tetrahydrofuran dimethanol, methyl isobutyl ketone, dimethyl sulfoxide, n-butanol, 2-butanol, ethyl acetate, dichloromethane, N,N - at least one of dimethylacetamide, pyrrolidone, chloroform, acetone.
  • the volume ratio of the water to the organic solvent is 5 ⁇ 10:1.
  • salt:solvent 1 ⁇ 10:1.
  • the carbohydrate compound includes at least one of monosaccharides, disaccharides, oligosaccharides and polysaccharides.
  • said monosaccharide, said disaccharide, said oligosaccharide and said polysaccharide independently comprise a six-carbon sugar basic structural unit.
  • salt solution:saccharide compound:catalyst 5 ⁇ 40:1 ⁇ 30:0.1.
  • the catalyst includes at least one of acid catalysts.
  • the acid catalyst is selected from solid acid catalysts.
  • the solid acid catalyst is selected from acidic ion exchange resins.
  • the acidic ion exchange resin is selected from Nafion-H, Nafion NR50, Dowex 50W-X8, Amberlite-IR 120, Amberlyst-15, Amberlyst-70 acidic ion exchange resin.
  • the catalyst can be reused after being calcined.
  • the process method under the one-step pressure condition, the process method is simple to operate, and the HMF yield has reached 60-99%.
  • the energy consumption required in the reaction process is large, the pressure conditions are severe, and the reaction progress is difficult to control.
  • the pressure reaction condition can be reduced to -0.08-0.04Mpa, and the reaction yield in this pressure range is stable at 90-99% with less by-products after repeated attempts.
  • the pressure conditions are carried out in gradients, and the progress of the reaction is controlled according to the control pressure.
  • the salt solution is used to increase the concentration of hydrogen ions or as a phase transfer catalyst to accelerate the target product and the reaction system in two immiscible solvents (liquid-liquid two-phase system or solid-liquid two-phase system), to avoid It prevents HMF from being consumed by hydration in the water phase, inhibits the formation of side reactions, and truly achieves efficient catalysis of fructose dehydration and efficient conversion of 5-hydroxymethylfurfural.
  • Scheme 1 Heat and stir the salt solution in the reactor, and add sugars and catalysts.
  • the ratio of system materials, salt solution: sugar: catalyst 5 ⁇ 40: 1 ⁇ 30: 0.1, stir during the reaction to make the system materials fully contact, adjust the pressure of the reaction system to -0.1 ⁇ -0.015MPa, and the reaction temperature is 50 ⁇ 100°C, the reaction time is 0.5 ⁇ 8h.
  • Scheme 2 heats and stirs the salt solution in the reactor, and adds sugars and catalysts.
  • the ratio of system materials, salt solution: sugar: catalyst 5 ⁇ 40: 1 ⁇ 30: 0.1, stirring during the reaction to make the system materials fully contact, adjust the pressure of the reaction system to -0.045 ⁇ -0.015MPa, so that all Said one starting sugar or at least one of said two or more starting sugars are converted to form HMF and thus form a product mixture, wherein the reaction temperature is 50-100° C. and the reaction time is 0.5-1.5 h.
  • the present invention has the following beneficial effects:
  • the present invention controls the progress of the reaction by controlling the pressure, timely fractionates water and low-boiling point by-products, and differentiates and matches the types of salt solutions for one-step decompression and two-step decompression methods , improve the distribution ratio of the product in the reaction phase and the water phase, avoid the degradation of HMF in the water phase due to hydration with water, and also reduce the generation of by-products such as huminin, thereby reducing the deactivation of the catalyst.
  • HMF has good selectivity, reduces by-products, is easy to separate, and improves the conversion rate of reactants and the yield of HMF.
  • Environmentally friendly not easy to cause equipment corrosion.
  • the mixture of salt and natural solvent water, organic solvent or water and organic solvent is used as the reaction medium to increase the acid density of the catalyst, strengthen the ionization degree of the catalyst, and make the two immiscible solvents (liquid-liquid A two-phase system or a solid-liquid two-phase system) reacts with substances.
  • the process is green and pollution-free, the operating conditions are mild, the process is simple and the cost is low.
  • the present invention can directly use biomass raw materials as reactants to directly prepare key intermediates of biomass energy or biomass materials.
  • the process is green and the yield is high, and the production process is very similar to the current petrochemical process. Great industrialization prospects and strategic significance.
  • the salt solution used is environmentally friendly, the operating conditions are mild, the process is simple, and the repeated use of the catalyst reduces the cost.
  • the new approach is conducive to promoting the preparation of petroleum-based chemicals and alternative fuels from biomass, and has strong industrial significance.
  • the present invention controls the material reaction in the system through decompression conditions during the reaction process to prevent coking by-products produced by excessive temperature; and optimizes the process to decompress in stages, which improves the reaction efficiency and the selectivity of the target product; This step is of great significance for the simplification of the process route in the actual production process, the reduction of cost, and the sustainable cycle of production.
  • the present invention provides a novel process for preparing HMF under reduced pressure.
  • the method has mild conditions, few by-products, 70-100% sugar conversion rate, and 75-99% HMF reaction yield. Due to the fractional distillation of a small amount of water, the acidic aqueous solution containing low-boiling point by-products and the introduction of inert carrier gas to bring out volatile by-products during the reaction decompression process; at the same time, the use of salt solution to increase the concentration of hydrogen ions; catalytic dehydration of fructose and efficient conversion 5 -Hydroxymethylfurfural.
  • the present invention preferably uses the liquid fluidity that forms in the mixture of salt and water, organic solvent, water and organic solvent, good fluidity, good dispersibility, improves catalyst acid density, strengthens the ionization degree of catalyst, makes in The conversion rate of sugar dehydration reaction can reach 100%. It also has the advantages of high boiling point, easy recovery, easy extraction and recyclable use. And as a liquid solvent, it has no pollution to the environment and is beneficial to the subsequent separation of products, thereby simplifying the process route and improving the yield of the target product.
  • sugar raw materials and chemicals in the examples of the present application were purchased through commercial channels.
  • the X-ray powder diffraction of the catalyst sample adopts D8 ADVANCE type powder diffractometer.
  • the 1260 HPLC of Agilent Company was used to analyze the products in the synthesis reaction of 5-hydroxymethylfurfural, and the external standard method was used for quantification.
  • the pressure of the reaction system was adjusted, the reaction temperature was 80° C., and the reaction time was 5 h.
  • the pressure of the reaction system in the first stage was adjusted, the reaction temperature was 80° C., and the reaction time was 1 h.
  • the pressure of the reaction system in the second stage was adjusted, wherein the reaction temperature was 80° C., and the reaction time was 4 h. Detection of sugar conversion rate and HMF reaction yield.
  • first stage pressure second stage pressure sugar conversion rate HMF reaction yield -0.015 -0.045 100% 79.1% -0.025 -0.055 100% 79.5% -0.035 -0.065 100% 94.6% -0.045 -0.075 100% 84.1% -0.045 -0.08 100% 84.9% -0.045 -0.095 100% 82.5% -0.025 -0.065 100% 90.7% -0.035 -0.075 100% 98.3% -0.025 -0.08 100% 94.1% -0.04 -0.075 100% 96.7% -0.04 -0.08 100% 97.0%
  • the pressure of the reaction system in the second stage was adjusted to -0.075MPa, the reaction temperature was 80°C, and the reaction time was 4h.
  • Salt sugar conversion rate HMF reaction yield Sodium chloride 100% 97.50% calcium chloride 100% 90.50% sodium sulfate 100% 91.30% potassium bromide 100% 94.10% magnesium sulfate 100% 94.30% lithium carbonate 100% 92.20% Tetraethylammonium bromide 100% 95.60% Tetrabutylammonium chloride 100% 95.90% 1-Ethyl-3-methylimidazole bromide 100% 94.70% 2-Pyridine acetate 100% 96.10% 4-Pyridine acetate 100% 95.00%
  • the pressure of the reaction system in the second stage was adjusted to -0.075MPa, the reaction temperature was 80°C, and the reaction time was 4h.
  • the pressure of the reaction system in the second stage was adjusted to -0.075MPa, the reaction temperature was 80°C, and the reaction time was 4h.
  • the present invention is applied to the method for preparing HMF from catalyzed sugars by controlling the pressure in the reaction process, which solves the problem of high reaction temperature under normal pressure and severe coking, controls the occurrence of side reactions in the reaction process, and improves the selectivity and efficiency of the target product. Yield.

Landscapes

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

Abstract

本发明公开了一种制备5-羟甲基糠醛的方法，将含有盐溶液、糖类化合物和催化剂的物料混合，反应I，得到所述5-羟甲基糠醛；所述反应I的压力为-0.1～-0.015Mpa。本申请的制备方法可以获得99％的HMF产率，同时调整反应体系的压力，有利于得到较高的反应物转化率和反应产物的选择性。

Description

一种制备5-羟甲基糠醛的方法 技术领域
本发明涉及一种制备5-羟甲基糠醛的方法，属于化工材料领域。
背景技术
随着化石燃料的过度开采和利用，全球面临着严峻的能源危机和环境污染。为了缓解这些问题，开发出清洁、可循环利用的化石燃料替代品的生物质燃料是目前研究的一大热点。HMF，即5-羟甲基糠醛作为一种平台化合物，在生物质能源领域具有重要地位，通过对其还原和氧化，能够得到大量衍生物，例如DMF，BHMF等，这些衍生物能充当化石燃料的替代品，从而缓解当前面临的能源危机。HMF由生物质脱水生成，分子中含有一个羟甲基，一个醛基和一个呋喃环，其化学性质较活泼，可以通过缩合、氢化和氧化等反应制备多种衍生物。HMF被认为是一种多用途的化学中间体，可以用来合成塑料，制药，精细化工和液体燃料。
目前，HMF制备的主要方式是使用催化剂常压催化糖类脱水得到，常用在水体系、有机溶剂体系或者水/有机溶剂双相体系中以及离子液体体系，反应基本上都在较高温度下进行，这种方式会更高可能的获得果糖向HMF的转化率，但不可避免地导致了不想获得的物质(包括胡敏素)的增加以及方法的复杂性和费用。WO2015113060A2公开了一种将果糖、水、酸催化剂和至少一种其他溶剂在80～180℃下60min内反应使HMF产率不超过80％。当完成指定的转化率时，应立即冷却反应组分，以最大程度地减少不需要的副产物的形成。该文献中公开的方法在部分转化终点处获得相对低的指定HMF产率的步骤，并且此后在部分转化终点处使果糖向HMF的转化猝灭，将这种方法增加了操作的复杂性，除分离HMF外还包含HMF合成的原材料或副产物的产物混合物中分离出HMF，并阻碍纯HMF的制备，造成产物复杂、难分离以及选择性低。为了避免使用高温所带来的弊端，人们开始尝试分子溶剂来进行生物质转化反应。但是这些体系所用溶 剂并不绿色，而且5-羟甲基糠醛产率不高，反应所需时间长。所以，开发热稳定性好、溶解性强、蒸汽压低、对环境污染小等优点的绿色高效可循环体系又能控制温度的工艺路线刻不容缓。
发明内容
本发明的目的在于提供一种简便的由含有六碳糖基本结构单元糖类压力制备HMF的方法，此过程条件温和、环境友好、催化剂可重复使用，以克服已有技术中成本高，能耗高，焦化严重，副产物多，HMF选择性不好，产率不高等缺点。
根据本申请的一个方面，提供了一种制备5-羟甲基糠醛的方法，将含有盐溶液、糖类化合物和催化剂的物料混合，反应I，得到所述5-羟甲基糠醛；所述反应I的压力为-0.1～-0.015Mpa，反应时间0.5～8h。
优选地，反应I的压力为-0.08～-0.04Mpa，反应时间1.5～5h。
可选地，所述反应I包括反应II-1和反应II-2；
所述反应II-1的压力为-0.045～-0.015Mpa，反应时间0～1.5h；
所述反应II-2的压力为-0.1～-0.045Mpa，反应时间0.5～6.5h。
优选地，反应II-1的压力为-0.04～-0.025Mpa，反应时间0.5～1.5h；
所述反应II-2的压力为-0.08～-0.065Mpa，反应时间1～3.5h。
盐溶液作为一种绿色溶剂以及相转移催化剂，由于其本身具备沸点高，易萃取，易回收等特点，得到了广泛的研究和应用。特别是生物质制备HMF的反应应用到季铵盐类液体溶剂，是近年来研究的一大热点。常压反应温度高，焦化严重。因此，本发明通过反应过程中通过负压条件，控制体系中的物料反应，防止温度过高产生的焦化副产物；又优化工艺为分阶段减压，提高了反应效率以及目标产物的选择性；这一步骤对于实际生产过程中工艺路线的简化，成本的降低，以及生产的可持续性循环具有重大意义。
可选地，所述盐溶液的盐包括无机盐、有机盐中的一种或多种。
优选地，所述反应I的盐溶液为无机盐溶液。
可选地，所述无机盐为金属盐。
可选地，所述金属包括钠、钾、锂、镁、锌、钙中的至少一种。
可选地，所述金属盐包括金属的氯化盐、碳酸盐、碳酸氢盐、硫酸盐、硫酸氢盐中的至少一种。
可选地，所述金属盐为金属的氯化盐。
可选地，所述金属的氯化盐包括氯化钠、氯化钾、氯化锂、氯化钙、氯化镁、氯化锌中的至少一种。
可选地，所述金属盐包括溴化钠、碳酸钠、碳酸氢钠、硫酸钠、硫酸氢钠、溴化钾、氯化钾、碳酸钾、溴化锂、硫酸镁中的至少一种。
优选地，所述反应II的盐溶液选自无机盐溶液；
可选地，所述有机盐包括咪唑类离子液体、吡啶类离子液体和季铵盐类离子液体中的至少一种。
可选地，所述有机盐包括卤化烷基铵盐、短链烷基咪唑类离子液体和烷基吡啶型离子液体中的至少一种。
可选地，所述盐溶液包括溶剂；所述溶剂包括水、有机溶剂中的至少一种。
可选地，所述有机溶剂包括醇类化合物、酮类化合物、砜类化合物、酯类化合物、卤化烷基类化合物以及酰胺类化合物中的至少一种。
可选地，所述有机溶剂包括2,5-四氢呋喃二甲醇、甲基异丁基酮、二甲基亚砜、正丁醇、2-丁醇、乙酸乙酯、二氯甲烷、N,N-二甲基乙酰胺、吡咯烷酮、氯仿、丙酮中的至少一种。
可选地，所述水与所述有机溶剂的体积比为5～10:1。
可选地，所述盐溶液中盐：溶剂＝1～10:1。
可选地，所述糖类化合物包括单糖、二糖、低聚糖和多糖中的至少一种。
可选地，所述单糖、所述二糖、所述低聚糖和所述多糖独立地包括六碳糖基本结构单元。
可选地，以质量计，盐溶液：糖类化合物：催化剂＝5～40:1～30:0.1。
可选地，所述催化剂包括酸催化剂中的至少一种。
可选地，所述酸催化剂选自固体酸催化剂。
可选地，所述固体酸催化剂选自酸性离子交换树脂。
可选地，所述酸性离子交换树脂选自Nafion-H、Nafion NR50、 Dowex 50W-X8、Amberlite-IR 120、Amberlyst-15、Amberlyst-70酸性离子交换树脂。
可选地，所述催化剂经过焙烧后可重复使用。
本方法中，一步法压力条件下，工艺方法操作简单，HMF产率已达到60～99％。但是反应过程中所需能耗大，压力条件严苛，反应进度不好控制。优选地，所述压力反应条件可缩小至-0.08～-0.04Mpa，经不断尝试此压力范围反应产率稳定在90～99％，副产物较少。可选地，压力条件分梯度进行，根据控制压力来控制反应的进度。低压力时，分馏出少量水；增加压力，分馏出包含低沸点副产物的酸性水溶液；高压力时，抑制反应内液温度的急剧上升，防止腐黑物胡敏素的产生。反应过程中利用盐溶液增加氢离子浓度或者作为相转移催化剂加速将目标产物和反应体系分别处于互不相溶的两种溶剂(液－液两相体系或固－液两相体系)中，避免了HMF在水相中被水合消耗，抑制副反应的生成，真正做到高效催化果糖脱水高效转化5-羟甲基糠醛。
本申请中具体的制备方法如下：
方案1在反应器中将盐溶液加热、搅拌，加入糖类、催化剂。体系物料量之比，盐溶液：糖类：催化剂＝5～40:1～30:0.1，反应过程中搅拌使体系物料充分接触，调整反应体系的压力为-0.1～-0.015MPa，反应温度为50～100℃，反应时间为0.5～8h。
方案2在反应器中将盐溶液加热、搅拌，加入糖类、催化剂。体系物料量之比，盐溶液：糖类：催化剂＝5～40:1～30:0.1，反应过程中搅拌使体系物料充分接触，调整反应体系的压力为-0.045～-0.015MPa，以使所述一种起始糖类或所述两种或更多种起始糖类中的至少一种转化形成HMF并由此形成产物混合物，其中反应温度为50～100℃，反应时间为0.5～1.5h。
调整第二阶段反应体系的压力为-0.1～-0.045MPa，其中反应温度为50～150℃，反应时间为0.5～6.5h。检测糖类转化率和HMF反应产率。
反应完的催化剂分离洗净后，350～850℃焙烧3～12h。焙烧后按 照质量比液体溶剂：糖类：催化剂＝5～40:1～30:0.1对焙烧后的催化剂进行催化性能评价。
相对于现有技术，本发明具有如下有益效果：
1与传统常压脱水制备HMF的方法相比，本发明通过控制压力来控制反应的进度，及时分馏出水以及低沸点副产物，又针对一步减压、二步减压法区别匹配盐溶液的种类，提高产物在反应相与水相中的分配比，避免HMF在水相中与水发生水合作用而降解，也减少了腐黑素等副产物的产生，从而减少了催化剂的失活，对HMF有很好的选择性，减少副产物，易于分离，提高了反应物的转化率和HMF收率。对环境友好，不易造成设备腐蚀。
2反应中以盐与天然溶剂水、有机溶剂或水与有机溶剂的混合物作为反应介质，提高催化剂酸密度，强化催化剂的电离度，又使分别处于互不相溶的两种溶剂(液－液两相体系或固－液两相体系)中的物质发生反应。过程绿色无污染，操作条件温和、工艺简单成本低。
3本发明可以直接以生物质原料作为反应物，直接制备生物质能源或生物质材料的关键中间体，过程绿色、收率高，且生产工艺与现行的石油化工工艺有很大相似性，具有很大的工业化前景和战略意义。
总之，本发明的负压反应过程HMF具有高选择性外，所用盐溶液对环境友好，操作条件温和，工艺简单，催化剂的重复使用降低了成本，为从生物质糖源出发工业化生产HMF提供了新途径，有利于推动以生物质为原料制备石油基化学品和替代燃料，具有很强的工业化意义。
因此，本发明通过反应过程中通过减压条件，控制体系中的物料反应，防止温度过高产生的焦化副产物；又优化工艺为分阶段减压，提高了反应效率以及目标产物的选择性；这一步骤对于实际生产过程中工艺路线的简化，成本的降低，以及生产的可持续性循环具有重大意义。
基于此，本发明提供了一种新型减压制备HMF的工艺方法。本方法条件温和，副产物少，糖类转化率70～100％，HMF反应产率75～99％。由于在反应减压过程中分别分馏出少量水、包含低沸点副产物的酸性 水溶液以及通入惰性载气带出易挥发的副产物；同时利用盐溶液增加氢离子浓度；催化果糖脱水高效转化5-羟甲基糠醛。通过高负压，抑制反应内温度的急剧上升，使反应点减缓，有效防止腐黑物胡敏素的产生。为了提高糖类的选择性，本发明优选使用盐与水、有机溶剂、水以及有机溶剂的混合物中形成的液体流动性好、分散性好、提高催化剂酸密度，强化催化剂的电离度，使得在糖类脱水反应时转化率可达100％。还具有沸点高、易回收、易萃取可循环使用的优点。以及作为液体溶剂对环境无污染，利于产品后续分离，从而简化工艺路线，提高目标产物的收率。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的糖类原料和化学药品均通过商业途径购买。
Figure PCTCN2022129612-appb-000001
实施例中，催化剂样品的X射线粉末衍射采用D8 ADVANCE型粉末衍射仪。
采用Agilent公司的1260型高效液相色谱仪对5-羟甲基糠醛合成反应中的产物进行分析，采用外标法进行定量。
5-羟甲基糠醛转化率基于碳摩尔数进行计算：
Figure PCTCN2022129612-appb-000002
Figure PCTCN2022129612-appb-000003
Figure PCTCN2022129612-appb-000004
实施例1
在反应器中将配置好的氯化钾∶水＝3∶1的盐溶液投入反应釜中，加热至80℃、搅拌均匀，加入结晶果糖∶盐溶液∶Nafion-H固体酸催化剂＝10∶3∶0.1。反应过程中加热、搅拌使体系物料充分接触。
调整反应体系的压力，反应温度为80℃，反应时间为5h。
压力 糖类转化率 HMF反应产率
-0.015 100％ 78.3％
-0.025 100％ 78.5％
-0.035 100％ 79.8％
-0.045 100％ 85.5％
-0.04 100％ 92.3％
-0.065 100％ 97.5％
-0.075 100％ 95.7％
-0.08 100％ 90.8％
-0.085 100％ 87.3％
-0.095 100％ 83.1％
-0.1 100％ 80.1％
实施例2
在反应器中将配置好的氯化钾∶水＝3∶1的盐溶液投入反应釜中，加热至80℃、搅拌均匀，加入结晶果糖∶盐溶液∶Nafion-H固体酸催化剂＝10∶3∶0.1。反应过程中加热、搅拌使体系物料充分接触。
调整第一阶段反应体系的压力，反应温度为80℃，反应时间为1h。
调整第二阶段反应体系的压力，其中反应温度为80℃，反应时间为4h。检测糖类转化率和HMF反应产率。
第一阶段压力 第二阶段压力 糖类转化率 HMF反应产率
-0.015 -0.045 100％ 79.1％
-0.025 -0.055 100％ 79.5％
-0.035 -0.065 100％ 94.6％
-0.045 -0.075 100％ 84.1％
-0.045 -0.08 100％ 84.9％
-0.045 -0.095 100％ 82.5％
-0.025 -0.065 100％ 90.7％
-0.035 -0.075 100％ 98.3％
-0.025 -0.08 100％ 94.1％
-0.04 -0.075 100％ 96.7％
-0.04 -0.08 100％ 97.0％
实施例3
在反应器中将配置好的盐∶水＝3∶1的盐溶液投入反应釜中，加热至80℃、搅拌均匀，加入结晶果糖∶盐溶液∶Nafion-H固体酸催化剂＝10∶3∶0.1。反应过程中加热、搅拌使体系物料充分接触。
调整反应体系的压力为-0.035MPa，反应温度为80℃，反应时间为1h。
调整第二阶段反应体系的压力为-0.075MPa，其中反应温度为80℃，反应时间为4h。
盐 糖类转化率 HMF反应产率
氯化钠 100％ 97.50％
氯化钙 100％ 90.50％
硫酸钠 100％ 91.30％
溴化钾 100％ 94.10％
硫酸镁 100％ 94.30％
碳酸锂 100％ 92.20％
四乙基溴化铵 100％ 95.60％
四丁基氯化铵 100％ 95.90％
溴化1-乙基-3-甲基咪唑 100％ 94.70％
2-吡啶乙酸盐 100％ 96.10％
4-吡啶乙酸盐 100％ 95.00％
实施例4
在反应器中将配置好的氯化钠∶水∶溶剂＝6∶1∶1的盐溶液投入反应釜中，加热至80℃、搅拌均匀，加入结晶果糖∶盐溶液∶Nafion-H固体酸催化剂＝10∶3∶0.1。反应过程中加热、搅拌使体系物料充分接触。
调整反应体系的压力为-0.035MPa，反应温度为80℃，反应时间为1h。
调整第二阶段反应体系的压力为-0.075MPa，其中反应温度为80℃，反应时间为4h。
溶剂 糖类转化率 HMF反应产率
2，5-四氢呋喃二甲醇 100％ 97.80％
甲基异丁基酮 100％ 94.70％
二甲基哑砜 100％ 93.30％
正丁醇 100％ 92.40％
2-丁醇 100％ 92.10％
乙酸乙酯 100％ 93.70％
二氯甲烷 100％ 94.50％
N，N-二甲基乙酰胺 100％ 91.60％
吡咯烷酮 100％ 94.10％
氯仿 100％ 93.70％
丙酮 100％ 94.30％
实施例5
在反应器中将配置好的氯化钠∶水＝3∶1的盐溶液投入反应釜中，加热至80℃、搅拌均匀，加入结晶果糖∶盐溶液∶催化剂＝10∶3∶0.1。反应过程中加热、搅拌使体系物料充分接触。
调整反应体系的压力为-0.035MPa，反应温度为80℃，反应时间为1h。
调整第二阶段反应体系的压力为-0.075MPa，其中反应温度为80℃，反应时间为4h。
催化剂 糖类转化率 HMF反应产率
Nafion NR50 100％ 97.70％
Dowex 50W-X8 100％ 96.30％
Amberlite-IR 120 100％ 96.10％
Amberlyst_x005f-15 100％ 97.50％
Amberlyst_x005f-70 100％ 98.00％
本发明通过控制反应过程中的压力，应用到催化糖类制备HMF的方法中，解决了常压反应温度高，焦化严重，控制了反应过程中副反应的发生，提高了目标产物的选择性和产率。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。

Claims (13)

  1. 一种制备5-羟甲基糠醛的方法，其特征在于，将含有盐溶液、糖类化合物和催化剂的物料混合，反应I，得到所述5-羟甲基糠醛；
    所述反应I的压力为-0.1～-0.015Mpa，反应时间0.5～8h；
    以质量计，盐溶液：糖类化合物：催化剂＝5～40:1～30:0.1；
    所述固体酸催化剂选自酸性离子交换树脂。
  2. 根据权利要求1所述的方法，其特征在于，所述反应I的压力为-0.08～-0.04Mpa，反应时间1.5～5h。
  3. 根据权利要求1所述的方法，其特征在于，所述反应I包括反应II-1和反应II-2；
    所述反应II-1的压力为-0.045～-0.015Mpa，反应时间0.5～1.5h；
    所述反应II-2的压力为-0.1～-0.045Mpa，反应时间0.5～6.5h。
  4. 根据权利要求3所述的方法，其特征在于，所述反应II-1的压力为-0.04～-0.025Mpa，反应时间0.5～1.5h；所述反应II-2的压力为-0.08～-0.065Mpa，反应时间1～3.5h。
  5. 根据权利要求1～4任一所述的方法，其特征在于，所述盐溶液的盐包括无机盐、有机盐中的一种或多种。
  6. 根据权利要求5所述的方法，其特征在于，所述无机盐包括金属盐。
  7. 根据权利要求6所述的方法，其特征在于，所述金属包括钠、钾、锂、镁、锌、钙中的至少一种。
  8. 根据权利要求6所述的方法，其特征在于，所述金属盐包括金属 的氯化盐、碳酸盐、碳酸氢盐、硫酸盐、硫酸氢盐中的至少一种。
  9. 根据权利要求8所述的方法，其特征在于，所述金属的氯化盐包括氯化钠、氯化钾、氯化锂、氯化钙、氯化镁、氯化锌中的至少一种。
  10. 根据权利要求6所述的方法，其特征在于，所述金属盐包括溴化钠、碳酸钠、碳酸氢钠、硫酸钠、硫酸氢钠、溴化钾、氯化钾、碳酸钾、溴化锂、硫酸镁中的至少一种。
  11. 根据权利要求5所述的方法，其特征在于，所述有机盐包括咪唑类离子液体、吡啶类离子液体和季铵盐类离子液体中的至少一种。
  12. 根据权利要求11所述的方法，其特征在于，所述有机盐包括卤化烷基铵盐、短链烷基咪唑类离子液体和烷基吡啶型离子液体中的至少一种。
  13. 根据权利要求1～4任一所述的方法，其特征在于，以质量计，所述盐溶液中盐：溶剂＝1～10:1。
PCT/CN2022/129612 2021-11-04 2022-11-03 一种制备5-羟甲基糠醛的方法 Ceased WO2023078361A1 (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP22889382.2A EP4393911A4 (en) 2021-11-04 2022-11-03 PROCESS FOR THE PREPARATION OF 5-HYDROXYMETHYLFURFURAL

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111301873.2 2021-11-04
CN202111301873.2A CN113861139B (zh) 2021-11-04 2021-11-04 一种制备5-羟甲基糠醛的方法

Publications (1)

Publication Number Publication Date
WO2023078361A1 true WO2023078361A1 (zh) 2023-05-11

Family

ID=78987037

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/129612 Ceased WO2023078361A1 (zh) 2021-11-04 2022-11-03 一种制备5-羟甲基糠醛的方法

Country Status (3)

Country Link
EP (1) EP4393911A4 (zh)
CN (1) CN113861139B (zh)
WO (1) WO2023078361A1 (zh)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861139B (zh) * 2021-11-04 2023-12-12 浙江糖能科技有限公司 一种制备5-羟甲基糠醛的方法
CN114805254A (zh) * 2022-04-11 2022-07-29 合肥利夫生物科技有限公司 一种5-羟甲基糠醛的制备方法
CN118005580A (zh) * 2022-08-22 2024-05-10 中国科学院大连化学物理研究所 一种5-羟甲基糠醛的制备方法
CN118005583A (zh) * 2022-08-24 2024-05-10 中国科学院大连化学物理研究所 一种使用无机盐的5-羟甲基糠醛的制备方法
CN115894406B (zh) * 2022-10-17 2024-10-15 中科国生(杭州)科技有限公司 一种利用果糖制备5-羟甲基糠醛的方法
CN118026970A (zh) * 2022-11-11 2024-05-14 中国科学院大连化学物理研究所 一种5-羟甲基糠醛的制备方法
CN118026971A (zh) * 2022-11-14 2024-05-14 中国科学院大连化学物理研究所 一种5-羟甲基糠醛的制备方法
CN118026973A (zh) * 2022-11-14 2024-05-14 中国科学院大连化学物理研究所 一种5-羟甲基糠醛的制备方法
CN118126000A (zh) * 2022-12-02 2024-06-04 中国科学院大连化学物理研究所 一种5-羟甲基糠醛的制备方法
CN117756757A (zh) * 2023-12-18 2024-03-26 杭州云上新材有限公司 一种两相连续化合成5-羟甲基糠醛的方法及装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333200A (zh) * 2008-08-06 2008-12-31 淮北民生化工科技有限公司 一种5-羟甲基糠醛的合成方法
CN101367783A (zh) * 2008-10-10 2009-02-18 中国科学技术大学 5-羟甲基糠醛的制备方法
WO2015113060A2 (en) 2014-01-27 2015-07-30 Rennovia, Inc. Conversion of fructose-containing feedstocks to hmf-containing product
CN113861139A (zh) * 2021-11-04 2021-12-31 浙江糖能科技有限公司 一种制备5-羟甲基糠醛的方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3076554B1 (fr) * 2018-01-10 2020-09-18 Ifp Energies Now Procede de production de 5-hydroxymethylfurfural
CN112830907B (zh) * 2019-12-20 2022-03-22 中国科学院宁波材料技术与工程研究所 制备5-羟甲基糠醛的方法
CN111995602A (zh) * 2020-08-13 2020-11-27 浙江恒澜科技有限公司 一种利用酸性树脂催化果糖合成5-羟甲基糠醛的方法
CN112608289B (zh) * 2020-12-21 2023-09-05 中国科学院广州能源研究所 一种有机溶剂-离子液体复合体系催化生物基果糖高效制取5-羟甲基糠醛的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101333200A (zh) * 2008-08-06 2008-12-31 淮北民生化工科技有限公司 一种5-羟甲基糠醛的合成方法
CN101367783A (zh) * 2008-10-10 2009-02-18 中国科学技术大学 5-羟甲基糠醛的制备方法
WO2015113060A2 (en) 2014-01-27 2015-07-30 Rennovia, Inc. Conversion of fructose-containing feedstocks to hmf-containing product
CN113861139A (zh) * 2021-11-04 2021-12-31 浙江糖能科技有限公司 一种制备5-羟甲基糠醛的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of EP4393911A4

Also Published As

Publication number Publication date
CN113861139B (zh) 2023-12-12
EP4393911A4 (en) 2025-09-03
CN113861139A (zh) 2021-12-31
EP4393911A1 (en) 2024-07-03

Similar Documents

Publication Publication Date Title
CN113861139B (zh) 一种制备5-羟甲基糠醛的方法
Sun et al. One-pot depolymerization of cellulose into glucose and levulinic acid by heteropolyacid ionic liquid catalysis
US10898888B2 (en) Preparation and application of magnetic metallic oxide cross-linked acidic polyionic liquid
CN102199136A (zh) 一种利用酸性离子液体制备5-羟甲基糠醛的方法
Wu et al. Co-production of HMF and gluconic acid from sucrose by chemo-enzymatic method
CN111995602A (zh) 一种利用酸性树脂催化果糖合成5-羟甲基糠醛的方法
CN103058962B (zh) 一种由糠醇制备2,5-呋喃二甲醇二烷基醚的方法
Shi et al. Catalytic conversion of fructose and sucrose to 5-hydroxymethylfurfural using simple ionic liquid/DMF binary reaction media
CN107722030B (zh) 一种制备异己糖醇的方法
CN112094187B (zh) 一种由果糖制备及分离乙酰丙酸的方法
WO2025020679A1 (zh) 一种双酸性催化剂及催化半纤维素或木糖制备糠醛的方法
EP4217336B1 (en) Process for producing levulinic acid
CN110003150A (zh) 一种利用木糖制备糠醛的方法
CN114315553A (zh) 一种固体酸在亲水性des中催化葡萄糖制备乙酰丙酸的方法
CN106928168A (zh) 一种在温和条件下将葡萄糖转化为5‑羟甲基糠醛的方法
CN112341414A (zh) 一种5-氯甲基糠醛水解氧化两步法制备2,5-呋喃二甲酸的方法
CN115368325B (zh) 一种由甲壳素制备5-羟甲基糠醛的方法
CN115709073B (zh) 一种锡基催化剂的制备方法及其在催化生物质糖制备乳酸甲酯中的应用
CN107954955A (zh) 一种n-乙酰氨基葡萄糖制备5-羟甲基糠醛的方法
JP6900801B2 (ja) カルボン酸エステル又はカルボン酸の製造方法
CN114805253B (zh) 一种制备5-羟甲基糠醛的方法
CN105330623A (zh) 无机盐催化合成5-羟甲基糠醛的方法
CN110776465A (zh) 双功能温控离子液体及其制备方法、应用及催化降解纤维素为5-羟甲基糠醛的方法
CN114075157B (zh) 一种连续生产生物基呋喃化合物的方法
CN103159707A (zh) 一种生物质催化转化制备呋喃衍生物的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22889382

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 22889382.2

Country of ref document: EP

Ref document number: 2022889382

Country of ref document: EP

ENP Entry into the national phase

Ref document number: 2022889382

Country of ref document: EP

Effective date: 20240327

NENP Non-entry into the national phase

Ref country code: DE