WO2019041583A1 - 一种利用离子液体催化木质素制备对羟基肉桂酸酯的方法 - Google Patents
一种利用离子液体催化木质素制备对羟基肉桂酸酯的方法 Download PDFInfo
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- WO2019041583A1 WO2019041583A1 PCT/CN2017/112102 CN2017112102W WO2019041583A1 WO 2019041583 A1 WO2019041583 A1 WO 2019041583A1 CN 2017112102 W CN2017112102 W CN 2017112102W WO 2019041583 A1 WO2019041583 A1 WO 2019041583A1
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- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0298—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature the ionic liquids being characterised by the counter-anions
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
- B01J31/30—Halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
- C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
- C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
Definitions
- the invention relates to the high-efficiency utilization technology of agricultural wastes and the high-value utilization of renewable resources, in particular to a method for preparing p-hydroxycinnamate by selective catalysis of lignin by ionic liquid.
- the method adopts the herb lignin widely used in agricultural and forestry waste as a raw material, and adopts a metal ionic liquid synthesized by a metal chloride and an imidazolium chloride salt as a catalyst, and the ionic liquid is low in cost and economic in the synthesis process.
- the use of C1-C4 fatty alcohol as a solvent not only makes the product highly selective for hydroxycinnamate, but also can separate the product and recycle the catalyst.
- the cation of the halogen metal salt ionic liquid is an alkyl imidazole; the anion is [FeCl 4 ] - , [CrCl 4 ] - , [AlCl 4 ] - , [MnCl 4 ] 2- , [CoCl 4 ] 2- , [ NiCl 4 ] 2- , [CuCl 4 ] 2- or [ZnCl 4 ] 2- .
- the structural formula of the halogen metal salt ionic liquid is:
- the mixing time at 30-80 ° C is 3-8 h; the extracting agent of step 1) is ethyl acetate.
- the solvent is a C1-C7 fatty alcohol
- the stirring speed is 150-600 r/min
- the lignin is agroforestry herbal lignin.
- the agricultural and forestry herbal lignin is bagasse, wheat straw, corn stover, corn cob, straw, bamboo or Miscanthus; when prepared, the organic dissolved lignin is extracted by the following method: 100 parts in parts by mass Ionic water, 150-250 parts ethanol, 0.5-1.5 parts of sulfuric acid, 15-30 parts of agricultural and forestry waste powder is added to the reaction kettle, reacted at 150-200 ° C for 2-6 hours, filtered and separated, and the liquid phase is deionized water and separated by filtration, and the obtained solid is organically dissolved. Lignin.
- the alkylimidazolium chloride salt is prepared according to the following steps: N-methylimidazole and 1-chloroalkane are thoroughly mixed according to a molar ratio of 0.1-1:0.12-1.2, and stirred at room temperature for 12-24 hours. The temperature was raised to 60-100 ° C, and stirring was continued for 24-36 h to obtain a mixed solution; the mixed solution was washed with diethyl ether and dried under vacuum to give a methyl imidazolium chloride salt.
- the halogen metal salt ionic liquid [C n mim] 2 [MCl 4 ] is prepared as follows: 2-50 mmol of manganese chloride or cobalt chloride or nickel chloride or copper chloride or zinc chloride and an equivalent amount of alkylimidazole Mix the chloride salt, stir at 60-80 ° C for 3-6 h, extract with 5-15 mL of dichloromethane, distill off the solvent, and dry at 60-80 ° C for 12-24 h to obtain a halogen metal salt ionic liquid [C n mim ] 2 [MCl 4 ].
- the principle of the present invention is that the H monomer (p-hydroxyphenyl lignin) based on the herb lignin in the present invention is mostly linked to lignin by an ester bond, while other G (guaiac wood lignin) and S ( The syringyl lignin unit is linked by more ether bonds and carbon-carbon bonds, and the halogen metal salt ionic liquid has a good selective fracture property for the ester bond in the lignin, thereby achieving the selection of the fracture-depolymerized lignin.
- the purpose is to break through the problems of poor selectivity to lignin catalytic degradation, low efficiency, difficult separation of target products and difficult recovery of catalysts, and achieve efficient use of agricultural and forestry waste and high-selective catalytic depolymerization of lignin.
- the halogen metal salt ionic liquid catalytic system realizes selective catalytic depolymerization of lignin of agricultural and forestry waste such as bagasse, and prepares p-hydroxycinnamate; the reaction conversion rate is 40-50%, and the volatile product yield is 100.
- the yield of -150 mg/g, methyl p-hydroxycinnamate is 60-80 mg/g, and the corresponding selectivity is 55-75%.
- the main product has a high quotient of p-hydroxycinnamate
- the application value can be used as a pharmaceutical intermediate and a fine chemical; wherein methyl p-hydroxycinnamate can also be used for liquid crystal and optical fiber materials.
- Figure 3 is a carbon spectrum nuclear magnetic diagram of the main product separated in Example 1.
- Figure 4 is a mass spectrum of the main product isolated in Example 1.
- a method for preparing p-hydroxycinnamate by using ionic liquid to catalyze lignin the operation steps are as follows:
- halogen metal salt ionic liquid [C 4 mim][FeCl 4 ] 20 mmol of ferric chloride and an equal mass of 1-butyl-4-methylimidazolium chloride C 4 mimCl were mixed and stirred at 30 ° C After 3 hours, it was extracted with 5 mL of dichloromethane, and the resulting solution was evaporated to dryness, and then dried under vacuum at 60 ° C for 12 to 24 hours to obtain a metal salt, a halogen ionic liquid [C 4 mim] [FeCl 4 ].
- the calculated lignin conversion was 48%, the volatile product yield was 120 mg/g, and the yield of methyl p-hydroxycinnamate was 87 mg/g, and the corresponding selectivity was 73%.
- Other products obtained by the GC/MS are methyl ferulate, vanillin, syringaldehyde, and other acids and esters.
- halogen metal salt ionic liquid [C 3 mim][FeCl 4 ] 20 mmol of ferric chloride and 20 mmol of 1-propyl-3-methylimidazolium chloride [C 3 mim]Cl were mixed at 40 ° C After stirring for 8 hours, it was extracted with 5 mL of dichloromethane, and the resulting solution was evaporated to dryness, and dried under vacuum at 60 ° C for 12 to 24 hours to obtain a metal salt, a halogen ionic liquid [C 3 mim] [FeCl 4 ].
Abstract
Description
重复次数 | 1 | 2 | 3 | 4 | 5 |
转化率(%) | 48 | 46 | 45 | 43 | 44 |
挥发性产物收率(mg/g) | 120 | 114 | 106 | 101 | 105 |
对羟基肉桂酸酯收率(mg/g) | 78 | 75 | 69 | 66 | 63 |
对羟基肉桂酸酯选择性(%) | 65 | 66 | 65 | 65 | 62 |
Claims (10)
- 一种利用离子液体催化木质素制备对羟基肉桂酸酯的方法,其特征在于包括以下操作步骤:1)离子液体的制备:将烷基咪唑氯盐和金属卤化物以摩尔比为1:1-2:1在30-80℃下混合,萃取后干燥,得到卤素金属盐离子液体;2)木质素的解聚方法:将步骤(1)所得卤素金属盐离子液体与有机溶木质素混合,加入溶剂,经N2置换后,加热到140-200℃,在搅拌下反应4-8h,将反应液过滤萃取后获得生物化学品,生物化学品经过浓缩分离后得到对羟基肉桂酸酯。
- 根据权利要求1所述的利用离子液体催化木质素制备对羟基肉桂酸酯的方法,其特征在于:步骤1)所述金属卤化物为氯化铝、氯化铁、氯化铬、氯化锰、氯化钴、氯化镍、氯化铜或氯化锌。
- 根据权利要求1所述的利用离子液体催化木质素制备对羟基肉桂酸酯的方法,其特征在于:所述卤素金属盐离子液体的阳离子为烷基咪唑;阴离子为:[FeCl4]-、[CrCl4]-、[AlCl4]-、[MnCl4]2-、[CoCl4]2-、[NiCl4]2-、[CuCl4]2-或[ZnCl4]2-。
- 根据权利要求1所述的利用离子液体催化木质素制备对羟基肉桂酸酯的方法,其特征在于:所述30-80℃下混合的时间为3-8h;步骤1)所述萃的萃取剂为乙酸乙酯。
- 根据权利要求1所述的利用离子液体催化木质素制备对羟基肉桂酸酯的方法,其特征在于:所述的溶剂为C1-C7的脂肪醇;所述搅拌的转速为150-600r/min;所述的木质素为农林草本木质素。
- 根据权利要求6所述的利用离子液体催化木质素制备对羟基肉桂酸酯的方法,其特征在 于:所述的农林草本木质素为蔗渣、小麦秸秆、玉米秸秆、玉米芯、稻草、竹子或芒草;制备时,有机溶木质素通过如下方法提取:以质量份数计,将100份去离子水,150-250份乙醇、0.5-1.5份硫酸,15-30份农林废弃物粉末加入到反应釜中,在150-200℃下反应2-6h后过滤分离,液相加去离子水后过滤分离,所得固体即为有机溶木质素。
- 根据权利要求1所述的利用离子液体催化木质素制备对羟基肉桂酸酯的方法,其特征在于:所述的将反应液过滤萃取后获得生物化学品的步骤如下:将去离子水加入至反应液,析出未反应的木质素,过滤,滤渣在60-80℃下烘干,滤液蒸干后加水转移到分液漏斗后用乙酸乙酯萃取三次,将萃取相蒸干得到对羟基肉桂酸酯、阿魏酸酯、酸类化合物、醛类化合物和酯类衍生物的生物化学品。
- 根据权利要求1所述的利用离子液体催化木质素制备对羟基肉桂酸酯的方法,其特征在于:所述的烷基咪唑氯盐按照以下步骤制备得到:将N-甲基咪唑和l-氯烷烃按照摩尔比0.1-1:0.12-1.2充分混合,在室温下搅拌12-24h后,升温至60-100℃,继续搅拌24-36h,得到混合溶液;混合溶液经乙醚洗涤后真空干燥,得到烷基咪唑氯盐。
- 根据权利要求4所述的利用离子液体催化木质素制备对羟基肉桂酸酯的方法,其特征在于:卤素金属盐离子液体[Cnmim][MCl4]按如下方法制备:2-50mmol氯化铁或氯化铝或氯化铬和等物质量的烷基咪唑氯盐混合,在30-50℃搅拌3-6h后用5-15mL二氯甲烷萃取,将所得溶液蒸除溶剂,60-80℃真空干燥12-24h,得到卤素金属盐离子液体[Cnmim][MCl4];卤素金属盐离子液体[Cnmim]2[MCl4]按如下方法制备:2-50mmol氯化锰或氯化钴或氯化镍或氯化铜或氯化锌和等物质量的烷基咪唑氯盐混合,在60-80℃搅拌3-6h后用5-15mL二氯甲烷萃取,将所得溶液蒸除溶剂,60-80℃真空干燥12-24h,得到卤素金属盐离子液体[Cnmim]2[MCl4]。
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