CN107973709A - A kind of biomass-based method for preparing methyl ester levulinate - Google Patents

A kind of biomass-based method for preparing methyl ester levulinate Download PDF

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Publication number
CN107973709A
CN107973709A CN201711180854.2A CN201711180854A CN107973709A CN 107973709 A CN107973709 A CN 107973709A CN 201711180854 A CN201711180854 A CN 201711180854A CN 107973709 A CN107973709 A CN 107973709A
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biomass
methyl ester
based method
ester levulinate
preparing methyl
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莫祖勇
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a kind of biomass-based method for preparing methyl ester levulinate, comprise the following steps：(1) biomass is placed in first reaction kettle, 13.5~18s is hydrolyzed under the conditions of being 1.15%~3.15%H2SO4 in 220~240 DEG C, concentration；(2) product of step (1) is placed in second reaction kettle, mixture hydrolyzes 20~30min generation levulic acids under the conditions of 200~215 DEG C, 3%~7%H2SO4；(3) levulic acid and methanol lactonize generation in catalyst, wherein, esterification reaction temperature is 110 130 DEG C, and absolute pressure is 2 3MPa, when reaction time of esterification is 1.5 3 small.

Description

A kind of biomass-based method for preparing methyl ester levulinate
Technical field
The present invention relates to biomass material preparing technical field, more particularly to a kind of biomass-based prepare methyl ester levulinate Method.
Background technology
Methyl ester levulinate is a kind of faint yellow, clear oil compound, is a kind of high-effect diesel fuel additives, can also make It is used alone for clean fuel.Product quality is required up to the requirement of EN590 standards, discharge up to ULSD standards.The product can be reduced 96% greenhouse gas emission, allows to blend use with 65% ratio and petroleum diesel, with grease biodiesel phase in Europe Decline 50% than, cost, sale price high 30 more than %.And have the characteristics that it is biodegradable, low it is solidifying, oxidation stability is good, be The developing direction of high-grade diesel fuel.
In recent years, solid acid catalyst is widely used in catalytic dehydration, alkyl as a kind of environmentally protective catalyst In the reaction process such as change, isomerization, esterification, cracking, it have easily separated with product, not etching apparatus, free from environmental pollution and can Many advantages, such as reuse.Study at present it is most commonly used be sulfate radical promote metal oxide catalyst, such solid Acid has shown good catalytic activity and heat endurance in many acid catalyzed reactions, thus is especially subject to domestic and international section skilled worker The favor of author.Frank Rataboul and Nadine Essayem are reported with solid acid catalyst in supercritical methanol (300 DEG C/10MPa/1min) directly conversion cellulose prepares methyl ester levulinate, find in CsxH3-xPW12O40 or SO42-/ZrO2 is catalyzed lower methyl ester levulinate yield close to 20%.But the reaction condition is harsh, it is desirable to higher Reacted under temperature and pressure.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of biomass-based method for preparing methyl ester levulinate, prepare Methyl ester levulinate purity it is high, high income.
The technical solution that the present invention solves above-mentioned technical problem is as follows：A kind of biomass-based side for preparing methyl ester levulinate Method, comprises the following steps：
(1) biomass is placed in first reaction kettle, is 1.15%~3.15%H in 220~240 DEG C, concentration2SO4 Under the conditions of hydrolyze 13.5~18s；
(2) product of step (1) is placed in second reaction kettle, mixture is in 200~215 DEG C, 3%~7%H2SO4 Under the conditions of hydrolyze 20~30min generation levulic acid；
(3) levulic acid and methanol lactonize generation in catalyst, wherein, esterification reaction temperature is 110-130 DEG C, absolutely It is 2-3MPa to pressure, when reaction time of esterification is 1.5-3 small.
Based on the above technical solutions, the present invention can also be improved as follows.
Further, in the step (1), the temperature of hydrolysis of the biomass in the first reaction kettle is 230- 235 DEG C, absolute pressure 2.3-2.5MPa, the time is 16-18 seconds.
Further, in the step (2), the temperature of hydrolysis of the biomass in the second reaction kettle is 200- 205 DEG C, absolute pressure 1.2-1.4MPa, time 15-20min.
Further, in the step (3), the catalyst is the zinc acetate solution that mass percent concentration is 8-14%, The weight of the zinc acetate solution and straw is (0.3-0.5)：1.
Further, in the step (3), the catalyst is the H that mass percent concentration is 8-14%2SO4Solution, institute State H2SO4The weight of solution and straw is (0.2-0.4)：1.
The beneficial effects of the invention are as follows：The purity of methyl ester levulinate prepared by the present invention is high, high income, with discarded object straw Bar biolobic material is raw material, had not only saved production cost but also had reduced environmental pollution, and had also created the economic value of higher, for industry The comprehensive utilization of metaplasia production methyl ester levulinate and straw provides realistic approach.
Embodiment
The principles and features of the present invention are described below, and the given examples are served only to explain the present invention, is not intended to limit Determine the scope of the present invention.
Embodiment one
The biomass-based method for preparing methyl ester levulinate of the present embodiment comprises the following steps：
(1) biomass is placed in first reaction kettle, in 220 DEG C, concentration 1.15%H2SO4Under the conditions of hydrolyze 13.5；
(2) product of step (1) is placed in second reaction kettle, mixture is in 200 DEG C, 3%H2SO4Under the conditions of hydrolyze 20min generates levulic acid；
(3) levulic acid and methanol lactonize generation in catalyst, wherein, esterification reaction temperature is 110 DEG C, absolute pressure Power is 2MPa, reaction time of esterification for 1.5 it is small when, the catalyst is the zinc acetate solution that mass percent concentration is 8%, institute The weight for stating zinc acetate solution and straw is 0.3： 1.
Embodiment two
The biomass-based method for preparing methyl ester levulinate of the present embodiment comprises the following steps：
(1) biomass is placed in first reaction kettle, in 240 DEG C, concentration 3.15%H2SO4Under the conditions of hydrolyze 18s；
(2) product of step (1) is placed in second reaction kettle, mixture is in 215 DEG C, 7%H2SO4Under the conditions of hydrolyze 30min generates levulic acid；
(3) levulic acid and methanol lactonize generation in catalyst, wherein, esterification reaction temperature is 130 DEG C, absolute pressure Power is 3MPa, and when reaction time of esterification is 3 small, the catalyst is the H that mass percent concentration is 14%2SO4Solution, it is described H2SO4The weight of solution and straw is 0.4：1.
Embodiment three
The biomass-based method for preparing methyl ester levulinate of the present embodiment comprises the following steps：
(1) biomass is placed in first reaction kettle, in 230 DEG C, concentration 2%H2SO4Under the conditions of hydrolyze 15s；
(2) product of step (1) is placed in second reaction kettle, mixture is in 210 DEG C, 5%H2SO4Under the conditions of hydrolyze 25min generates levulic acid；
(3) levulic acid and methanol lactonize generation in catalyst, wherein, esterification reaction temperature is 120 DEG C, absolute pressure Power is 2.5MPa, and when reaction time of esterification is 2 small, the catalyst is the zinc acetate solution that mass percent concentration is 12%, The weight of the zinc acetate solution and straw is 0.4： 1.
The foregoing is merely presently preferred embodiments of the present invention, is not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent replacement, improvement and so on, should all be included in the protection scope of the present invention.

Claims (5)

  1. A kind of 1. biomass-based method for preparing methyl ester levulinate, it is characterised in that comprise the following steps：
    (1) biomass is placed in first reaction kettle, is 1.15%~3.15%H in 220~240 DEG C, concentration2SO4Under the conditions of Hydrolyze 13.5~18s；
    (2) product of step (1) is placed in second reaction kettle, mixture is in 200~215 DEG C, 3%~7%H2SO4Condition 20~30min of lower hydrolysis generates levulic acid；
    (3) levulic acid and methanol lactonize generation in catalyst, wherein, esterification reaction temperature is 110-130 DEG C, absolute pressure For 2-3MPa, reaction time of esterification for 1.5-3 it is small when.
  2. A kind of 2. biomass-based method for preparing methyl ester levulinate according to claim 1, it is characterised in that the step Suddenly in (1), the temperature of hydrolysis of the biomass in the first reaction kettle is 230-235 DEG C, absolute pressure 2.3- 2.5MPa, time are 16-18 seconds.
  3. A kind of 3. biomass-based method for preparing methyl ester levulinate according to claim 1, it is characterised in that the step Suddenly in (2), the temperature of hydrolysis of the biomass in the second reaction kettle is 200-205 DEG C, absolute pressure 1.2- 1.4MPa, time 15-20min.
  4. 4. a kind of biomass-based method for preparing methyl ester levulinate according to any one of claims 1 to 3, its feature exist In in the step (3), the catalyst is the zinc acetate solution that mass percent concentration is 8-14%, and the zinc acetate is molten The weight of liquid and straw is (0.3-0.5)：1.
  5. 5. a kind of biomass-based method for preparing methyl ester levulinate according to any one of claims 1 to 3, its feature exist In in the step (3), the catalyst is the H that mass percent concentration is 8-14%2SO4Solution, the H2SO4Solution with The weight of straw is (0.2-0.4)：1.
CN201711180854.2A 2017-11-23 2017-11-23 A kind of biomass-based method for preparing methyl ester levulinate Withdrawn CN107973709A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108913225A (en) * 2018-07-03 2018-11-30 安徽圣宝新能源科技有限公司 A kind of technique preparing alcohol-based fuel using levulic acid

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101148458A (en) * 2007-09-06 2008-03-26 中国科学院研究生院 Cogeneration method for sugar and acetylpropionic acid by utilizing lignocellulose-like biomass
CN102060704A (en) * 2009-11-18 2011-05-18 北京金骄生物质化工有限公司 Method for preparing methyl levulinate by utilizing plant straws
CN102558106A (en) * 2011-12-15 2012-07-11 北京金骄生物质化工有限公司 Method for preparing 2-methyltetrahydrofuran from waste biomass
CN103058862A (en) * 2012-12-14 2013-04-24 北京金骄生物质化工有限公司 New method for producing dialkyl ester carbonate by using forestry and agricultural residues as initial raw materials
CN105669421A (en) * 2016-02-26 2016-06-15 河南省科学院能源研究所有限公司 Method for preparing levulinic acid and furfural by hydrolyzing biomass

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101148458A (en) * 2007-09-06 2008-03-26 中国科学院研究生院 Cogeneration method for sugar and acetylpropionic acid by utilizing lignocellulose-like biomass
CN102060704A (en) * 2009-11-18 2011-05-18 北京金骄生物质化工有限公司 Method for preparing methyl levulinate by utilizing plant straws
CN102558106A (en) * 2011-12-15 2012-07-11 北京金骄生物质化工有限公司 Method for preparing 2-methyltetrahydrofuran from waste biomass
CN103058862A (en) * 2012-12-14 2013-04-24 北京金骄生物质化工有限公司 New method for producing dialkyl ester carbonate by using forestry and agricultural residues as initial raw materials
CN105669421A (en) * 2016-02-26 2016-06-15 河南省科学院能源研究所有限公司 Method for preparing levulinic acid and furfural by hydrolyzing biomass

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108913225A (en) * 2018-07-03 2018-11-30 安徽圣宝新能源科技有限公司 A kind of technique preparing alcohol-based fuel using levulic acid
CN108913225B (en) * 2018-07-03 2020-12-08 安徽圣宝新能源科技有限公司 Process for preparing alcohol-based fuel by utilizing levulinic acid

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