CN115536512A - Method and device for continuously synthesizing levulinic acid - Google Patents
Method and device for continuously synthesizing levulinic acid Download PDFInfo
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- CN115536512A CN115536512A CN202211124514.9A CN202211124514A CN115536512A CN 115536512 A CN115536512 A CN 115536512A CN 202211124514 A CN202211124514 A CN 202211124514A CN 115536512 A CN115536512 A CN 115536512A
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- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 title claims abstract description 88
- 229940040102 levulinic acid Drugs 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 23
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 18
- 239000002245 particle Substances 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 230000002378 acidificating effect Effects 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- 229930091371 Fructose Natural products 0.000 claims description 13
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 13
- 239000005715 Fructose Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 8
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 7
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 7
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims description 5
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims description 4
- 229920001429 chelating resin Polymers 0.000 claims description 4
- 239000003456 ion exchange resin Substances 0.000 claims description 4
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010924 continuous production Methods 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 17
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 6
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 3
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZGXJTSGNIOSYLO-UHFFFAOYSA-N 88755TAZ87 Chemical compound NCC(=O)CCC(O)=O ZGXJTSGNIOSYLO-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- VKOUCJUTMGHNOR-UHFFFAOYSA-N Diphenolic acid Chemical compound C=1C=C(O)C=CC=1C(CCC(O)=O)(C)C1=CC=C(O)C=C1 VKOUCJUTMGHNOR-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- JOOXCMJARBKPKM-UHFFFAOYSA-M 4-oxopentanoate Chemical compound CC(=O)CCC([O-])=O JOOXCMJARBKPKM-UHFFFAOYSA-M 0.000 description 1
- 108700032845 Ala(2)- enkephalinamide-Met Proteins 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229960002749 aminolevulinic acid Drugs 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 229940058352 levulinate Drugs 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 150000002772 monosaccharides Chemical class 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
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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
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
-
- 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
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method and a device for continuously synthesizing levulinic acid, wherein the method comprises the following steps: adding a compound aqueous solution with the mass concentration of 0.1-50% into a closed container filled with acidic catalyst particles, and reacting for 10s-30min at the temperature of 50-200 ℃ and under the pressure of 0-3 MPa to obtain the levulinic acid. The device comprises a raw material tank, a raw material pump, a filling type micro-reactor and a back pressure valve; the filling type microreactor is a closed container filled with acidic catalyst particles, the liquid outlet of the stock tank is connected with the liquid inlet of the filling type microreactor, a stock pump is arranged on a connecting pipeline of the stock tank and the filling type microreactor, and a back pressure valve is arranged on an outlet pipeline of the filling type microreactor. The device and the method realize the continuous production of the synthesized levulinic acid.
Description
Technical Field
The invention relates to a method and a device for continuously synthesizing levulinic acid, and belongs to the field of biomass catalytic conversion.
Background
Levulinic acid is a high value-added biomass-derived platform chemical, and is also selected by the U.S. department of energy as one of the 12 most valuable platform compounds. Levulinic acid is mainly used for producing gamma-valerolactone (GVL), aminolevulinic acid (DALA), diphenolic acid (DPA), methyltetrahydrofuran, various ester chemicals, resins and the like, and can be widely applied to the fields of medicines, foods, energy sources, chemical industry and the like. Levulinic acid is mainly derived from the acid-catalyzed reaction of monosaccharides (glucose, fructose, xylose, etc.), for glucose and xylose it is first isomerized by Lewis acid sites of the catalyst and then based on
The acid sites catalyze and undergo dehydration and hydration reactions to ultimately produce levulinic acid. The conversion of fructose to levulinic acid is considered to be a more accessible reaction means than glucose and xylose due to the short reaction path (fructose → 5-hydroxymethylfurfural → levulinic acid) and high yield.
Based on the traditional stirred tank reactor, under the action of catalysts such as sulfuric acid, hydrochloric acid, phosphoric acid, transition metal chloride and the like, the high levulinic acid yield (up to 80 percent) can be obtained. However, the disadvantages of using homogeneous acid catalysts are well known: severely corroding equipment, difficult separation of products caused by using a large amount of homogeneous catalysts, environmental pollution and the like. The use of the solid acid catalyst can effectively reduce the corrosion to reaction equipment, has the characteristics of easy recovery, recyclability and the like, and is beneficial to the separation and refining of reactants and products. In addition, the fluid back-mixing of a batch reactor (such as a reaction kettle) is large, the diffusion distance of the fluid in the reactor is long, the mass transfer and heat transfer rate is slow, the conversion rate of reactants and the yield of target products are low, and the reaction time is long, particularly under the condition of using green solvent pure water. In addition, the reaction temperature and pressure for converting fructose into levulinic acid are high (70-220 ℃, 0-3 MPa), and a large-scale batch stirred tank reactor has potential safety hazards. In recent years, a filled microreactor has attracted much attention that has a small supported catalyst particle size, has rapid mixing and excellent liquid-solid transfer characteristics while maintaining the original fixed-bed plug flow characteristics (back-mixing close to 0), and is easy to produce continuously and on a large scale. The filling type microreactor is applied to converting levulinate by fructose, can effectively strengthen the liquid-solid reaction process, obviously shorten the reaction time, and is easy for industrial continuous production and amplification.
Disclosure of Invention
The invention aims to solve the problems of low reaction efficiency, long reaction time, difficulty in continuous production, low safety and the like in the traditional intermittent levulinic acid synthesis process, and provides a method and a device for continuously synthesizing levulinic acid.
The purpose of the invention is realized by the following technical scheme:
the invention relates to a method for continuously synthesizing levulinic acid, which comprises the following specific synthesis steps:
adding a compound aqueous solution with the mass concentration of 0.1-50% into a closed container filled with acidic catalyst particles, and reacting for 10s-30min at the temperature of 50-200 ℃ and under the pressure of 0-3 MPa to obtain levulinic acid; the adding flow rate of the compound water solution is 0.01 ml/min-20 ml/min;
the compound aqueous solution is a fructose aqueous solution or a 5-hydroxymethylfurfural aqueous solution;
the acidic catalyst particles are ion exchange resin catalysts; preferably Amberlyst 15 particles, amberlyst 70 particles, HND-8 particles, HND-12 particles or HND-580 particles;
the acidic catalyst particles have a diameter of from 50 μm to 2000. Mu.m, preferably from 100 μm to 500. Mu.m.
The mass concentration of the compound aqueous solution is preferably 1-10 wt%.
The addition flow rate of the aqueous solution of the compound is preferably 0.05 to 3ml/min.
The reaction temperature and pressure are preferably 100-150 ℃ and 1-2MPa.
The invention relates to a device for continuously synthesizing levulinic acid, which comprises a raw material tank, a raw material pump, a filling type microreactor and a back pressure valve;
the filling type microreactor is a closed container filled with acidic catalyst particles, and the upper end of the filling type microreactor is provided with a liquid inlet and the lower end of the filling type microreactor is provided with a liquid outlet; the acidic catalyst particles are ion exchange resin catalysts; preferably Amberlyst 15 particles, amberlyst 70 particles, HND-8 particles, HND-12 particles, HND-580 particles;
the diameter of the acidic catalyst particles is 50 μm to 2000 μm, preferably 100 μm to 500 μm;
a compound aqueous solution with the mass concentration of 0.1-50% is filled in the raw material tank, and the compound is a fructose aqueous solution or a 5-hydroxymethylfurfural aqueous solution;
the liquid outlet of head tank with the inlet of filled microreactor links to each other, be equipped with the former feed pump on the connecting pipeline of head tank and filled microreactor, be equipped with the back pressure valve on the outlet pipeline of filled microreactor.
The filled microreactor preferably adopts a vertically-placed long cylindrical structure, and the length-diameter ratio of the filled microreactor is more than 30.
And a heating pipeline is sleeved on the outer wall of the filled microreactor.
Advantageous effects
The device and the method improve the reaction efficiency of the levulinic acid synthesis process, have short reaction time, realize continuous production and have high safety. The invention utilizes the characteristics of high liquid holding capacity and plug flow of the filled microreactor, strengthens the inter-phase transfer rate in the reaction process, effectively reduces the generation of intermediate products and side reactions, is easy to fixedly separate and reuse the catalyst, controls the reaction progress by accurately controlling the retention time, and improves the greenness and safety of the continuous synthesis process of the levulinic acid.
Drawings
FIG. 1 is a schematic structural diagram of a synthesis apparatus according to the present invention;
in the figure: 1-raw material tank, 2-raw material pump, 3-filled micro reactor, 4-back pressure valve.
Detailed Description
The invention will be further described with reference to the following drawings and examples
Example 1
A method for continuously synthesizing levulinic acid is realized by adopting a special synthesis device, and the device comprises the following steps: as shown in fig. 1, a raw material tank 1, a raw material pump 2, a packed microreactor 3, a back pressure valve 4;
the filling type microreactor 3 is a closed container filled with spherical acidic catalyst particles, the closed container is of a long cylindrical structure with the length-diameter ratio of 36, a liquid inlet is formed in the upper end of the filling type microreactor 3, a heating pipeline is sleeved on the outer wall of the filling type microreactor 3, and a liquid outlet is formed in the lower end of the filling type microreactor 3; the acidic catalyst particles are HND-580 particles; the acidic catalyst particles have a diameter of 500 μm;
the fructose solution with the mass concentration of 8% is filled in the raw material tank 1, the raw material tank 1 is connected with a liquid inlet of the filling type microreactor 3 through a pipeline, a raw material pump 3 is arranged on a connecting pipeline of the raw material tank 1 and the filling type microreactor 3, and a back pressure valve 4 is arranged on an outlet pipeline of the filling type microreactor 3.
The method for continuously synthesizing the levulinic acid by the filled microreactor comprises the following specific steps:
pumping 8% of fructose aqueous solution with mass concentration in the raw material tank 1 into the packed bed microreactor 3 by adopting the raw material pump 2 at the flow rate of 0.1ml/min, heating the temperature in the packed microreactor 3 to 150 ℃, adjusting the operating pressure of a back pressure valve 4 to be 1.5MPa, discharging levulinic acid from an outlet pipeline by the packed microreactor 3 after reacting for 8min, and calculating that the conversion rate and the yield of the levulinic acid are 99% and 65% respectively.
Example 2
A method for continuously synthesizing levulinic acid is realized by adopting a special synthesis device, and the device comprises the following steps: a raw material tank 1, a raw material pump 2, a filling type microreactor 3 and a back pressure valve 4;
the filling type microreactor 3 is a closed container filled with spherical acidic catalyst particles, the closed container is of a long cylindrical structure with the length-diameter ratio of 36, a liquid inlet is formed in the upper end of the filling type microreactor 3, a heating pipeline is sleeved on the outer wall of the filling type microreactor 3, and a liquid outlet is formed in the lower end of the filling type microreactor 3; the acidic catalyst particles are HND-580 particles; the acidic catalyst particles have a diameter of 500 μm;
the raw material tank 1 is internally provided with a 5-hydroxymethylfurfural aqueous solution with the mass concentration of 10%, the raw material tank 1 is connected with a liquid port of the filling type microreactor 3 through a pipeline, a raw material pump 3 is arranged on a connecting pipeline of the raw material tank 1 and the filling type microreactor 3, and an outlet pipeline of the filling type microreactor 3 is provided with a back pressure valve 4.
The method for continuously synthesizing the levulinic acid by the filled microreactor comprises the following specific steps:
and pumping a 5-hydroxymethylfurfural aqueous solution with the mass concentration of 10% in the raw material tank 1 into the packed bed microreactor 3 by using the raw material pump 2 at the flow rate of 0.1ml/min, heating the temperature in the packed microreactor 3 to 150 ℃, adjusting the operating pressure range of the backpressure valve 4 to be 2MPa, and after reacting for 8min, discharging levulinic acid from an outlet pipeline by using the packed microreactor 3, wherein the conversion rate and the yield of the levulinic acid are calculated to be 100% and 99% respectively.
Example 3
A method for continuously synthesizing levulinic acid is realized by adopting a special synthesis device, and the device comprises the following steps: a raw material tank 1, a raw material pump 2, a filling type microreactor 3 and a back pressure valve 4;
the filling type microreactor 3 is a closed container filled with spherical acidic catalyst particles, the closed container is of a long cylindrical structure with the length-diameter ratio of 36, a liquid inlet is formed in the upper end of the filling type microreactor 3, a heating pipeline is sleeved on the outer wall of the filling type microreactor 3, and a liquid outlet is formed in the lower end of the filling type microreactor 3; the acidic catalyst particles are Amberlyst 15 particles; the acidic catalyst particles have a diameter of 500 μm;
fructose aqueous solution is equipped with in the head tank 1, and head tank 1 links to each other through the liquid mouth of pipeline with filled microreactor 3, is equipped with feedstock pump 3 on the connecting line of head tank 1 and filled microreactor 3, is equipped with back pressure valve 4 on the outlet pipeline of filled microreactor 3.
The method for continuously synthesizing the levulinic acid by the filled microreactor comprises the following specific steps:
pumping 2% of fructose aqueous solution with mass fraction in the raw material tank 1 into the packed bed microreactor 3 by using the raw material pump 2 at a flow rate of 0.2ml/min, heating the temperature in the packed microreactor 3 to 150 ℃, adjusting the operating pressure range of the back pressure valve 4 to be 3MPa, discharging levulinic acid from an outlet pipeline by the packed microreactor 3 after reacting for 6min, and calculating the conversion rate and the yield of the levulinic acid to be 98% and 74.9% respectively.
Claims (10)
1. A method for continuously synthesizing levulinic acid is characterized by comprising the following specific synthesis steps:
adding a compound aqueous solution with the mass concentration of 0.1-50% into a closed container filled with acidic catalyst particles, and reacting for 10s-30min at the temperature of 50-200 ℃ and under the pressure of 0-3 MPa to obtain levulinic acid; the adding flow rate of the compound water solution is 0.01 ml/min-20 ml/min;
the compound aqueous solution is a fructose aqueous solution or a 5-hydroxymethylfurfural aqueous solution;
the acidic catalyst particles are ion exchange resin catalysts, and the diameter of the acidic catalyst particles is 50-2000 mu m.
2. A process for the continuous synthesis of levulinic acid according to claim 1, characterized in that: the acidic catalyst particles are Amberlyst 15 particles, amberlyst 70 particles, HND-8 particles, HND-12 particles or HND-580 particles.
3. A process for the continuous synthesis of levulinic acid according to claim 1 or 2, characterized in that: the acidic catalyst particles have a diameter of 100 μm to 500. Mu.m.
4. A process for the continuous synthesis of levulinic acid according to claim 1, characterized in that: the mass concentration of the compound aqueous solution is 1-10 wt%.
5. A process for the continuous synthesis of levulinic acid according to claim 1, characterized in that: the adding flow rate of the compound water solution is 0.05-3ml/min.
6. A device for continuously synthesizing levulinic acid is characterized in that: comprises a raw material tank, a raw material pump, a filling type micro-reactor and a back pressure valve;
the filling type microreactor is a closed container filled with acidic catalyst particles, and the upper end of the filling type microreactor is provided with a liquid inlet and the lower end of the filling type microreactor is provided with a liquid outlet; the acidic catalyst particles are ion exchange resin catalysts, and the diameter of the acidic catalyst particles is 50-2000 mu m;
a compound aqueous solution with the mass concentration of 0.1-50% is filled in the raw material tank, and the compound is a fructose aqueous solution or a 5-hydroxymethylfurfural aqueous solution;
the liquid outlet of head tank with the inlet of filling formula microreactor links to each other, be equipped with the feedstock pump on the connecting pipeline of head tank and filling formula microreactor, be equipped with the back pressure valve on the outlet pipeline of filling formula microreactor.
7. The apparatus for continuously synthesizing levulinic acid according to claim 6, wherein: the acidic catalyst particles are Amberlyst 15 particles, amberlyst 70 particles, HND-8 particles, HND-12 particles, or HND-580 particles.
8. An apparatus for the continuous synthesis of levulinic acid according to claim 6 or 7, wherein: the acidic catalyst particles are 100-500 μm.
9. The apparatus for continuously synthesizing levulinic acid according to claim 6, wherein: the filling type microreactor adopts a vertically-arranged long cylindrical structure, and the length-diameter ratio of the filling type microreactor is larger than 30.
10. The apparatus for continuously synthesizing levulinic acid according to claim 6, wherein: and a heating pipeline is sleeved on the outer wall of the filling type microreactor.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101020629A (en) * | 2007-03-09 | 2007-08-22 | 浙江大学 | Process of separating acetylpropionic acid with active carbon |
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