CN114634411A - Method for preparing itaconic acid from citric acid - Google Patents
Method for preparing itaconic acid from citric acid Download PDFInfo
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- CN114634411A CN114634411A CN202210396741.0A CN202210396741A CN114634411A CN 114634411 A CN114634411 A CN 114634411A CN 202210396741 A CN202210396741 A CN 202210396741A CN 114634411 A CN114634411 A CN 114634411A
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 title claims abstract description 95
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 6
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims abstract description 4
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Inorganic materials O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000009471 action Effects 0.000 claims abstract description 3
- 239000013078 crystal Substances 0.000 claims abstract description 3
- 229960004106 citric acid Drugs 0.000 claims description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 3
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 claims description 2
- 229960002303 citric acid monohydrate Drugs 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 5
- 239000002028 Biomass Substances 0.000 abstract description 3
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 229910001220 stainless steel Inorganic materials 0.000 description 6
- 239000010935 stainless steel Substances 0.000 description 6
- 239000012295 chemical reaction liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000001354 calcination Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000000855 fermentation Methods 0.000 description 3
- 230000004151 fermentation Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- -1 polytetrafluoroethylene Polymers 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 239000001124 (E)-prop-1-ene-1,2,3-tricarboxylic acid Substances 0.000 description 2
- 229940091181 aconitic acid Drugs 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- GTZCVFVGUGFEME-IWQZZHSRSA-N cis-aconitic acid Chemical compound OC(=O)C\C(C(O)=O)=C\C(O)=O GTZCVFVGUGFEME-IWQZZHSRSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GTZCVFVGUGFEME-UHFFFAOYSA-N trans-aconitic acid Natural products OC(=O)CC(C(O)=O)=CC(O)=O GTZCVFVGUGFEME-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 229910000667 (NH4)2Ce(NO3)6 Inorganic materials 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 241000228197 Aspergillus flavus Species 0.000 description 1
- 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 1
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000006386 memory function Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000013379 molasses Nutrition 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/377—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups
- C07C51/38—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by splitting-off hydrogen or functional groups; by hydrogenolysis of functional groups by decarboxylation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing itaconic acid from citric acid. The method comprises the following steps: and under the action of a catalyst, placing citric acid in water for reaction, and obtaining the itaconic acid after the reaction is finished. The catalyst is a powdery monoclinic phase with high specific surface areaZrO2Tetragonal phase ZrO2Monoclinic tetragonal mixed crystal phase ZrO2(hereinafter, the symbol is m, t-ZrO)2)、ZrxCe1‑xO2(x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9), SnO2、TiO2、Nb2O5And the like. The raw material used in the invention is derived from biomass, and the solvent used is H2O, in N2The reaction is carried out in the atmosphere, the reaction process is green, and byproducts harmful to the environment are not generated. The conversion rate of the citric acid is high and can reach 92.2 percent, and the yield of the itaconic acid reaches 70.2 percent. Has important application value.
Description
Technical Field
The invention belongs to the field of preparation of chemical raw materials, and particularly relates to a method for preparing itaconic acid from citric acid.
Background
Itaconic acid is used as a monomer to synthesize polyitaconic acid, or is copolymerized with other monomers to obtain a polymer with special performance, and the polymer is widely applied to the fields of synthetic resin, synthetic fiber and the like. The polyester in the form of hydrogel obtained from itaconic acid has good biocompatibility and biodegradability, and can be applied to the fields of drug transportation, biological tissue engineering and the like. For example, high molecular polyester has a shape memory function, and can restore its shape by heating it to a temperature higher than the glass transition temperature after it is deformed and damaged at a temperature lower than the glass transition temperature. The material obtained by filling the nano-silica with the copolymer of adipic acid, propylene glycol and butylene glycol can be used as the transparent rubber. Itaconic acid, acrylic acid and methacrylic acid can be used as biodegradable coating and printing material after copolymerization. At present, itaconic acid is mainly obtained by fermentation in industry. Glucose, pretreated molasses and other saccharide raw materials are converted into itaconic acid by aspergillus flavus fermentation at a certain temperature and pH, the global annual output reaches 8 million tons, and the market price is about $ 2 per kilogram. Although the synthesis of itaconic acid by a fermentation method is advanced to a certain extent, the large-scale application of itaconic acid is limited by the production scale and the product price of itaconic acid, so the development of high-efficiency catalytic conversion for synthesizing itaconic acid is particularly critical.
Disclosure of Invention
The invention aims to provide a method for preparing itaconic acid from citric acid. The citric acid raw material used in the invention is derived from renewable biomass, and the preparation process is environment-friendly, green and pollution-free.
The method for preparing itaconic acid by citric acid provided by the invention comprises the following steps: and under the action of a catalyst, placing citric acid in water for reaction, and obtaining the itaconic acid after the reaction is finished.
In the method, the catalyst is powdery monoclinic phase ZrO with high specific surface area2(hereinafter, the symbol is m-ZrO)2) Powdery tetragonal phase ZrO2(hereinafter referred to as t-ZrO)2) Powdered monoclinic tetragonal mixed crystal phase ZrO2(toWith the subscript m, t-ZrO2)、ZrxCe1-xO2(x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9), SnO2、TiO2、Nb2O5And the like.
The citric acid is at least one selected from citric acid monohydrate and citric acid anhydrous.
The dosage of the catalyst is 52-260% of the mass of the citric acid, and specifically can be 52%, 104%, 156%, 208% and 260%. The concentration of citric acid in the reaction solution is 0.01-0.1M, and specifically may be 0.01, 0.03, 0.05, 0.07, 0.1M. .
In the method, the reaction temperature of the reaction is 160-200 ℃, and specifically can be 160, 170, 180, 190, 200 ℃, and preferably 180 ℃. The reaction time of the reaction is 1-5h, preferably 3 h. The reaction is in N2The reaction is carried out under an atmosphere at a pressure of 1-4MPa, preferably 2 MPa.
In the method, the m-ZrO2Can be prepared according to the following method: ZrO (NO)3)2The mixed aqueous solution of the m-ZrO and the urea is generated under the hydrothermal condition2Precursor of m-ZrO2The precursor is obtained by roasting, wherein the roasting temperature is 300-500 ℃.
In the method, the t-ZrO2Can be prepared according to the following method: ZrO (NO)3)2Generating t-ZrO from mixed methanol solution of urea under methanol thermal condition2Precursor of t-ZrO2Precursor is in N2Roasting at 400 deg.c to obtain the product.
The invention provides a method for synthesizing itaconic acid by directly starting from citric acid. The method is characterized in that under the condition of hot water, a metal oxide catalyst is introduced to promote citric acid to generate a dehydration reaction to generate an aconitic acid intermediate, and aconitic acid is automatically decarboxylated in the hot water to generate itaconic acid. The invention has the following advantages: the raw material used in the invention is derived from biomass, and the solvent used is H2O in N2The reaction is carried out in the atmosphere, the reaction process is green, and byproducts harmful to the environment are not generated. The conversion rate of the citric acid is very high,92.2 percent and the itaconic acid yield reaches 70.2 percent. Has important application value.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
In the following examples, specific metal oxide catalysts were prepared as follows:
1.m-ZrO2preparation of
80mL ZrO (NO) was added to a 100mL stainless steel kettle with a Teflon liner3)2And urea, wherein the concentrations of metal ions and the urea are 0.2M and 3M respectively, and the ZrO is obtained by reacting in an oven at 140 ℃ for 24 hours under the pressure generated by a hydrothermal kettle2And (3) precursor. The solid precipitate obtained by the solvothermal method was thoroughly centrifuged with water, washed to neutrality and dried in an oven at 110 ℃ overnight. The dried sample was placed in a tube furnace and fired for 4h while maintaining an air flow rate of 40 mL/min. The calcination temperature is 300-500 deg.C, and specifically 300, 350, 400, 450, 500 deg.C.
2.t-ZrO2Preparation of
80mL ZrO (NO) was added to a 100mL stainless steel kettle with a Teflon liner3)2And urea, wherein the concentration of metal ions and the concentration of urea are 0.2M and 3M respectively, and the ZrO is obtained by reacting in an oven at 140 ℃ for 24 hours under the pressure generated by a hydrothermal kettle2And (3) precursor. The solid precipitate obtained by the solvothermal method was thoroughly centrifuged with methanol, washed to neutrality and dried in an oven at 110 ℃ overnight. The dried sample was placed in a tube furnace and fired for 4h while maintaining N2The flow rate was 40mL/min and the calcination temperature was 400 ℃.
3.m,t-ZrO2Preparation of
To a 250mL circle with a magnetic stirrer50mL of ZrO (NO) was added to the bottom flask3)2The aqueous solution (0.2M) and 50mL of an aqueous urea solution (2M) were reacted for 8 hours at room temperature with electromagnetic stirring (500rpm) to obtain ZrO2And (3) precursor. The resulting solid precipitate was thoroughly centrifuged with water, washed to neutrality and dried in an oven at 110 ℃ overnight. The dried sample was calcined at 400 ℃ for 4 hours in a tube furnace to obtain a catalyst while maintaining an air flow rate of 40 mL/min.
4.ZrxCe1-xO2Preparation of
To a 100mL stainless steel kettle with a Teflon liner was added 80mL ZrO (NO3)2、(NH4)2Ce(NO3)6And urea, wherein the concentrations of metal ions and the urea are 0.2M and 3M respectively, and the Zr is obtained by reacting in an oven at 140 ℃ for 24 hours under the pressure generated by a hydrothermal kettlexCe1-xO2And (3) precursor. The solid precipitate obtained by the solvothermal method was thoroughly centrifuged with water, washed to neutrality and dried in an oven at 110 ℃ overnight. The dried sample was placed in a tube furnace and fired for 4h while maintaining an air flow rate of 40 mL/min. The calcination temperature was 500 ℃.
In the following examples:
conversion ═ molar pre-reaction-molar post-reaction citric acid)/molar pre-reaction citric acid%
Selectivity is the molar amount of itaconic acid after reaction/(molar amount of citric acid before reaction-molar amount of citric acid after reaction) × 100%
Yield-conversion-selectivity/100%
Example 1 baking at 300 ℃ to obtain m-ZrO2The catalyst is exemplified for non-limiting illustration
To a polytetrafluoroethylene inner liner of a 50mL stainless steel autoclave equipped with a stirrer were added 1mmol of citric acid and 500mg of m-ZrO2Catalyst and 20mL of water in N2And sequentially inflating and deflating in the atmosphere, and inflating to 2MPa after circulating for three times. The temperature was raised to 180 ℃ with electromagnetic stirring (500 rpm). Naturally cooling to room temperature after the reaction is finished for 5h, carrying out reduced pressure suction filtration on the reaction mixture, separating the solid catalyst from the reaction liquid, and reactingThe reaction solution is subjected to volume fixing and then is analyzed by high performance liquid chromatography. And after being fully washed, the solid catalyst is dried in a vacuum oven at 60 ℃ overnight to carry out a recovery cycle experiment or characterization of the catalyst after reaction. The product analysis used high performance liquid chromatography (HPLC, Shimadzu LC-20A), the detector was a differential Refractive Index Detector (RID), the column was Shodex-SH1011, the mobile phase was 0.01M dilute sulfuric acid solution, the flow rate of the mobile phase was 1.0mL/min, and the column operating temperature was 50 ℃. Under these conditions, the citric acid conversion was 92.2%, the itaconic acid selectivity was 76.1%, and the yield was 70.2%.
Example 2 calcination of the obtained t-ZrO at 400 deg.C2The catalyst is exemplified for non-limiting illustration
To a polytetrafluoroethylene inner liner of a 50mL stainless steel autoclave equipped with a stirrer, 1mmol of citric acid and 300mg of t-ZrO were added2Catalyst and 20mL of water in N2And sequentially inflating and deflating in the atmosphere, and inflating to 2MPa after circulating for three times. The temperature was raised to 180 ℃ with electromagnetic stirring (500 rpm). And naturally cooling to room temperature after the reaction is finished for 3 hours, carrying out reduced pressure suction filtration on the reaction mixture, separating the solid catalyst from the reaction liquid, and carrying out high performance liquid chromatography analysis on the reaction liquid after constant volume. And after being fully washed, the solid catalyst is dried in a vacuum oven at 60 ℃ overnight to carry out a recovery cycle experiment or characterization of the catalyst after reaction. The product analysis used high performance liquid chromatography (HPLC, Shimadzu LC-20A), the detector was a differential Refractive Index Detector (RID), the column was Shodex-SH1011, the mobile phase was 0.01M dilute sulfuric acid solution, the flow rate of the mobile phase was 1.0mL/min, and the column operating temperature was 50 ℃. Under these conditions, the citric acid conversion was 16.5%, the itaconic acid selectivity was 85.7%, and the yield was 14.1%.
Example 3 with TiO2The catalyst is exemplified for non-limiting illustration
Adding 1mmol of citric acid and 300mg of TiO into a polytetrafluoroethylene lining of a 50mL stainless steel high-pressure reaction kettle with a stirrer2Catalyst and 20mL of water in N2And sequentially inflating and deflating in the atmosphere, and inflating to 2MPa after circulating for three times. The temperature was raised to 180 ℃ with electromagnetic stirring (500 rpm). After the reaction is finished for 3 hours, the mixture is naturally cooled to room temperature, and the reaction mixture is subjected to reduced pressure suction filtrationSeparating the solid catalyst from the reaction liquid, and analyzing the reaction liquid by high performance liquid chromatography after constant volume. And after being fully washed, the solid catalyst is dried in a vacuum oven at 60 ℃ overnight to carry out a recovery cycle experiment or characterization of the catalyst after reaction. The product analysis used high performance liquid chromatography (HPLC, Shimadzu LC-20A), the detector was a differential Refractive Index Detector (RID), the column was Shodex-SH1011, the mobile phase was 0.01M dilute sulfuric acid solution, the flow rate of the mobile phase was 1.0mL/min, and the column operating temperature was 50 ℃. Under these conditions, the citric acid conversion was 18.6%, the itaconic acid selectivity was 88.2%, and the yield was 16.4%.
Claims (7)
1. A process for the preparation of itaconic acid from citric acid comprising the steps of: under the action of a catalyst, citric acid is placed in water for reaction, and the itaconic acid is obtained after the reaction is finished;
the catalyst is selected from at least one of the following: powdered monoclinic phase ZrO2Tetragonal phase ZrO2Monoclinic tetragonal mixed crystal phase ZrO2、ZrxCe1-xO2、SnO2、TiO2、Nb2O5；
Wherein, ZrxCe1-xO2Wherein x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8 or 0.9.
2. The method of claim 1, wherein: the reaction temperature is 160-200 ℃; the reaction time is 1-5h, preferably 3 h; the reaction is carried out in N2And the reaction is carried out under an atmosphere.
3. The method according to claim 1 or 2, characterized in that: the dosage of the catalyst is 52-260% of the mass of the citric acid.
4. The method according to any one of claims 1-3, wherein: the concentration of citric acid in the reaction solution of the reaction is 0.01-0.1M.
5. The method according to any one of claims 1-4, wherein: the citric acid is at least one selected from citric acid monohydrate and citric acid anhydrous.
6. The method according to any one of claims 1-5, wherein: the m-ZrO2The preparation method comprises the following steps: ZrO (NO)3)2The mixed aqueous solution of the m-ZrO and the urea is generated under the hydrothermal condition2Precursor of m-ZrO2The precursor is obtained by roasting, and the roasting temperature is 300-500 ℃.
7. The method according to any one of claims 1-5, wherein: the t-ZrO2Can be prepared according to the following method: ZrO (NO)3)2Generating t-ZrO from mixed methanol solution of urea under methanol thermal condition2Precursor of t-ZrO2Precursor is in N2Roasting at 400 deg.c to obtain the product.
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| CN1327973A (en) * | 2000-06-14 | 2001-12-26 | 中国科学院上海药物研究所 | Process for fully synthesizing shaerweixin as novel antineoplastic |
| US20170044320A1 (en) * | 2014-04-25 | 2017-02-16 | Polyone Corporation | Aliphatic polyimides from a 1:1 molar ratio of diamine and unsaturated monoanhydride or unsaturated diacid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327973A (en) * | 2000-06-14 | 2001-12-26 | 中国科学院上海药物研究所 | Process for fully synthesizing shaerweixin as novel antineoplastic |
| US20170044320A1 (en) * | 2014-04-25 | 2017-02-16 | Polyone Corporation | Aliphatic polyimides from a 1:1 molar ratio of diamine and unsaturated monoanhydride or unsaturated diacid |
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| KHAN, SYAMANTAK ET AL: "Small molecular organic nanocrystals resemble carbon nanodots in terms of their properties", 《CHEMICAL SCIENCE》 * |
| LI, ZHAOWEI ET AL: "Efficient conversion of bio-renewable citric acid to high-value carboxylic acids on stable solid catalysts", 《GREEN CHEMISTRY》 * |
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