CN112979447B - Preparation method of fumaric acid - Google Patents
Preparation method of fumaric acid Download PDFInfo
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- CN112979447B CN112979447B CN201911286268.5A CN201911286268A CN112979447B CN 112979447 B CN112979447 B CN 112979447B CN 201911286268 A CN201911286268 A CN 201911286268A CN 112979447 B CN112979447 B CN 112979447B
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Abstract
The application discloses a preparation method of fumaric acid, which takes malic acid as a raw material, and the malic acid is catalyzed to carry out dehydration reaction under the condition of no solvent or in a hydrocarbon medium to obtain the fumaric acid. The preparation method has simple and direct reaction process, and the key raw material malic acid can be obtained by biomass fermentation, which is a supplement to the existing production route to relieve the dependence on fossil resources. In addition, compared with the traditional production method of fumaric acid, the method avoids the use of high-pollution catalysts such as thiourea, bromine-containing oxides and the like, and the dehydration reaction can be carried out under the normal pressure condition, thus being green and safe. The used catalyst and the reaction process thereof are efficient and clean.
Description
Technical Field
The application belongs to the field of chemistry and chemical engineering, relates to a preparation method of fumaric acid, and particularly relates to a method for preparing fumaric acid by taking malic acid as a raw material.
Background
Fumaric acid (Fumaric acid), also known as Fumaric acid and Fumaric acid, is an important organic chemical raw material and a fine chemical product, is widely used in the fields of coatings, synthetic resins, synthetic medicines, plasticizers and the like, and can be used as a food additive and a feed additive. Industrially, fumaric acid is produced mainly by using benzene or butylene as raw material, and through catalytic oxidation to produce maleic acid (or maleic anhydride), and double bond isomerization. The commonly used isomerization catalysts at present comprise thiourea, NH4Br, LiBr and KBr-H2O2Hydrochloric acid, bromine-containing oxidizing agents, and the like. But do notThe above catalyst has obvious disadvantages, wherein the thiourea catalyst is easily decomposed by heating to release toxic gases such as oxides of nitrogen and sulfur, and the thiourea catalyst is also contained in the reaction liquid, so that environmental pollution is caused; when the bromine-containing oxidant and strong acid are used as catalysts, the corrosion to equipment is serious in the production process, the iron content and the chromaticity of the product are unqualified, the product needs alkali washing, the discharge amount of waste water is large, and the recycling cost is increased. In view of the above disadvantages and drawbacks of the production methods, development of a novel, green fumaric acid production route is urgently required.
Malic acid (DL-Malic acid, Malic acid) is an important natural organic acid, widely distributed in plant, animal and microbial cells. Malic acid as a biomass platform molecule can be obtained in large quantities by microbial fermentation of biomass raw materials (straw, corncob, starch, sucrose, glucose, etc.). The existing functional groups in the biomass derivatives are fully utilized, and the further preparation of important chemicals is an important way for utilizing biomass resources, is favorable for getting rid of the dependence on stone resources such as petroleum and the like, and meets the requirements of sustainable development of human society. CN 103159624A discloses a new route for converting malic acid into malonic diester in one step by coupling esterification and oxidation reactions, wherein malic acid is used as a raw material, oxygen or air is used as an oxygen source, alcohol is used as a solvent, and a vanadium oxide compound is used as a catalyst. Although this route is green and efficient, one carbon atom is lost. By comparing the molecular structures of fumaric acid and malic acid, the structures of the fumaric acid and the malic acid are similar, and fumaric acid can be obtained by removing one molecule of water from the malic acid, so that the malic acid has high carbon atom economy. However, studies on the synthesis of fumaric acid from malic acid as a raw material have been reported in the literature.
Disclosure of Invention
The invention discloses a process for efficiently preparing fumaric acid by taking heteropoly acid, acidic metal oxide, molecular sieve and the like as catalysts and carrying out dehydration reaction on malic acid under the solvent-free condition or in a hydrocarbon medium. The reaction process of the industrial production route of fumaric acid and the preparation of fumaric acid by malic acid proposed by the invention is shown as follows.
The invention discloses a preparation method of fumaric acid, which takes malic acid as a raw material, and the malic acid is subjected to catalytic dehydration reaction under the solvent-free condition or in a hydrocarbon medium to obtain the fumaric acid.
In a preferred embodiment, the malic acid is subjected to a dehydration reaction in the presence of a catalyst; the catalyst is an acid catalyst; the acid catalyst includes at least one of a heteropolyacid, an acidic metal oxide and a molecular sieve.
In a preferred embodiment, the heteropolyacid comprises at least one of silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, phosphomolybdovanadophosphoric acid, niobium molybdovanadophosphoric acid and tantalum molybdovanadophoric acid.
In a preferred embodiment, the acidic metal oxide comprises at least one of alumina, zinc oxide, zirconia, lanthana, and ceria.
In a preferred embodiment, the molecular sieve comprises at least one of a protonated type A molecular sieve, a type X molecular sieve, a type Y molecular sieve, a beta molecular sieve, mordenite, ZSM-5, ZSM-22, ZSM-23, SAPO-11, and SAPO-34.
In a preferred embodiment, the amount of the catalyst is 0.1-30 wt% of the substrate malic acid by mass percent; preferably, the dosage of the catalyst is 0.5-20 wt% of the substrate malic acid feeding; more preferably, the dosage of the catalyst is 1.0-10 wt% of the substrate malic acid feeding.
In a preferred embodiment, the hydrocarbon medium comprises aliphatic hydrocarbons and aromatic hydrocarbons.
In a preferred embodiment, the aliphatic hydrocarbon comprises at least one of hexane, heptane, octane, nonane, decane, the aliphatic hydrocarbon being a linear or branched alkane; the aromatic hydrocarbon includes at least one of toluene, ethylbenzene, ortho-xylene, meta-xylene, and para-xylene.
In a preferred embodiment, the mass ratio of the malic acid to the reaction medium is 0.5 to 50 wt%; preferably 5 to 40 wt%; more preferably 10 to 30 wt%.
The reaction medium is a hydrocarbon medium.
In a preferred embodiment, the dehydration reaction temperature is 50-280 ℃; preferably, the dehydration reaction temperature is 100-250 ℃; more preferably, the dehydration reaction temperature is 150-200 ℃.
In a preferred embodiment, the dehydration reaction time is 0.1-24 h; preferably, the dehydration reaction time is 0.5-10 h; more preferably, the dehydration reaction time is 1-6 h.
The beneficial effects that this application can produce include:
1) the novel method for preparing the fumaric acid by using the DL-malic acid as the raw material through the catalytic dehydration reaction has the advantages that the reaction process is simple, and the key raw material malic acid can be obtained by fermenting biomass; the invention relates to a route for preparing important chemical fumaric acid by using biomass resources, which is a supplement to the existing production route so as to relieve the dependence on fossil resources.
2) The invention is green and environment-friendly. Compared with the traditional production method of fumaric acid, the method avoids the use of high-pollution catalysts such as thiourea, bromine-containing oxides and the like, and the dehydration reaction can be carried out under the normal pressure condition, thus being green and safe. The used catalyst and the reaction process thereof are efficient and clean.
Drawings
FIG. 1 shows malic acid dehydration reaction product1H NMR spectrum.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The invention aims to provide a novel method for directly producing fumaric acid from DL-malic acid, wherein the raw material malic acid can be obtained from biomass raw materials in a large amount by a fermentation method; the fumaric acid prepared by catalyzing the dehydration of the malic acid is a new reaction route, the reaction route avoids the use of high-pollution catalysts such as thiourea, bromine-containing oxides and the like, and the reaction steps are shortened.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
under the condition of no solvent or in hydrocarbon medium, adding catalyst such as heteropoly acid, acidic metal oxide, molecular sieve and malic acid as substrate, and under the condition of keeping a certain reaction temperature in nitrogen atmosphere, the malic acid is subjected to dehydration reaction, the main product is fumaric acid, and simultaneously a very small amount of maleic acid is generated.
The specific process method comprises the following steps: adding no solvent or added medium such as aliphatic hydrocarbon or aromatic hydrocarbon into a high-pressure reaction kettle with a polytetrafluoroethylene lining, and sequentially adding a reaction raw material DL-malic acid and a catalyst heteropoly acid, an acidic metal oxide or a molecular sieve, wherein the mass ratio of the malic acid to the reaction medium is 0.5-50 wt%, and the dosage of the catalyst is 0.1-30 wt% of the added substrate malic acid; under the atmosphere of nitrogen, the reaction temperature is controlled to be 50-280 ℃, the reaction time is 0.1-24 hours, the main product is fumaric acid, and a small amount of maleic acid is byproduct. By optimizing the process conditions, the conversion rate of the malic acid can reach more than 99 percent, and the selectivity of the fumaric acid can reach more than 98 percent.
The fumaric acid obtained by the dehydration reaction of the malic acid under the action of the acid catalyst can be carried out in a glass reaction tube, an autoclave and the like. The examples of the present invention were subjected to performance evaluation and process condition test in an autoclave, but are not limited to the autoclave.
The aliphatic hydrocarbon reaction medium is one or more of hexane, heptane, octane, nonane and decane, wherein the aliphatic hydrocarbon can be straight-chain alkane or branched-chain alkane and the like; the aromatic hydrocarbon comprises one or more of toluene, ethylbenzene, o-xylene, m-xylene, p-xylene and the like; the mass ratio of the raw material malic acid to the reaction medium such as aliphatic hydrocarbon or aromatic hydrocarbon is 0.5-50 wt%, preferably 5-40 wt%, and most preferably 10-30 wt%.
The malic acid dehydration catalyst is at least one of heteropoly acid (silicotungstic acid, phosphotungstic acid, phosphomolybdic acid, phosphomolybdovanadophosphoric acid, niobium-molybdenum heteropoly acid and tantalum-molybdenum heteropoly acid), acidic metal oxide (aluminum oxide, zinc oxide, zirconium oxide, lanthanum oxide and cerium oxide) and molecular sieve (A type molecular sieve, X type molecular sieve, Y type molecular sieve, beta-molecular sieve, mordenite, ZSM-5, ZSM-22, ZSM-23, SAPO-11 and SAPO-34). The amount of the catalyst is 0.1-30 wt%, preferably 0.5-20 wt%, and most preferably 1-10 wt%, based on the mass percentage of the catalyst and the malic acid.
In the process conditions of the invention, the dehydration reaction temperature of the malic acid is 50-280 ℃, preferably 100-250 ℃, and most preferably 150-200 ℃; the dehydration reaction time of the malic acid is 0.1-24h, preferably 0.5-10h, and most preferably 1-6 h.
EXAMPLE 1 dehydration of malic acid in different reaction media in the absence of solvent
This example studies the performance of malic acid dehydration in different reaction media without solvent and without additional catalyst. Since the dehydration reaction is facilitated in the nonpolar medium, the reaction medium in the present invention is concentrated on nonpolar aliphatic hydrocarbons or aromatic hydrocarbons, etc. Malic acid and products of maleic acid and fumaric acid are insoluble in a nonpolar medium at room temperature, the melting point of the malic acid is about 130 ℃, and the malic acid is gradually melted at the reaction temperature; the melted malic acid has acidity, can be subjected to autocatalytic dehydration reaction, and after the reaction is finished and cooled to room temperature, the unreacted malic acid, the products maleic acid and fumaric acid directly exist in a solid form. And (3) carrying out qualitative analysis on the product by adopting a nuclear magnetic resonance technology. The conversion rate of malic acid and the selectivity of maleic acid and fumaric acid were quantitatively determined by high performance liquid chromatography. High performance liquid chromatography: waters e2695, UV-detector (2489, Waters); a chromatographic column: SunAire C18 column,5 μm,4.6 mm. times.150 mm; chromatographic analysis conditions: ultraviolet detection wavelength, 210nm, mobile phase: 0.1 wt% H3PO4Aqueous solution/CH3OH-80/20 (ultrasonic degassing), mobile phase flow rate: 0.5ml/min, sample size: 5 μ L, column temperature: 35 ℃ is carried out.
1.34g of malic acid is added into an autoclave with a polytetrafluoroethylene lining, the mass ratio of the malic acid to the reaction medium is 10 wt% under the condition of no solvent or a proper amount of the reaction medium is added, the temperature is raised to 150 ℃ by adopting an electric heating mode under the atmosphere of nitrogen, and the reaction is carried out for 2 hours under the magnetic stirring of 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, filtering and removing the reaction medium (reacting under the condition of no solvent)Direct vacuum drying), washing the obtained reaction solid with cyclohexane for several times, and vacuum drying overnight at 50 ℃ to obtain the total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and treated with deuterated dimethyl sulfoxide (DMSO-d)6) Dissolving, and performing qualitative analysis on the reaction product by nuclear magnetic resonance (nuclear magnetic spectrum is shown in FIG. 1). Accurately measure 0.20g of the reaction sample (denoted as m)sample) Dissolving the reaction sample in a 25mL volumetric flask by using a mobile phase, diluting, fixing the volume, carrying out quantitative analysis by using HPLC (high performance liquid chromatography), and recording the mass of the reactants and the product m detected by chromatographic analysisdetectedMass m of each substance after reactioni＝mdetected×(mtotal/msample). The conversion rate of malic acid and the selectivity of the product were calculated based on the following formulas:
the results of the dehydration reaction of malic acid in the absence of solvent and in different reaction media are shown in Table 1. In the absence of an additional catalyst, after dehydration reaction is carried out for 2 hours at 150 ℃, the conversion rate of malic acid is 20.5 percent, and the selectivity of fumaric acid is 97.0 percent; when the catalyst is reacted in an n-octane medium under the same conditions, the conversion rate of malic acid is 28.6 percent, and the selectivity of fumaric acid is 99.0 percent.
TABLE 1 results of dehydration of malic acid in the absence of solvent and in different reaction media
aOthers include the formation of polymerization products and unknown by-products, among others.
EXAMPLE 2 Effect of reaction temperature on dehydration of malic acid in the absence of solvent
This example investigated the use of a solvent-free solventAnd under the condition of no additional catalyst, the reaction temperature has influence on the dehydration reaction of the malic acid. The product was qualitatively and quantitatively analyzed by the analytical method in example 1. 1.34g of malic acid is added into an autoclave with a polytetrafluoroethylene lining, the temperature is raised to 150 ℃ by adopting an electric heating mode under the atmosphere of nitrogen, and the reaction is carried out for 2 hours under the magnetic stirring of 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, and vacuum drying at 50 ℃ overnight to obtain the total mass m of the sampletotalWeighing 0.10g of sample in a nuclear magnetic tube, and using DMSO-d6Dissolving, and qualitatively analyzing the reaction product by nuclear magnetic resonance. Accurately measure 0.20g of the reaction sample (denoted as m)sample) The reaction sample was dissolved in a 25mL volumetric flask with the mobile phase, diluted, and subjected to volume fixing and quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results of the dehydration reaction of malic acid at different temperatures are shown in Table 2. Under the conditions of no solvent and no additional catalyst, after the reaction is carried out for 2 hours at 200 ℃, the conversion rate of malic acid is 53.1 percent, and the selectivity of fumaric acid is 97.6 percent; when the reaction temperature was increased to 220 ℃, the malic acid conversion increased to 60.3%, whereas the selectivity for fumaric acid decreased to 93.5%.
TABLE 2 results of malic acid dehydration reaction in the absence of solvent at different reaction temperatures
aOthers include the formation of polymerization products and unknown by-products, among others.
EXAMPLE 3 Effect of reaction time on dehydration of malic acid in the absence of solvent
This example investigated the effect of reaction time on dehydration of malic acid in the absence of a solvent and in the absence of an added catalyst. The product was qualitatively and quantitatively analyzed by the analytical method in example 1.
Adding 1.34g of malic acid into an autoclave with a polytetrafluoroethylene lining, heating to 200 ℃ by adopting an electric heating mode under the atmosphere of nitrogen, and reacting under magnetic stirring at 1000rpm1-6 h. Stopping stirring, naturally cooling the reaction kettle to room temperature, and vacuum drying at 50 ℃ overnight to obtain the total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and DMSO-d is used6Dissolving, and qualitatively analyzing the reaction product by nuclear magnetism. Accurately measure 0.20g of the reaction sample (denoted as m)sample) The reaction sample was dissolved in a 25mL volumetric flask with the mobile phase, diluted, and subjected to volume fixing and quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results of the dehydration reaction of malic acid at different reaction times are shown in Table 3. Under the conditions of no solvent and no additional catalyst, after the reaction is carried out for 4 hours at 200 ℃, the conversion rate of malic acid is 66.1 percent, and the selectivity of fumaric acid is 97.5 percent; when the reaction time was extended to 6h, the malic acid conversion increased to 71.5%, whereas the selectivity to fumaric acid decreased to 95.1%.
TABLE 3 influence of reaction time on malic acid dehydration reaction results under solvent-free conditions
aOthers include the formation of polymerization products and unknown by-products, among others.
Example 4 evaluation of the Performance of the heteropolyacid catalyst for dehydration reaction of malic acid
This example studies the performance of heteropolyacids to catalyze the dehydration reaction of malic acid. By using1And (2) performing qualitative and quantitative analysis on the reaction product by using H NMR and HPLC methods respectively, wherein different from the example 1, after removing a reaction medium by filtering, completely dissolving a solid sample by using ethyl acetate, separating and removing the catalyst to obtain a sample solution, removing the solvent ethyl acetate by rotary evaporation, and performing vacuum drying to obtain the reaction sample.
1.34g of malic acid, 13.4g of n-octane medium (malic acid reacts with) are introduced into an autoclave with a polytetrafluoroethylene liningThe mass ratio of the medium is 10 wt%), and 1 wt% of heteropolyacid catalyst calculated according to the mass fraction of malic acid, and the reaction is carried out for 2 hours under the nitrogen atmosphere by adopting an electric heating mode to heat to 150 ℃ and magnetic stirring at 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, filtering to remove a reaction medium, washing a solid sample for a plurality of times by using cyclohexane, completely dissolving the sample by using ethyl acetate, filtering to remove a solid catalyst, performing rotary evaporation to remove ethyl acetate, and performing vacuum drying at 50 ℃ overnight to obtain the total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and washed with (DMSO-d)6Dissolving, and qualitatively analyzing the reaction product by nuclear magnetic resonance. Accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results of the evaluation of the heteropoly acid catalyst are shown in Table 4. In an n-octane medium, under the catalysis of niobium-molybdenum heteropoly acid, malic acid reacts for 2 hours at 150 ℃, the conversion rate is 43.6 percent, and the selectivity of fumaric acid is 98.5 percent.
TABLE 4 results of dehydration reaction of malic acid catalyzed by heteropoly acid
aOthers include the formation of polymerization products and unknown by-products, among others.
Example 5 evaluation of the Performance of an acidic Metal oxide catalyst for dehydration of malic acid
This example investigates the performance of acidic metal oxides to catalyze the dehydration reaction of malic acid. By using1And (2) performing qualitative and quantitative analysis on the reaction product by using H NMR and HPLC methods respectively, wherein different from the example 1, after removing a reaction medium by filtering, completely dissolving a solid sample by using ethyl acetate, separating and removing the catalyst to obtain a sample solution, removing the solvent ethyl acetate by rotary evaporation, and performing vacuum drying to obtain the reaction sample.
1.34g of a polytetrafluoroethylene-lined autoclave were charged in successionMalic acid, 13.4g of n-octane medium (the mass ratio of the malic acid to the solvent is 10 wt%), and 1 wt% of acidic metal oxide catalyst calculated according to the mass fraction of the malic acid, wherein the malic acid is heated to 150 ℃ by adopting an electric heating mode in a nitrogen atmosphere, and the malic acid is reacted for 2 hours under magnetic stirring at 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, filtering to remove a reaction medium, washing a solid sample for a plurality of times by using cyclohexane, completely dissolving the sample by using ethyl acetate, filtering to remove a solid catalyst, performing rotary evaporation to remove ethyl acetate, and performing vacuum drying at 50 ℃ overnight to obtain the total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and DMSO-d is used6Dissolving, and qualitatively analyzing the reaction product by nuclear magnetic resonance. Accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results of evaluation of the acidic metal oxide catalyst are shown in Table 5. In an n-octane medium, under the catalysis of zirconia, after malic acid reacts for 2 hours at 150 ℃, the conversion rate is 35.4 percent, and the selectivity of fumaric acid is 98.0 percent.
TABLE 5 results of acid metal oxide catalyzed malic acid dehydration reaction
aOthers include double bond products formed and unknown by-products, among others.
Example 6 evaluation of Performance of molecular sieve-based catalyst for dehydration reaction of malic acid
This example studies the performance of various molecular sieves in catalyzing the dehydration reaction of malic acid. By using1And (2) performing qualitative and quantitative analysis on the reaction product by using H NMR and HPLC methods respectively, wherein different from the example 1, after removing a reaction medium by filtering, completely dissolving a solid sample by using ethyl acetate, separating and removing the catalyst to obtain a sample solution, removing the solvent ethyl acetate by rotary evaporation, and performing vacuum drying to obtain the reaction sample.
At the belt with1.34g of malic acid, 13.4g of n-octane medium (the mass ratio of the malic acid to the solvent is 10 wt%) and 1 wt% of acidic metal oxide catalyst calculated according to the mass fraction of the malic acid are sequentially added into a polytetrafluoroethylene-lined autoclave, and the mixture is heated to 150 ℃ by adopting an electric heating mode under the atmosphere of nitrogen, and is magnetically stirred at 1000rpm for reaction for 2 hours. Stopping stirring, naturally cooling the reaction kettle to room temperature, filtering to remove a reaction medium, washing a solid sample for a plurality of times by using cyclohexane, completely dissolving the sample by using ethyl acetate, filtering to remove a solid catalyst, performing rotary evaporation to remove ethyl acetate, and performing vacuum drying at 50 ℃ overnight to obtain the total mass m of the sampletotalWeighing 0.10g of sample in a nuclear magnetic tube, and using DMSO-d6Dissolving, and qualitatively analyzing the reaction product by nuclear magnetism. Accurately weighed 0.20g of the reaction sample (m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results of evaluation of the molecular sieve-based catalyst are shown in Table 6. In an n-octane medium, under the catalysis of HZSM-5, after malic acid reacts for 2 hours at 150 ℃, the conversion rate is 46.9 percent, and the selectivity of fumaric acid is 98.3 percent.
TABLE 6 results of malic acid dehydration catalyzed by different molecular sieves
aOthers include double bond products formed and unknown by-products, among others.
EXAMPLE 7 Effect of the amount of catalyst H-Beta on the dehydration reaction
This example investigates the effect of the amount of catalyst H-Beta used on the dehydration reaction in an n-octane reaction medium. By using1The qualitative and quantitative analysis of the reaction products was carried out by H NMR and HPLC methods, respectively, in which, in contrast to example 1, the removal by filtrationAfter the reaction medium is reacted, the solid sample is completely dissolved by utilizing ethyl acetate, the catalyst is separated and removed to obtain a sample solution, the solvent ethyl acetate is removed by rotary evaporation, and then the reaction sample is obtained by vacuum drying.
1.34g of malic acid, 13.4g of n-octane medium (the mass ratio of the malic acid to the reaction medium is 10 wt%) and a certain amount of H-Beta catalyst calculated according to the mass fraction of the malic acid are sequentially added into an autoclave with a polytetrafluoroethylene lining, and the mixture is heated to 150 ℃ by adopting an electric heating mode under the atmosphere of nitrogen, and is magnetically stirred at 1000rpm for reaction for 2 hours. Stopping stirring, naturally cooling the reaction kettle to room temperature, filtering to remove reaction medium, washing the solid with cyclohexane for several times, completely dissolving the sample with ethyl acetate, filtering to remove solid catalyst to obtain sample solution, removing ethyl acetate by rotary evaporation, and vacuum drying at 50 ℃ overnight to obtain the total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and DMSO-d is used6Dissolving, and qualitatively analyzing the reaction product by nuclear magnetism. Accurately weighed 0.20g of the reaction sample (m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The reaction results of different feeding ratios of H-Beta and malic acid are shown in Table 7. In an n-octane medium, when the dosage of the catalyst H-Beta is 4wt% of the substrate feeding, after malic acid reacts for 2 hours at 150 ℃, the conversion rate is 59.3%, and the selectivity of fumaric acid is 98.3%.
TABLE 7 reaction results of different feeding ratios of catalyst H-Beta and raw material malic acid
aOthers include double bond products formed and unknown by-products, among others.
EXAMPLE 8 Effect of the feed ratio of malic acid as raw Material to the reaction Medium on the dehydration reaction
This example investigates the effect of the charge of substrate malic acid on the dehydration reaction in an n-octane reaction medium. By using1And (2) performing qualitative and quantitative analysis on the reaction product by using H NMR and HPLC methods respectively, wherein different from the example 1, after removing a reaction medium by filtering, completely dissolving a solid sample by using ethyl acetate, separating and removing the catalyst to obtain a sample solution, removing the solvent ethyl acetate by rotary evaporation, and performing vacuum drying to obtain the reaction sample.
Sequentially adding a certain amount of malic acid, 13.4g of n-octane medium and 4wt% of H-Beta catalyst calculated according to the mass fraction of the malic acid into an autoclave with a polytetrafluoroethylene lining, heating to 150 ℃ by adopting an electric heating mode under the atmosphere of nitrogen, and reacting for 2 hours under the magnetic stirring of 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, filtering to remove reaction medium, washing the solid with cyclohexane for several times, completely dissolving the sample with ethyl acetate, filtering to remove solid catalyst to obtain sample solution, removing ethyl acetate by rotary evaporation, and vacuum drying at 50 ℃ overnight to obtain the total mass m of the sampletotalWeighing a certain amount of sample in a nuclear magnetic tube, and using DMSO-d6Dissolving, and qualitatively analyzing the reaction product by nuclear magnetism. Accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The reaction results of different feed amounts of malic acid are shown in Table 8. When the feeding amount of the substrate is 15wt% of the normal octane and the reaction is carried out for 2 hours at 150 ℃, the conversion rate of malic acid is 59.2 percent, and the selectivity of fumaric acid is 98.6 percent.
TABLE 8 reaction results of malic acid with reaction Medium in different feed ratios
aOthers include the formation of polymerization products and unknown by-products, among others.
Example 9 Effect of reaction temperature on H-Beta catalyzed malic acid dehydration reaction
This example investigated the effect of reaction temperature on malic acid dehydration reaction under H-Beta catalysis. The qualitative and quantitative analysis of the product was carried out by the analytical methods of example 1 and example 4.
2.01g of malic acid, 13.4g of n-octane medium (the mass ratio of the malic acid to the reaction medium is 15 wt%) and 4wt% of H-Beta catalyst calculated according to the mass fraction of the malic acid are sequentially added into an autoclave with a polytetrafluoroethylene lining, the temperature is raised to the specified reaction temperature by adopting an electric heating mode under the atmosphere of nitrogen, and the reaction is carried out for 2 hours under the magnetic stirring of 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, filtering to remove reaction medium, washing the solid with cyclohexane for several times, completely dissolving the sample with ethyl acetate, filtering to remove solid catalyst to obtain sample solution, removing ethyl acetate by rotary evaporation, and vacuum drying at 50 ℃ overnight to obtain the total mass m of the sampletotalWeighing a certain amount of sample in a nuclear magnetic tube, and using DMSO-d6Dissolving, and qualitatively analyzing the reaction product by nuclear magnetism. Accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results at different reaction temperatures are shown in table 9. In an n-octane medium, when the dosage of the catalyst H-Beta is 4wt% of the substrate feeding, after malic acid reacts for 2 hours at 200 ℃, the conversion rate is 78.8%, and the selectivity of fumaric acid is 98.2%.
TABLE 9 results of H-Beta catalyzed malic acid dehydration reaction at different reaction temperatures
aOthers include the formation of polymerization products and unknown by-products, among others.
Example 10 Effect of reaction time on H-Beta catalyzed malic acid dehydration reaction
This example investigated the effect of reaction time on dehydration of malic acid under H-Beta catalysis. The qualitative and quantitative analysis of the product was carried out using the analytical methods of example 1 and example 4.
2.01g of malic acid, 13.4g of n-octane medium (the mass ratio of the malic acid to the reaction medium is 15 wt%) and 4wt% of H-Beta catalyst calculated according to the mass fraction of the malic acid are sequentially added into an autoclave with a polytetrafluoroethylene lining, and the mixture is heated to 200 ℃ by adopting an electric heating mode under the atmosphere of nitrogen, and reacts for 1 to 6 hours under magnetic stirring at 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, filtering to remove reaction medium, washing the solid with cyclohexane for several times, completely dissolving the sample with ethyl acetate, filtering to remove solid catalyst to obtain sample solution, removing ethyl acetate by rotary evaporation, and vacuum drying at 50 ℃ overnight to obtain the total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and DMSO-d is used6Dissolving, and qualitatively analyzing the reaction product by nuclear magnetic resonance. Accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The results at different reaction times are shown in Table 10. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. In an n-octane medium, when the dosage of the catalyst H-Beta is 4wt% of the substrate feeding, after malic acid reacts for 5 hours at 200 ℃, the conversion rate is 99.3%, and the selectivity of fumaric acid is 98.4%.
TABLE 10 results of H-Beta catalyzed malic acid dehydration at different reaction times
aOthers include the formation of polymerization products and unknown by-products, among others.
From the above examples, it can be seen that the preparation method of fumaric acid provided by the present invention uses malic acid as a raw material, and uses heteropolyacid, acidic metal oxide, molecular sieve, etc. as catalysts under a solvent-free condition or in an aliphatic hydrocarbon or aromatic hydrocarbon reaction medium, and the malic acid is subjected to a high-efficiency catalytic dehydration reaction to obtain fumaric acid, and when the conversion rate of the malic acid is above 99%, the selectivity of the fumaric acid exceeds 98%. The raw material malic acid in the method is derived from renewable and environment-friendly biomass, so that the dependence on petroleum resources can be reduced; the reaction process is simple, the conditions are mild, the fumaric acid is obtained with high yield, and the reaction process has high atom economy and is a competitive technical route.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (1)
1. The preparation method of the fumaric acid is characterized in that malic acid is used as a raw material, and the malic acid is subjected to catalytic dehydration reaction in n-octane to obtain the fumaric acid;
the malic acid is subjected to dehydration reaction in the presence of an H-Beta catalyst;
based on the mass percentage of the malic acid, the using amount of the H-Beta catalyst is 4wt% of the malic acid feed as a substrate;
the mass ratio of the malic acid to the n-octane is 15 wt%;
the dehydration reaction temperature is 200 DEG CoAnd C, the dehydration reaction time is 4 h.
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Non-Patent Citations (4)
| Title |
|---|
| Jennifer J. Lee等.Upgrading malic acid to bio-based benzoates via a Diels-Alder-initiated sequence with the methyl coumalate platform.《RSC Advances》.2014,第4卷(第86期), * |
| Production of Plant Phthalate and its Hydrogenated Derivative from Bio-Based Platform Chemicals;Rui Lu等;《ChemSusChem》;20180425;第11卷(第10期);第1621-1627页+ Supporting Information第1-5页+第13-14页 * |
| Thermal Reactions of Malic Acid Benzylamine Salts;T.MUNEGUMI等;《Asian Journal of Chemistry 》;20131231;第25卷(第13期);第7451-7456页 * |
| Upgrading malic acid to bio-based benzoates via a Diels-Alder-initiated sequence with the methyl coumalate platform;Jennifer J. Lee等;《RSC Advances》;20140915;第4卷(第86期);第45657-45664页+ Supporting Information第S1-S3页 * |
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