CN117658793A - Technological method for preparing succinic acid by aqueous phase hydrogenation of maleic anhydride - Google Patents
Technological method for preparing succinic acid by aqueous phase hydrogenation of maleic anhydride Download PDFInfo
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- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 111
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 55
- 239000001384 succinic acid Substances 0.000 title claims abstract description 50
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 129
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011949 solid catalyst Substances 0.000 claims abstract description 24
- 238000002425 crystallisation Methods 0.000 claims abstract description 18
- 230000008025 crystallization Effects 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 238000009835 boiling Methods 0.000 claims abstract description 15
- 239000007789 gas Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 6
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 30
- 230000008569 process Effects 0.000 claims description 24
- 238000006460 hydrolysis reaction Methods 0.000 claims description 23
- 230000007062 hydrolysis Effects 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
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- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 27
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 229940014800 succinic anhydride Drugs 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- -1 polybutylene succinate Polymers 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
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- 239000002638 heterogeneous catalyst Substances 0.000 description 3
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- 229920002961 polybutylene succinate Polymers 0.000 description 3
- 239000004631 polybutylene succinate Substances 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A technological method for preparing succinic acid by aqueous phase hydrogenation of maleic anhydride hydrolyzes maleic anhydride with concentration of 10-75wt%, and hydrogen is introduced into a hydrogenation reaction kettle, the top of the hydrogenation reaction kettle is provided with a gas outlet, and a solid catalyst is fixed in the hydrogenation reaction kettle to catalyze maleic anhydride hydrogenation reaction; in the reaction process, the reaction pressure is regulated to keep the reaction temperature at 40-180 ℃, water in the reaction system is kept in a boiling state by regulating the pressure, water vapor and unreacted hydrogen are continuously discharged from a gas outlet, and after the reaction is finished, the reaction product is subjected to solid-liquid separation and/or crystallization separation to obtain succinic acid crystals. The invention takes the aqueous solution of maleic anhydride as the raw material, and the water in the reaction system is kept in a boiling state by utilizing the adjustment of pressure, so that the heat of the reaction system can be taken out in time by utilizing the water phase change, the problem of temperature rise of the technology for preparing succinic acid by hydrogenating maleic anhydride is well solved, and the method is simple and easy to operate and is convenient for industrial popularization and application.
Description
Technical Field
The invention relates to the technical field of succinic acid preparation by maleic anhydride hydrogenation, in particular to a process method for preparing succinic acid by aqueous phase hydrogenation.
Background
As the problem of plastic contamination increases, the demand for PBS (polybutylene succinate) series copolyesters has increased due to their excellent properties of degradable materials. However, although the polymerization technology of PBS series copolyester degradable plastic products is mature, the synthesis technology of large-scale low-cost succinic acid monomer materials is not complete, and the popularization and application of high-quality degradable materials are restricted.
The currently mainstream production processes of succinic acid mainly comprise three methods of biological fermentation, maleic anhydride electrolysis and direct maleic anhydride hydrogenation. The first two methods have low yield, high energy consumption, large pollution and defects in mass production. The direct hydrogenation method of maleic anhydride, which is focused by current researchers, is considered as the most promising method for industrially producing succinic acid in the future due to the simple process and low cost.
However, the reaction for generating succinic anhydride by maleic anhydride catalytic hydrogenation is double bond saturation reaction, so that the reaction is easy to carry out, and meanwhile, the reaction is highly exothermic (delta H= -128 KJ/mol), so that the temperature rise of the maleic anhydride hydrogenation reaction is large. In addition, various unsaturated bonds such as C=C and C=O exist in the direct hydrogenation reaction of maleic anhydride, the reaction temperature sensitivity is high, and if the temperature is increased in the hydrogenation reaction of maleic anhydride, the saturation of C=O double bonds is very easy to occur, and by-products such as butyrolactone and the like are generated, so that the reaction effect is influenced.
Because of the intense heat generated by the hydrogenation of maleic anhydride, different methods have been used by current researchers to solve this problem, and thus the smooth progress of the reaction has been achieved. In patent CN103570650a, a mixed solution of an organic solvent and maleic anhydride is used as a raw material, heterogeneous catalysts such as silicon-aluminum are used, a two-stage reactor reaction method is adopted, the first-stage reactor is used for pre-hydrogenation, the reaction heat generation is reduced, and the two-stage reactor is used for realizing the conversion of high selectivity and high conversion rate of maleic anhydride hydrogenation. Rectifying and separating the generated reaction product, recycling the solvent, and hydrolyzing and crystallizing the separated succinic anhydride to generate succinic acid.
Patent CN102311332a discloses a method for producing succinic acid, which uses butyrolactone as a solvent, uses heterogeneous catalyst of alumina and other carriers, prepares maleic anhydride/gamma-butyrolactone solution, uses latent heat of gamma-butyrolactone solution to realize temperature control, and further realizes smooth reaction. And separating and hydrolyzing the generated succinic anhydride, and crystallizing to obtain the high-purity succinic acid.
In patent CN112979455a, water is used as a solution, heterogeneous catalysts such as Pd are used, and at the same time, a low boiling point solvent such as methyl ether is added into a reaction solution, so that the reaction temperature is controlled by latent heat of water and evaporation heat of the low boiling point solvent such as methyl ether, and high selectivity conversion is realized.
Although the above research method realizes high selectivity conversion of maleic anhydride, it can be seen that in order to reduce the influence caused by reaction heat, researchers usually adopt a large amount of solvent to dilute maleic anhydride, reduce the total heat release amount of the reaction in the same reaction volume in the reaction system, and realize reduction of temperature rise by using latent heat, however, the measure needs to increase working sections such as solvent circulation, product separation and the like, and increases the investment of reaction devices and the cost of material consumption and energy consumption. The method of adding the low boiling point solvent into the aqueous solution is adopted, and the solvent separation is needed in the follow-up process, so that the energy consumption is still relatively high.
Meanwhile, in the prior art, if a high-purity succinic acid product is required to be obtained, further cooling crystallization operation is required, and the operation is intermittent operation, but because the concentration of maleic anhydride in the raw materials is low, the concentration of succinic acid in the product is also low, and the reaction cost is correspondingly increased by the succinic acid crystallization operation.
Disclosure of Invention
In the research aiming at the technical problems, the inventor thinks that if water is used as a solvent for the reaction, and the phase change enthalpy of the water is far higher than the enthalpy change of the temperature rise of liquid water, by utilizing the point, the temperature rise of the high exothermic reaction can be effectively controlled by adopting a water evaporation mode as a belt heating mode in the reaction process, the accurate control of the reaction temperature is realized, so that the concentration range of the maleic anhydride which can be processed in the prior art can be widened, and the direct hydrolysis hydrogenation of the maleic anhydride solution with high concentration is realized on the basis of ensuring the conversion rate and the selectivity of the reaction.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a technological method for preparing succinic acid by aqueous phase hydrogenation of maleic anhydride hydrolyzes maleic anhydride with concentration of 10-75wt%, and hydrogen is introduced into a hydrogenation reaction kettle, the top of the hydrogenation reaction kettle is provided with a gas outlet, and a solid catalyst is fixed in the hydrogenation reaction kettle to catalyze maleic anhydride hydrogenation reaction; in the reaction process, the reaction pressure is regulated to keep the reaction temperature at 40-180 ℃, water in the reaction system is kept in a boiling state by regulating the pressure, water vapor and unreacted hydrogen are continuously discharged from a gas outlet, and after the reaction is finished, the reaction product is subjected to solid-liquid separation and/or crystallization separation to obtain succinic acid crystals.
Further, a stirring device is arranged in the hydrogenation reaction kettle.
Further, the solid catalyst is fixed at a position outside the bottom of the hydrogenation reaction kettle, so that the contact with succinic acid crystallized after the reaction is avoided as much as possible, the adhesion of the succinic acid on the surface of the catalyst is prevented, and the catalytic effect is influenced. Preferably, the solid catalyst is fixed on a stirring device of the hydrogenation reaction kettle, more specifically, the catalyst is fixed on a stirring paddle of the stirring device after being packaged into a single catalytic unit, and is preferably packaged in a porous net bag and fixed on the stirring paddle, so that the solid catalyst not only realizes fixation, but also can rotate along with the stirring paddle, enhances the contact with reaction materials, and reduces the adhesion of succinic acid along with the scouring of the materials in the rotating process.
Further, the concentration of maleic anhydride is preferably 10wt% to 70wt%, more preferably 20wt% to 60wt%, and most preferably 20wt% to 35wt%. The invention adopts the water phase change heat-taking mode, well solves the temperature rise problem, greatly improves the concentration of the maleic anhydride which can be treated, and can obtain more products by one reaction in the range of controlling the temperature rise from the economic point of view.
Further, the hydrogenation reaction temperature is preferably 50℃to 120℃and most preferably 60℃to 100 ℃. The hydrogenation reaction time is 20min-5h, preferably 40min-2h.
Further, the hydrogen is added in a molar ratio of hydrogen to maleic anhydride of 0.1 to 1000:1, preferably 1 to 100:1, most preferably 1 to 10:1.
Further, maleic anhydride and hydrogen are mixed in advance or in a hydrogenation reaction device. It will be appreciated by those skilled in the art that hydrogen has a low solubility in water and therefore the gas-liquid mixing is enhanced by some means. Specifically, when maleic anhydride raw material and hydrogen are mixed in advance, a gas-liquid mixer is preferably used to enhance hydrogen dissolution; when maleic anhydride raw material and hydrogen are mixed in the hydrogenation reaction device, the hydrogen is preferably introduced into the hydrogenation reaction device by adopting a membrane disperser or a porous distribution mode.
Further, the hydrogen can be added in sections or continuously introduced. Hydrogen is added from the bottom of the reaction kettle or introduced into a net bag filled with catalyst through a conduit.
Further, the active component of the solid catalyst is at least one selected from Pd, pt, ru, ni and Cu, and the carrier is an acid-resistant carrier. The acid-resistant carrier is at least one selected from C, resin and inorganic refractory oxide, and comprises a carrier modified on the basis of the acid-resistant carrier to have acid resistance.
Further, the solid catalyst is most preferably a resin palladium-based catalyst.
Further, the dosage of the solid catalyst is 1-50% of the volume of the reaction liquid in the reaction kettle, preferably 5-20% by volume.
In the technical scheme of the invention, the solubility of maleic anhydride in water is relatively large, the solubility of succinic acid in water is relatively small, succinic acid crystals are continuously separated out along with continuous generation of succinic acid under the condition of high concentration of raw material maleic anhydride in the reaction process, and meanwhile, water vapor formed by boiling water is continuously discharged out of a reaction system, so that the separation of succinic acid crystals is further promoted. Maleic anhydride continuously reacts in the solution, after the reaction is finished, succinic acid is separated out through crystallization, and crystallization is separated through filtration or centrifugal separation and other means.
Further, the crystallization is cooling crystallization at a temperature of 0 ℃ to 60 ℃, preferably 15 ℃ to 40 ℃.
Furthermore, after the reaction of the invention is completed, the product can be directly cooled and crystallized in the reaction kettle without taking out, and a plurality of devices and procedures are omitted.
Further, the mother liquor after crystallization and separation contains unreacted complete maleic anhydride, and the rest is water, so the method further comprises the step of recycling the mother liquor after crystallization and separation to the maleic anhydride hydrolysis unit.
Further, the process further comprises the step of condensing the water vapor at the gas outlet and unreacted hydrogen to recover hydrogen.
Further, the maleic anhydride is solid anhydride or liquid anhydride, the hydrolysis temperature is 40-70 ℃, preferably 60-70 ℃, and the hydrolysis reaction time is 1-5h, preferably 2-4h.
By adopting the technical scheme of the invention, the method has the following advantages:
(1) The process method of the invention takes the aqueous solution of maleic anhydride as the raw material, and uses the adjustment of pressure to keep the water in the reaction system in a boiling state, thereby timely taking out the heat of the reaction system by utilizing water phase change, well solving the temperature rise problem of the technology for preparing succinic acid by hydrogenating maleic anhydride, and the method is simple and easy to operate, and is convenient for industrial popularization and application.
(2) The maleic anhydride concentration range in the raw materials which can be treated by the process method is widened, and the raw materials with higher concentration can be used for reaction in the range capable of controlling temperature rise from the economical point of view, so that more products can be obtained by one-step reaction, the reaction production efficiency is greatly improved, and the upper limit of the concentration of the raw materials which can be treated by the process method cannot be achieved by other technical schemes in the field.
(3) The process method adopts the solid catalyst, and in the preferred embodiment, the solid catalyst is packaged and fixed, so that the catalyst is fully contacted with the reaction materials, the adhesion of succinic acid crystals is reduced, the catalytic effect is ensured, and the service life of the solid catalyst is prolonged.
(4) In the process method, the solubility of the succinic acid in water is greatly lower than that of maleic anhydride, the succinic acid is continuously separated out in the reaction process, and solvent water in a reaction system is continuously reduced by continuously evaporating the water, so that the separation of the succinic acid is further promoted, and under proper reaction conditions, the succinic acid can be obtained even into slurry or wet matter of the succinic acid through crystallization and cooling, and qualified succinic acid can be obtained by slightly processing, so that the production efficiency is greatly improved.
(5) As the concentration of maleic anhydride in the reaction raw materials is greatly improved, the succinic acid content in the product is high, part of succinic acid products can be separated by a filtering or centrifugal mode, and the rest is separated by a cooling crystallization mode, compared with the prior art, the coupling of the reaction and crystallization technology is realized, the crystallization operation steps and the technology energy consumption are reduced, and the technology is greatly simplified.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The hydrogenation reaction vessel used in the following examples had the following structure: the top of the hydrogenation reaction kettle is provided with a gas outlet, the bottom of the hydrogenation reaction kettle is provided with a material outlet, and the bottom outlet is closed during reaction; in the reaction process, controlling the pressure in the hydrogenation reaction kettle through a back pressure valve; the hydrogenation reaction kettle is internally provided with a stirring device so as to uniformly mix reaction materials, and the solid catalyst is arranged in the porous net bag and is suspended on the stirring slurry.
Example 1
(1) Maleic anhydride hydrolysis: adding solid maleic anhydride and water into a hydrolysis reaction kettle, wherein the concentration of maleic anhydride is 15wt%, heating and stirring at 60 ℃ to hydrolyze maleic anhydride for 2 hours, analyzing by a gas chromatography method, measuring the content of maleic anhydride, and calculating the hydrolysis rate of maleic anhydride to be 89.4%;
(2) Maleic anhydride hydrogenation reaction: adding hydrolyzed maleic anhydride and hydrogen into a hydrogenation reaction kettle for reaction, wherein a solid catalyst in the hydrogenation reaction kettle takes Ni as an active component and silicon dioxide as a carrier (the content of the active component Ni is 35 percent based on the total weight of the catalyst), and the dosage of the catalyst is 10 percent of the total volume of reaction raw materials based on the total volume of maleic anhydride solution added into the hydrogenation reaction kettle; hydrogen is added into a hydrogenation reactor through a membrane disperser, the molar ratio of the hydrogen to maleic anhydride in reaction materials (the ratio of the hydrogen to the maleic anhydride) is 2:1, a vacuum pump and a back pressure valve are adopted to control the absolute pressure in the reaction system to be 0.2bar, the reaction system is kept boiling, water vapor is discharged from a gas outlet to realize heat extraction, the reaction temperature is 60 ℃ at the moment, the reaction time is 3 hours, and the maleic anhydride conversion rate and the succinic acid selectivity result are shown in table 1.
(3) Product separation: after the reaction is finished, the temperature of the kettle-type reactor is reduced to 20-40 ℃, the product is taken out, the product is centrifuged, leaching is carried out for 2 times in the centrifugal separation process, and mother liquor after leaching is conveyed into a maleic anhydride hydrolysis reaction kettle; drying the solid at a temperature not higher than 160 ℃ to prevent overheating dehydration of the succinic acid, and detecting that the purity of the succinic acid is more than or equal to 99.5%.
Example 2
(1) Maleic anhydride hydrolysis: the maleic anhydride is hydrolyzed by heating and stirring an aqueous solution with the concentration of 20 weight percent of raw material maleic anhydride at 70 ℃ for 3 hours, and the hydrolysis rate of the maleic anhydride is 99.7 percent.
(2) Maleic anhydride hydrogenation reaction: the solid catalyst is a catalyst which takes Cu as an active component and silicon dioxide as a carrier (the Cu content of the active component is 25 percent based on the total weight of the catalyst), and the dosage of the catalyst is 10 percent of the total volume of the reaction raw materials based on the total volume of maleic anhydride solution added into a hydrogenation reaction kettle; the procedure was as in (2) of example 1, and the other conditions and results are shown in Table 1.
(3) And (3) in the same step (3) in the embodiment 1, detecting that the purity of the succinic acid is more than or equal to 99.5 percent.
Example 3
(1) Maleic anhydride hydrolysis: the raw material is water solution with maleic anhydride concentration of 30wt% and is heated and stirred at 65 ℃ to hydrolyze maleic anhydride for 3.5 hours, and the hydrolysis rate of maleic anhydride is 99.2%.
(2) Maleic anhydride hydrogenation reaction: the solid catalyst is a resin palladium catalyst (the Pd content of the active component is 1 percent based on the total weight of the catalyst), and the dosage of the catalyst is 10 percent of the total volume of the reaction raw materials based on the total volume of maleic anhydride solution added into a hydrogenation reaction kettle; the absolute pressure in the reaction system was controlled to be 0.31bar by using a vacuum pump and a back pressure valve, the reaction system was kept boiling, the reaction temperature was 70℃and the reaction was carried out for 4 hours, and the other operation procedures were the same as in (2) in example 1, and the other conditions and results are shown in Table 1.
(3) And (3) in the same step (3) in the embodiment 1, detecting that the purity of the succinic acid is more than or equal to 99.5 percent.
Example 4
(1) Maleic anhydride hydrolysis: the raw material is water solution with maleic anhydride concentration of 30wt% and is heated and stirred at 60 ℃ to hydrolyze maleic anhydride for 3 hours, and the hydrolysis rate of maleic anhydride is 98.3%.
(2) Maleic anhydride hydrogenation reaction: the solid catalyst is a catalyst which takes Ni as an active component and silicon dioxide as a carrier (the content of the active component Ni is 30 percent based on the total weight of the catalyst), and the dosage of the catalyst is 15 percent of the total volume of the reaction raw materials based on the total volume of maleic anhydride solution added into a hydrogenation reaction kettle; other procedures were as in (3) of example 1, and other conditions and results are shown in Table 1.
(3) And (3) in the same step (3) in the embodiment 1, detecting that the purity of the succinic acid is more than or equal to 99.5 percent.
Example 5
(1) Maleic anhydride hydrolysis: the raw material is water solution with maleic anhydride concentration of 40wt% and is heated and stirred at 70 ℃ to hydrolyze maleic anhydride for 2 hours, and the hydrolysis rate of maleic anhydride is 99.7%.
(2) Maleic anhydride hydrogenation reaction: the solid catalyst is resin palladium (the Pd content of the active component is 2 percent based on the total weight of the catalyst), and the dosage of the catalyst is 10 percent of the total volume of the reaction raw materials based on the total volume of maleic anhydride solution added into a hydrogenation reaction kettle; the absolute pressure in the reaction system was controlled to be 0.39bar by using a vacuum pump and a back pressure valve, the reaction system was kept boiling, the reaction temperature was 75 ℃, the reaction was carried out for 4 hours, and other operation procedures were the same as in (3) in example 1, and other conditions and results are shown in Table 1.
(3) And (3) in the same step (3) in the embodiment 1, detecting that the purity of the succinic acid is more than or equal to 99.5 percent.
Example 6
(1) Maleic anhydride hydrolysis: the raw material is aqueous solution with maleic anhydride concentration of 50wt percent, and the aqueous solution is heated and stirred at 70 ℃ to hydrolyze the maleic anhydride for 2 hours, and the hydrolysis rate of the maleic anhydride is 99.6 percent.
(2) Maleic anhydride hydrogenation reaction: the solid catalyst is a catalyst which takes Cu as an active component and silicon dioxide as a carrier (the Cu content of the active component is 30 percent based on the total weight of the catalyst), and the dosage of the catalyst is 10 percent of the total volume of the reaction raw materials based on the total volume of maleic anhydride solution added into a hydrogenation reaction kettle; the absolute pressure in the reaction system was controlled to be 0.47bar by using a vacuum pump and a back pressure valve, the reaction system was kept boiling, the reaction temperature was 80℃and the reaction was carried out for 4 hours, and the other operation procedures were the same as in (3) in example 1, and the other conditions and results are shown in Table 1.
(3) And (3) in the same step (3) in the embodiment 1, detecting that the purity of the succinic acid is more than or equal to 99.5 percent.
Example 7
(1) Maleic anhydride hydrolysis: the raw material is water solution with 65wt% of maleic anhydride, and the water solution is heated and stirred at 70 ℃ to hydrolyze the maleic anhydride for 2 hours, and the hydrolysis rate of the maleic anhydride is 99.6%.
(2) Maleic anhydride hydrogenation reaction: the solid catalyst is a resin palladium catalyst (the Pd content of the active component is 3 percent based on the total weight of the catalyst), and the dosage of the catalyst is 10 percent of the total volume of the reaction raw materials based on the total volume of maleic anhydride solution added into a hydrogenation reaction kettle; the absolute pressure in the reaction system was controlled to be 0.7bar by using a vacuum pump and a back pressure valve, the reaction system was kept boiling, the reaction temperature was 90℃and the reaction was carried out for 4 hours, and the other operation procedures were the same as in (3) in example 1, and the other conditions and results are shown in Table 1.
(3) And (3) in the same step (3) in the embodiment 1, detecting that the purity of the succinic acid is more than or equal to 99.5 percent.
TABLE 1
Comparative example 1
The method comprises the steps of preparing maleic anhydride solution with the mass concentration of 10% by taking r-butyrolactone as a solvent, reacting by a fixed bed reactor at the reaction temperature of 80 ℃ and the reaction pressure of 3MPa, wherein the catalyst adopts a catalyst with an active component Ni supported by a silicon-aluminum carrier, and circularly taking heat by adopting heat conducting oil in the reaction process. Separating the reacted product by a light component removing tower, a heavy component removing tower and a solvent refining tower in sequence to obtain a succinic anhydride product, hydrolyzing and crystallizing the succinic anhydride to obtain wet succinic acid, and drying the wet succinic acid to obtain the succinic acid product. Maleic anhydride conversion, succinic acid selectivity and energy consumption are shown in table 2.
In the comparative example, maleic anhydride concentration can only be about 10% due to rapid heat release of the reaction, heat transfer oil is required to be used for circularly taking heat, and the reaction process cannot be controlled due to high concentration.
Comparative example 2
The concentration of maleic anhydride raw material was 10%, maleic anhydride solution, the same catalyst as in example 3 and hydrogen gas with a hydrogen anhydride ratio of 2 were injected into an adiabatic closed reaction vessel before the reaction, and the initial reaction temperature was 80 ℃. Gas is not extracted outwards in the reaction process.
Because heat removal is not adopted, the reaction pressure and the reaction temperature are rapidly increased in the reaction process, and the product after the reaction pressure is stabilized for 1h is taken out and cooled, dried and crystallized.
Comparative example 3
The concentration of maleic anhydride raw material is 30%, maleic anhydride solution, the catalyst of the embodiment 6 and hydrogen with the hydrogen anhydride ratio of 3 are injected into a reaction kettle before the reaction, the initial reaction temperature is 80 ℃, the reaction pressure is kept at 0.5Mpa, at this time, water is in a non-boiling state, the reaction kettle adopts external circulating cooling water to take out heat, hydrogen (possibly with a small amount of water vapor entrained therein) is collected at the outlet of the top of the reactor, and the product after 4 hours of reaction is taken out and cooled for crystallization.
In the comparative example, because the concentration of maleic anhydride is higher, an external heat transfer measure is needed, otherwise, the temperature in the reactor is seriously increased, and the reaction cannot be completed.
Comparative example 4
The concentration of maleic anhydride raw material is 65% at most, maleic anhydride solution and the catalyst of example 7 are injected into a reaction kettle before reaction, and the ratio of hydrogen anhydride is 4h -1 The hydrogen in the reaction system is controlled to maintain the liquid phase state, the reaction kettle adopts external circulating cooling water to take heat, the initial reaction temperature is 65 ℃, and the initial reaction pressure is 0.5MPa. Unreacted hydrogen is extracted from the top end of the reaction kettle (a small amount of water vapor is difficult to avoid being entrained in the reaction kettle), and the product after 4 hours of reaction is taken out and cooled for crystallization.
In this comparative example, since maleic anhydride concentration is high, an external heat transfer measure must be used, and even if the initial temperature is lower than that of example 7 and an external heat transfer measure is used, the reaction temperature rise cannot be controlled, the temperature rise is rapid, the side reaction is serious, and the succinic acid selectivity is extremely low.
TABLE 2
Wherein, the energy consumption comprises the refining energy consumption of the succinic acid in the hydrogenation reaction process.
Claims (14)
1. A process for preparing succinic acid by aqueous phase hydrogenation of maleic anhydride is characterized in that maleic anhydride with the concentration of 10-75wt% is hydrolyzed and then is introduced into a hydrogenation reaction kettle together with hydrogen, the top of the hydrogenation reaction kettle is provided with a gas outlet, and a solid catalyst is fixed in the gas outlet to catalyze maleic anhydride hydrogenation reaction; in the reaction process, the reaction pressure is regulated to keep the reaction temperature at 40-180 ℃, water in the reaction system is kept in a boiling state by regulating the pressure, water vapor and unreacted hydrogen are continuously discharged from a gas outlet, and after the reaction is finished, the reaction product is subjected to solid-liquid separation and/or crystallization separation to obtain succinic acid crystals.
2. The process according to claim 1, wherein a stirring device is arranged in the hydrogenation reaction kettle.
3. The process of claim 1 wherein the solid catalyst is fixed to a location outside the bottom of the hydrogenation reactor.
4. The process of claim 2 wherein the solid catalyst is fixed to a stirring device.
5. The process of claim 4 wherein the solid catalyst is encapsulated in a porous mesh bag and is secured to a stirring paddle.
6. Process according to claim 1, characterized in that the concentration of maleic anhydride is 10% to 70% by weight, preferably 20% to 60% by weight, more preferably 20% to 35% by weight.
7. Process according to claim 1, characterized in that the temperature of the hydrogenation reaction is 50-120 ℃, preferably 60-100 ℃.
8. Process according to claim 1, characterized in that the hydrogenation reaction time is 20min-5h, preferably 40min-2h.
9. The process according to claim 1, wherein the hydrogen is introduced in a molar ratio of hydrogen to maleic anhydride of 0.1 to 1000:1.
10. The process of claim 5, wherein hydrogen is introduced from the bottom of the hydrogenation reactor or from a conduit into a net bag containing catalyst.
11. The process of claim 1, wherein the active component of the solid catalyst is at least one selected from Pd, pt, ru, ni and Cu, and the carrier is an acid-resistant carrier.
12. The process of claim 1, further comprising the step of recycling the mother liquor after crystallization separation to the maleic anhydride hydrolysis unit.
13. The process of claim 1 further comprising the step of condensing the water vapor at the gas outlet and unreacted hydrogen to recover hydrogen.
14. The process according to claim 1, wherein the maleic anhydride is a solid anhydride or a liquid anhydride, the hydrolysis temperature is 40-70 ℃ and the hydrolysis reaction time is 1-5h.
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