CN117658792A - Intermittent maleic anhydride aqueous phase hydrogenation process for preparing succinic acid - Google Patents
Intermittent maleic anhydride aqueous phase hydrogenation process for preparing succinic acid 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 108
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 title claims abstract description 95
- 239000001384 succinic acid Substances 0.000 title claims abstract description 46
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 45
- 239000008346 aqueous phase Substances 0.000 title claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 138
- 238000000034 method Methods 0.000 claims abstract description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 32
- 239000001257 hydrogen Substances 0.000 claims abstract description 32
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 28
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 25
- 239000002815 homogeneous catalyst Substances 0.000 claims abstract description 23
- 230000007062 hydrolysis Effects 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 17
- 238000009835 boiling Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 239000013078 crystal Substances 0.000 claims abstract description 5
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 230000008569 process Effects 0.000 claims description 34
- 239000000243 solution Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 19
- 238000002425 crystallisation Methods 0.000 claims description 17
- 230000008025 crystallization Effects 0.000 claims description 17
- 238000002156 mixing Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 4
- 239000012452 mother liquor Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 238000004064 recycling Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 5
- 239000012071 phase Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000002904 solvent Substances 0.000 description 12
- 239000003446 ligand Substances 0.000 description 10
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- -1 polybutylene succinate Polymers 0.000 description 7
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Substances C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 6
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 229940014800 succinic anhydride Drugs 0.000 description 5
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002638 heterogeneous catalyst Substances 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- 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
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- YSWYYGKGAYSAOJ-UHFFFAOYSA-N phosphane Chemical group P.P YSWYYGKGAYSAOJ-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- VYFPSYVVFFFYBF-UHFFFAOYSA-N sodium;triphenylphosphane Chemical compound [Na].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 VYFPSYVVFFFYBF-UHFFFAOYSA-N 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C07C51/083—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A process for preparing succinic acid by intermittent aqueous phase hydrogenation of maleic anhydride uses aqueous solution with concentration of 20-75wt% as raw material, after maleic anhydride is hydrolyzed, hydrolysis liquid of maleic anhydride, hydrogen and homogeneous catalyst are reacted in hydrogenation reaction device, reaction pressure is regulated to keep reaction temperature at 40-200 deg.C, water in reaction system is kept in boiling state by regulating pressure, gas outlet is set on hydrogenation reaction device, water vapor and unreacted hydrogen are continuously discharged from gas outlet, after reaction, reaction product is crystallized and separated to obtain succinic acid crystal. The invention adopts intermittent reaction, takes aqueous solution of maleic anhydride as raw material, and uses pressure adjustment to keep water in the reaction system in boiling state, thereby timely taking out heat of the reaction system by utilizing water phase change, well solving the temperature rise problem of succinic acid preparation technology by maleic anhydride hydrogenation, 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 intermittent 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 process for preparing succinic acid by intermittent aqueous phase hydrogenation of maleic anhydride uses aqueous solution of maleic anhydride as raw material, wherein the concentration of maleic anhydride is 20-75wt%, after maleic anhydride is hydrolyzed, the hydrolyzed solution of maleic anhydride, hydrogen and homogeneous catalyst are reacted in a hydrogenation reaction device, the reaction pressure is adjusted to keep the reaction temperature at 40-200 ℃, water in the reaction system is kept in a boiling state by adjusting the pressure, a gas outlet is arranged on the hydrogenation reaction device, water vapor and unreacted hydrogen are continuously discharged from the gas outlet, and after the reaction, the reaction product is crystallized and separated to obtain succinic acid crystals.
Further, the concentration of maleic anhydride in the aqueous solution of maleic anhydride is 25wt% to 60wt%, preferably 30wt% to 50wt%. In the technical scheme of the invention, batch reaction is adopted, and the problem of temperature rise is well solved by utilizing water phase, so that in the range of temperature rise control, the higher the raw material concentration is, the higher the reaction efficiency is, more products can be obtained in one batch reaction, the maleic anhydride concentration in the raw material is preferably 25-60 wt%, most preferably 30-50 wt%, the temperature rise can be well ensured, the higher reaction efficiency can be ensured, and the lower concentration limit is greatly improved compared with the raw material concentration in the prior art.
Further, the hydrogenation reaction temperature is 50℃to 200℃and more preferably 50℃to 120℃and most preferably 60℃to 100 ℃. The hydrogenation reaction time is 20min-5h, preferably 40min-2h.
Further, the homogeneous catalyst is an aqueous solution containing a soluble salt of at least one of the following metals: pd, ti, co, V, fe, ir, rh, au, pt, ni, ag, sn, mo, zn, mn, cu and Ru. Among them, co, ni, pd, pt and Ru are preferable.
Further, the soluble salt is preferably RuCl 3 、PdCl 2 、CoCl 2 、NiCl 2 And H 2 PtCl 4 At least one of them.
Further, the homogeneous catalyst also comprises a corresponding water-soluble ligand which keeps the metal salt solution stable in dissolution, wherein the water-soluble ligand is specifically selected from at least one of triphenylphosphine sodium sulfonate, diphenylphosphine diethyl carboxylic acid, polyhydroxy phosphine ligand and quaternary phosphonium salt phosphine ligand.
Further, the concentration of the homogeneous catalyst in the reaction raw material formed after mixing the hydrolysis liquid of maleic anhydride and the homogeneous catalyst is not less than 0.001mmol/L, preferably not less than 1mmol/L, in terms of metal element; further preferably 1 to 20mmol/L, most preferably 5 to 15mmol/L.
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, the maleic anhydride raw material and the 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 process method further comprises the step of recycling the crystallization mother liquor containing the homogeneous catalyst obtained after crystallization separation.
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, crystallization is separated through filtration or centrifugal separation and the like, and mother liquor dissolved with the homogeneous catalyst is recycled.
Further, the crystallization is cooling crystallization at a temperature of 0 ℃ to 60 ℃, preferably 15 ℃ to 40 ℃.
Further, the hydrogenation reaction device is a reaction kettle. And a stirring device is arranged in the reaction kettle, so that the materials are fully stirred and mixed during reaction.
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 gas outlet is arranged at the upper part of the hydrogenation reaction device.
Furthermore, a stirring device is arranged in the hydrogenation reaction device, so that the hydrogen is fully dispersed, and the reaction is promoted.
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 intermittent reaction is adopted in the process method, the water solution of maleic anhydride is used as a raw material, and the pressure is adjusted to keep the water in the reaction system in a boiling state, so that the heat of the reaction system can be timely taken out by utilizing water phase change, the problem of temperature rise in the technology of 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.
(2) The maleic anhydride concentration range in the raw materials which can be treated by the process method is widened, intermittent reaction is adopted, the raw materials with higher concentration can be adopted for reaction in the range capable of controlling temperature rise from the economical point of view, more products can be obtained by one-time intermittent 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 homogeneous catalyst, part of succinic acid products are separated by filtration or centrifugation, and part of succinic acid products are separated by cooling crystallization, so that compared with the prior art, the process method realizes the coupling of reaction and crystallization process, reduces crystallization operation steps and process energy consumption, and greatly simplifies the process.
(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, the water is used for phase change for heat extraction, the solvent in a reaction system is continuously reduced by evaporation of the water, the separation of the succinic acid is further promoted, and under proper reaction conditions, the succinic acid can be obtained even by crystallization and cooling to obtain slurry or wet matter of the succinic acid, and qualified succinic acid can be obtained by slightly treating the slurry or wet matter, so that the production efficiency is greatly improved.
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.
Example 1
(1) Maleic anhydride hydrolysis: adding solid maleic anhydride and water into a hydrolysis reaction kettle, wherein the concentration of maleic anhydride is 20wt%, 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, hydrogen and a homogeneous catalyst into a kettle reactor for reaction, wherein the homogeneous catalyst is RuCl 3 The concentration of Ru element in the reaction solution formed after initial mixing is 6mmol/L, the concentration of water-soluble ligand m-triphenylphosphine sodium sulfonate is 8mmol/L, hydrogen is added into a hydrogenation reactor by a membrane disperser, the molar ratio of the hydrogen to maleic anhydride in the reaction material (the ratio of the hydrogen anhydride) is 2:1, the absolute pressure in the reaction system is controlled to be 0.25bar by adopting a vacuum pump and a back pressure valve, the reaction system is kept boiling, a gas outlet is arranged at the top of the kettle reactor, water vapor is discharged from the outlet to realize heat extraction, the reaction temperature is 65 ℃ at the moment, the reaction time is 3h, and the maleic anhydride conversion rate and 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, the leached mother liquor is conveyed into a maleic anhydride hydrolysis reaction kettle or a hydrogenation reaction kettle, the solid is dried, the drying temperature is not higher than 160 ℃, the overheating dehydration of succinic acid is prevented, and the purity of the detected succinic acid is not less than 99.5%.
Example 2
(1) Maleic anhydride hydrolysis: the maleic anhydride is hydrolyzed by heating and stirring an aqueous solution with the concentration of raw material maleic anhydride of 30 weight percent at 70 ℃ for 3 hours, and the hydrolysis rate of the maleic anhydride is 99.7 percent.
(2) Maleic anhydride hydrogenation reaction: the homogeneous catalyst is H 2 PtCl 4 The reaction solution formed after the initial mixing had a concentration of 6mmol/L of Pt element and a concentration of 8mmol/L of diphenylphosphine diethyl carboxylic acid as a water-soluble ligand, and the procedure was the same as in (2) of example 1, with other conditions and results 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 40wt% 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 homogeneous catalyst is RuCl 3 The concentration of Ru element in the reaction solution formed after initial mixing is 8mmol/L, the concentration of water-soluble ligand sodium m-triphenylphosphine sulfonate is 10mmol/L, the absolute pressure in the reaction system is controlled to be 0.47bar by adopting a vacuum pump and a back pressure valve, the reaction system is kept boiling, the reaction temperature is 80 ℃, the reaction is carried out for 4 hours, other operation processes are the same as in (2) in the embodiment 1, and other conditions and results are shown in the 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 aqueous solution with maleic anhydride concentration of 50wt percent, and the aqueous solution is heated and stirred at 60 ℃ to hydrolyze the maleic anhydride for 3 hours, and the hydrolysis rate of the maleic anhydride is 98.3 percent.
(2) Maleic anhydride hydrogenation reaction: the homogeneous catalyst is NiCl 2 The concentration of Ni element in the reaction solution formed after initial mixing is 6mmol/L, and the water-soluble ligandThe concentration of the sodium m-triphenylphosphine sulfonate is 8mmol/L, the absolute pressure in the reaction system is controlled to be 0.47bar by adopting a vacuum pump and a back pressure valve, the reaction system is kept boiling, the reaction temperature is 80 ℃, the reaction is carried out for 4 hours, other operation processes are the same as (2) in the example 1, and other conditions and results are shown in the 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 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 99.7 percent.
(2) Maleic anhydride hydrogenation reaction: the homogeneous catalyst is CoCl 2 The concentration of Co element in the reaction solution formed after initial mixing is 9mmol/L, the concentration of water-soluble ligand sodium m-triphenylphosphine sulfonate is 10mmol/L, the absolute pressure in the reaction system is controlled to be 0.57bar by adopting a vacuum pump and a back pressure valve, the reaction system is kept boiling, the reaction temperature is 85 ℃, the reaction is carried out for 4 hours, other operation processes are the same as in (2) in the example 1, and other conditions and results are shown in the 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 60wt% and 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 homogeneous catalyst is PdCl 2 The concentration of Pd element in the reaction solution formed after initial mixing is 8mmol/L, the concentration of water-soluble ligand sodium m-triphenylphosphine sulfonate is 10mmol/L, the absolute pressure in the reaction system is controlled to be 0.70bar by adopting a vacuum pump and a back pressure valve, the reaction system is kept boiling, the reaction temperature is 90 ℃, the reaction is carried out for 4 hours, other operation processes are the same as in (2) in the example 1, and other conditions and results are shown in the 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 aqueous solution with the concentration of 70wt% of maleic anhydride, and the maleic anhydride 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 homogeneous catalyst is RuCl 3 The concentration of Ru element in the reaction solution formed after initial mixing is 8mmol/L, the concentration of water-soluble ligand sodium m-triphenylphosphine sulfonate is 10mmol/L, the absolute pressure in the reaction system is controlled to be 0.70bar by adopting a vacuum pump and a back pressure valve, the reaction system is kept boiling, the reaction temperature is 90 ℃, the reaction is carried out for 4 hours, other operation processes are the same as in (2) in the embodiment 1, and other conditions and results are shown in the 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 7 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 up to 70%, maleic anhydride solution and the catalyst of example 7 are injected into a reaction kettle before the reaction, and the ratio of the 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 (15)
1. A process for preparing succinic acid by intermittent aqueous phase hydrogenation of maleic anhydride is characterized in that aqueous solution of maleic anhydride is used as raw material, wherein the concentration of maleic anhydride is 20-75wt%, after maleic anhydride is hydrolyzed, hydrolysis liquid of maleic anhydride, hydrogen and homogeneous catalyst are reacted in a hydrogenation reaction device, reaction pressure is adjusted to keep reaction temperature at 40-200 ℃, water in the reaction system is kept in boiling state by adjusting the pressure, a gas outlet is arranged on the hydrogenation reaction device, water vapor and unreacted hydrogen are continuously discharged from the gas outlet, and after the reaction is finished, the reaction product is crystallized and separated to obtain succinic acid crystals.
2. Process according to claim 1, characterized in that the concentration of maleic anhydride in the aqueous solution of maleic anhydride is 25% to 60% by weight, preferably 30% to 50% by weight.
3. Process according to claim 1, characterized in that the temperature of the hydrogenation reaction is 50-150 ℃, more preferably 50-120 ℃, most preferably 60-100 ℃.
4. The process according to claim 1, characterized in that the material residence time of the hydrogenation reaction is 20min-5h, preferably 40min-2h.
5. The process according to claim 1, characterized in that the homogeneous catalyst is an aqueous solution containing soluble salts of at least one of the following metals: pd, ti, co, V, fe, ir, rh, au, pt, ni, ag, sn, mo, zn, mn, cu and Ru.
6. The process of claim 4, wherein the homogeneous catalyst is an aqueous solution comprising at least one of Co, ni, pd, pt and Ru soluble salts; the soluble salt is preferably RuCl 3 、PdCl 2 、CoCl 2 、NiCl 2 And H 2 PtCl 4 At least one of them.
7. The process according to claim 1, wherein the homogeneous catalyst is used in an amount such that the concentration of the metal element in the reaction raw material formed after mixing the hydrolysis solution of maleic anhydride and the homogeneous catalyst is not less than 0.001mmol/L.
8. The process according to claim 1, wherein the hydrogen is introduced in a molar ratio of hydrogen to maleic anhydride of 1-1000:1.
9. The process according to claim 1, further comprising the step of recycling the crystallized mother liquor containing the homogeneous catalyst obtained after crystallization separation.
10. The process of claim 1, wherein the crystallization is a cooling crystallization at a temperature of 0 ℃ to 60 ℃.
11. The process according to claim 1, wherein the product is not taken out after the completion of the reaction, and is directly cooled and crystallized in the reaction vessel.
12. The process according to claim 1, wherein the hydrogenation reaction device is a reaction kettle, and a stirring device is arranged in the reaction kettle.
13. The process of claim 1, wherein the gas outlet is disposed in an upper portion of the hydrogenation reaction apparatus.
14. The process of claim 1 further comprising the step of condensing the water vapor at the gas outlet and unreacted hydrogen to recover hydrogen.
15. 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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