CN117658962A - Technological method for preparing succinic anhydride by maleic anhydride hydrogenation - Google Patents
Technological method for preparing succinic anhydride by maleic anhydride hydrogenation 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 72
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 70
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229940014800 succinic anhydride Drugs 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 113
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 62
- 239000001257 hydrogen Substances 0.000 claims abstract description 62
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000003960 organic solvent Substances 0.000 claims abstract description 25
- 238000009835 boiling Methods 0.000 claims abstract description 24
- 239000011949 solid catalyst Substances 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000007789 gas Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 238000002425 crystallisation Methods 0.000 claims abstract description 7
- 230000008025 crystallization Effects 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 3
- 239000003054 catalyst Substances 0.000 claims description 34
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 14
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012452 mother liquor Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- 238000006460 hydrolysis reaction Methods 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 11
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000047 product Substances 0.000 description 25
- 239000000463 material Substances 0.000 description 19
- 239000000243 solution Substances 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 13
- 239000007787 solid Substances 0.000 description 10
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 10
- 230000001276 controlling effect Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 238000002386 leaching Methods 0.000 description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- -1 polybutylene succinate Polymers 0.000 description 7
- 150000008064 anhydrides Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000001965 increasing effect Effects 0.000 description 4
- 229920002961 polybutylene succinate Polymers 0.000 description 4
- 239000004631 polybutylene succinate Substances 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 2
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 2
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 2
- 229930188620 butyrolactone Natural products 0.000 description 2
- 239000002638 heterogeneous catalyst Substances 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000007670 refining Methods 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
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000009991 scouring Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The technological process of hydrogenating maleic anhydride to prepare succinic anhydride includes dissolving maleic anhydride in organic solvent with boiling point no higher than 150 deg.c and no reaction with maleic anhydride, reaction with hydrogen and solid catalyst in hydrogenation reactor, regulating the reaction pressure to 30-150 deg.c, maintaining the solvent in the reaction system in boiling state, setting gas outlet on the hydrogenation reactor, exhausting organic solvent and unreacted hydrogen continuously from the gas outlet, and solid-liquid separation and/or crystallization separation of the reacted product to obtain succinic anhydride. The invention takes the organic solution for dissolving maleic anhydride as the raw material, and the solution 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 timely taken out by utilizing the phase change of the organic solvent, the problem of temperature rise of the technology for preparing succinic anhydride by hydrogenating maleic anhydride is 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 a process method for preparing succinic anhydride by maleic anhydride hydrogenation, belonging to the technical field of catalytic processes.
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.
At present, a succinic acid and butanediol polymerization method is adopted to produce PBS materials, and water is required to be removed in the polymerization reaction, so that the molecular weight of the materials and the properties of synthetic materials are influenced. And succinic anhydride is directly polymerized with butanediol, and the product quality is higher than that of an acid-alcohol polymerization material because the polymerization process is compared with succinic acid, and the succinic anhydride product has a higher development prospect.
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.
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 reaction in the same reaction volume in the reaction system, realize temperature rise reduction by using latent heat, the concentration of maleic anhydride which can be treated is low, and the sections of solvent circulation, product separation and the like are increased, thus increasing the investment of reaction devices and the cost of material consumption and energy consumption.
Disclosure of Invention
In the research aiming at the technical problems, the inventor thinks that if the solvent is subjected to phase change by controlling the reaction conditions, the phase change enthalpy of the solvent is far higher than the enthalpy change of the temperature rise of the solvent, and the solvent after the phase change is taken out in time, so that the temperature rise of the high exothermic reaction can be effectively controlled as a heating mode, the accurate control of the reaction temperature is realized, the concentration range of the maleic anhydride which can be processed in the prior art can be widened, and the direct hydrogenation of the maleic anhydride solution to prepare the succinic anhydride is realized on the basis of ensuring the reaction conversion rate and the selectivity.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a process for preparing succinic anhydride by hydrogenating maleic anhydride includes such steps as dissolving maleic anhydride in organic solvent with boiling point not higher than 150 deg.C and concentration of 10-75 wt%, reaction with hydrogen and solid catalyst in hydrogenation reactor, regulating reaction pressure to 30-150 deg.C, boiling solvent in reaction system, setting gas outlet on hydrogenation reactor, continuously discharging organic solvent and unreacted hydrogen from gas outlet, and solid-liquid separation and/or crystallizing separation.
Further, the boiling point of the organic solvent is preferably not higher than 120 ℃, more preferably not higher than 100 ℃.
Further, the organic solvent is at least one selected from tetrahydrofuran (atmospheric boiling point 66 ℃), diethyl ether (atmospheric boiling point 34.5 ℃), methyl formate (atmospheric boiling point 31.5 ℃) and methyl acetate (atmospheric boiling point 56.8 ℃), preferably tetrahydrofuran.
Further, a stirring device is arranged in the hydrogenation reaction device.
Further, the solid catalyst is fixed at a position outside the bottom of the hydrogenation reaction device, so that the contact with the succinic anhydride crystallized after the reaction is avoided as much as possible, and the adhesion of the succinic anhydride 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 device, more specifically, the catalyst is fixed on a stirring paddle of the stirring device after being packaged into a plurality of catalytic units, and is preferably packaged in a plurality of porous net bags and is fixed on the stirring paddle in a dispersing manner, 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 anhydride along with the scouring of the materials in the rotating process.
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 dosage of the solid catalyst is 1% -50%, preferably 5% -20% of the volume of the reaction liquid in the reaction kettle.
Further, the concentration of maleic anhydride is preferably 15wt% to 70wt%, more preferably 25wt% to 60wt%, and most preferably 30wt% to 50wt%. According to the technical scheme, the temperature rise problem is well solved by utilizing the phase change heat extraction of the organic solvent, so that the higher the raw material concentration is, the higher the reaction efficiency is, and more products can be obtained through one-step reaction in the range of temperature rise control from the economic point of view.
Further, the hydrogenation reaction temperature is 40 ℃ to 120 ℃, more 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, the maleic anhydride raw material and the hydrogen are mixed in advance or in a hydrogenation reaction device. When the maleic anhydride raw material and the hydrogen are mixed in advance, a gas-liquid mixer is preferably used for enhancing the dissolution of the hydrogen; 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.
In the technical scheme of the invention, the solubility of maleic anhydride in the selected organic solvent is relatively large, the solubility of succinic anhydride is relatively small, succinic anhydride crystals are continuously separated out along with the continuous generation of succinic anhydride under the condition of high concentration of raw material maleic anhydride in the reaction process, and vapor formed by boiling the solvent is continuously discharged out of the reaction system, so that the separation of succinic anhydride crystals is further promoted. Maleic anhydride continuously reacts in the solution, after the reaction is finished, succinic anhydride is separated out through crystallization, part of succinic anhydride is separated through means such as filtration or centrifugal separation, and the rest of succinic anhydride is separated through crystallization, and crystallization mother liquor is recycled.
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 gas outlet is arranged at the upper part of the hydrogenation reaction device.
Further, the process further comprises the step of condensing the organic solvent and unreacted hydrogen at the gas outlet to recover hydrogen.
Further, the maleic anhydride is a solid anhydride or a liquid anhydride, preferably a liquid anhydride.
By adopting the technical scheme of the invention, the method has the following advantages:
(1) In the process method, the organic solution for dissolving the maleic anhydride is taken as a raw material, and the solution 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 timely taken out by utilizing the phase change of the organic solvent, the problem of temperature rise of the technology for preparing the succinic anhydride by hydrogenating the maleic anhydride is well solved, an external heat taking mode is not needed, 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 anhydride crystals is reduced, the catalytic effect is ensured, and the service life of the solid catalyst is prolonged.
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.
In the following examples, a hydrogenation reaction was carried out using a hydrogenation reaction vessel having the following structure: the top is provided with a gas outlet, the bottom 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 a plurality of porous net bags and is dispersedly suspended on the stirring slurry.
Example 1
The solid catalyst is a resin palladium catalyst (the load of palladium on the catalyst is 1 percent based on the total weight of the catalyst), and the dosage of the resin palladium catalyst is 10 percent based on the total volume of maleic anhydride added into the hydrogenation reaction kettle.
Preparing maleic anhydride with concentration of 10wt% by tetrahydrofuran, introducing the solution and hydrogen into a hydrogenation reaction kettle, adding hydrogen by a membrane disperser, controlling absolute pressure in a reaction system to be 1bar by adopting a vacuum pump and a back pressure valve, keeping the reaction system boiling, wherein the reaction temperature is 66 ℃, and tetrahydrofuran vapor and unreacted hydrogen are discharged from a gas outlet and react for 2 hours, wherein the mole ratio of the hydrogen to the maleic anhydride in the reaction material (the ratio of the hydrogen anhydride) is 1:1.
After the reaction is finished, the hydrogenation reaction kettle is cooled to 20-40 ℃, the product is taken out, the product is centrifuged, the organic solvent is leached for 2 times in the centrifugal separation process, the mother liquor after leaching is conveyed to a hydrogenation reaction unit, the separated succinic anhydride solid is dried, the drying temperature is 150 ℃, and the purity of the succinic anhydride is detected to be more than or equal to 99.5%.
The maleic anhydride conversion and succinic anhydride selectivity results of the hydrogenation reaction are shown in Table 1.
Example 2
The solid catalyst is a resin palladium catalyst (the load of palladium on the catalyst is 1 percent based on the total weight of the catalyst), and the dosage of the resin palladium catalyst is 10 percent based on the total volume of maleic anhydride added into the hydrogenation reaction kettle.
Preparing maleic anhydride with concentration of 30wt% by tetrahydrofuran, introducing the solution and hydrogen into a hydrogenation reaction kettle, adding hydrogen by a membrane disperser, controlling absolute pressure in a reaction system to be 1.5bar by adopting a vacuum pump and a back pressure valve, keeping the reaction system boiling, wherein the reaction temperature is 80 ℃, and tetrahydrofuran vapor and unreacted hydrogen are discharged from a gas outlet and react for 2 hours, wherein the mole ratio of the hydrogen to the maleic anhydride in the reaction material (the ratio of the hydrogen anhydride) is 2:1.
After the reaction is finished, the hydrogenation reaction kettle is cooled to 20-40 ℃, the product is taken out, the product is centrifuged, the organic solvent is leached for 2 times in the centrifugal separation process, the mother liquor after leaching is conveyed to a hydrogenation reaction unit, the separated succinic anhydride solid is dried, the drying temperature is 150 ℃, and the purity of the succinic anhydride is detected to be more than or equal to 99.5%.
The maleic anhydride conversion and succinic anhydride selectivity results of the hydrogenation reaction are shown in Table 1.
Example 3
The solid catalyst is Ni catalyst (Ni load is 30% based on the total weight of the catalyst), and the dosage of the catalyst is 10% based on the total volume of maleic anhydride added into the hydrogenation reaction kettle.
Preparing maleic anhydride with concentration of 40wt% by tetrahydrofuran, introducing the solution and hydrogen into a hydrogenation reaction kettle, adding hydrogen by a membrane disperser, controlling the molar ratio of the hydrogen to maleic anhydride in the reaction material (the ratio of the hydrogen to the maleic anhydride) to be 3:1, controlling the absolute pressure in the reaction system to be 1.5bar by adopting a vacuum pump and a back pressure valve, keeping the reaction system boiling, wherein the reaction temperature is 80 ℃, discharging tetrahydrofuran vapor and unreacted hydrogen from a gas outlet, and reacting for 3 hours.
After the reaction is finished, the hydrogenation reaction kettle is cooled to 20-40 ℃, the product is taken out, the product is centrifuged, the organic solvent is leached for 2 times in the centrifugal separation process, the mother liquor after leaching is conveyed to a hydrogenation reaction unit, the separated succinic anhydride solid is dried, the drying temperature is 150 ℃, and the purity of the succinic anhydride is detected to be more than or equal to 99.5%.
Example 4
The solid catalyst is a Cu catalyst (Cu loading is 35 percent based on the total weight of the catalyst), and the dosage of the catalyst is 10 percent based on the total volume of maleic anhydride added into the hydrogenation reaction kettle.
Preparing maleic anhydride with concentration of 40wt% by tetrahydrofuran, introducing the solution and hydrogen into a hydrogenation reaction kettle, adding hydrogen by a membrane disperser, controlling absolute pressure in a reaction system to be 2bar by adopting a vacuum pump and a back pressure valve, keeping the reaction system boiling, wherein the reaction temperature is 90 ℃, and tetrahydrofuran vapor and unreacted hydrogen are discharged from a gas outlet and react for 3 hours, wherein the mole ratio of the hydrogen to the maleic anhydride in the reaction material (the ratio of the hydrogen anhydride) is 3:1.
After the reaction is finished, the hydrogenation reaction kettle is cooled to 20-40 ℃, the product is taken out, the product is centrifuged, the organic solvent is leached for 2 times in the centrifugal separation process, the mother liquor after leaching is conveyed to a hydrogenation reaction unit, the separated succinic anhydride solid is dried, the drying temperature is 150 ℃, and the purity of the succinic anhydride is detected to be more than or equal to 99.5%.
Example 5
The solid catalyst is a Cu catalyst (Cu loading is 35 percent based on the total weight of the catalyst), and the dosage of the catalyst is 10 percent based on the total volume of maleic anhydride added into the hydrogenation reaction kettle.
The maleic anhydride with the concentration of 30 weight percent is prepared by methyl formate, the solution and hydrogen are introduced into a hydrogenation reaction kettle together, the hydrogen is added by a membrane disperser, the molar ratio of the hydrogen to the maleic anhydride in the reaction material (the ratio of the hydrogen to the anhydride) is 4:1, a vacuum pump and a back pressure valve are adopted to control the absolute pressure in the reaction system to be 2bar, so that the reaction system is kept boiling, the reaction temperature is 51 ℃, methyl formate vapor and unreacted hydrogen are discharged from a gas outlet, and the reaction is carried out for 4 hours.
After the reaction is finished, the hydrogenation reaction kettle is cooled to 20-40 ℃, the product is taken out, the product is centrifuged, the organic solvent is leached for 2 times in the centrifugal separation process, the mother liquor after leaching is conveyed to a hydrogenation reaction unit, the separated succinic anhydride solid is dried, the drying temperature is 150 ℃, and the purity of the succinic anhydride is detected to be more than or equal to 99.5%.
Example 6
The solid catalyst is Ni catalyst (Ni load is 35% based on the total weight of the catalyst), and the dosage of the catalyst is 10% based on the total volume of maleic anhydride added into the hydrogenation reaction kettle.
The maleic anhydride with the concentration of 50 weight percent is prepared by methyl formate, the solution and hydrogen are introduced into a hydrogenation reaction kettle together, the hydrogen is added by a membrane disperser, the molar ratio of the hydrogen to the maleic anhydride in the reaction material (the ratio of the hydrogen to the anhydride) is 4:1, a vacuum pump and a back pressure valve are adopted to control the absolute pressure in the reaction system to be 4.7bar, so that the reaction system is kept boiling, the reaction temperature is 80 ℃, methyl formate vapor and unreacted hydrogen are discharged from a gas outlet, and the reaction is carried out for 4 hours.
After the reaction is finished, the hydrogenation reaction kettle is cooled to 20-40 ℃, the product is taken out, the product is centrifuged, the organic solvent is leached for 2 times in the centrifugal separation process, the mother liquor after leaching is conveyed to a hydrogenation reaction unit, the separated succinic anhydride solid is dried, the drying temperature is 150 ℃, and the purity of the succinic anhydride is detected to be more than or equal to 99.5%.
Example 7
The solid catalyst is Ni catalyst (Ni load is 35% based on the total weight of the catalyst), and the dosage of the catalyst is 20% based on the total volume of maleic anhydride added into the hydrogenation reaction kettle.
Preparing 65wt% maleic anhydride by tetrahydrofuran, introducing the solution and hydrogen into a hydrogenation reaction kettle, adding hydrogen by a membrane disperser, controlling the absolute pressure in a reaction system to be 2bar by adopting a vacuum pump and a back pressure valve, keeping the reaction system boiling, wherein the reaction temperature is 90 ℃, and tetrahydrofuran vapor and unreacted hydrogen are discharged from a gas outlet and react for 4 hours, wherein the mole ratio of the hydrogen to the maleic anhydride in the reaction material (the ratio of the hydrogen anhydride) is 4:1.
After the reaction is finished, the hydrogenation reaction kettle is cooled to 20-40 ℃, the product is taken out, the product is centrifuged, the organic solvent is leached for 2 times in the centrifugal separation process, the mother liquor after leaching is conveyed to a hydrogenation reaction unit, the separated succinic anhydride solid is dried, the drying temperature is 150 ℃, and the purity of the succinic anhydride is detected to be more than or equal to 99.5%.
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. And separating the reacted product by sequentially adopting a light component removing tower, a heavy component removing tower and a solvent refining tower to obtain the succinic anhydride product. Maleic anhydride conversion, succinic anhydride 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 maleic anhydride solution with the concentration of 40wt% is prepared by adopting r-butyrolactone as a solvent, the solid catalyst is Ni catalyst (Ni loading amount is 30 percent based on the total weight of the catalyst), and the dosage of the catalyst is 10 percent based on the total volume of maleic anhydride added into a hydrogenation reaction kettle. The molar ratio of hydrogen to maleic anhydride in the reaction mass (hydrogen anhydride ratio) was 3:1, except that: the absolute pressure in the reaction system is controlled to be 1.5bar by a vacuum pump and a back pressure valve, the reaction temperature is 80 ℃, the reaction system is not in a boiling state, the reaction kettle adopts external heat conduction oil to take heat, and unreacted hydrogen is discharged from a gas outlet for reaction for 3 hours. During the reaction, it was found that the internal temperature was elevated although the heat transfer oil was outside.
And after the reaction is finished, cooling the hydrogenation reaction kettle to 20-40 ℃, taking out the product, centrifuging, leaching the organic solvent for 2 times in the centrifugal separation process, conveying the leached mother liquor to a hydrogenation reaction unit, and drying the succinic anhydride solid obtained by separation.
Comparative example 3
Tetrahydrofuran is used as a solvent, and the conditions of maleic anhydride concentration, catalyst setting mode, hydrogen gas inlet mode, and hydrogen anhydride ratio are the same as those in example 7, except that: the absolute pressure in the reaction system is controlled to be 15bar by adopting a vacuum pump and a back pressure valve, the reaction temperature in the reaction kettle is controlled to be 100 ℃, and the reaction kettle is not in a boiling state because the pressure is higher, so that the reaction temperature is kept to be about 100 ℃ and does not fly, the reaction kettle needs to take heat by adopting external circulating cooling water, unreacted hydrogen is discharged from a gas outlet, and the reaction is carried out for 3 hours.
And after the reaction is finished, cooling the hydrogenation reaction kettle to 20-40 ℃, taking out the product, centrifuging, leaching the organic solvent for 2 times in the centrifugal separation process, conveying the leached mother liquor to a hydrogenation reaction unit, and drying the succinic anhydride solid obtained by separation.
The maleic anhydride conversion, succinic anhydride selectivity and energy consumption for producing succinic anhydride of example 3, example 7, and comparative examples 1-3 are shown in Table 2.
TABLE 2
Wherein, the energy consumption comprises the energy consumption of the refining of the succinic anhydride in the hydrogenation reaction process.
Claims (15)
1. A process for preparing succinic anhydride by hydrogenating maleic anhydride includes such steps as dissolving maleic anhydride in organic solvent with boiling point not higher than 150 deg.C and concentration of 10-75 wt%, reaction with hydrogen and solid catalyst in hydrogenation reactor, regulating reaction pressure to 30-150 deg.C, boiling solvent in reaction system, setting gas outlet on hydrogenation reactor, continuously discharging organic solvent and unreacted hydrogen from gas outlet, and solid-liquid separation and/or crystallizing separation.
2. Process according to claim 1, characterized in that the boiling point of the organic solvent is not higher than 120 ℃, more preferably not higher than 100 ℃.
3. The process according to claim 1, wherein the organic solvent is selected from at least one of tetrahydrofuran, diethyl ether, methyl formate and methyl acetate.
4. The process according to claim 1, wherein a stirring device is arranged in the hydrogenation reaction device.
5. The process of claim 1 wherein the solid catalyst is fixed to a location outside the bottom of the hydrogenation reactor.
6. The process of claim 4 wherein the solid catalyst is fixed to a stirring device.
7. The process of claim 6 wherein the solid catalyst is encapsulated in a plurality of porous gauze bags and is dispersedly affixed to the paddles.
8. 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.
9. Process according to claim 1, characterized in that the concentration of maleic anhydride is 20% to 70% by weight, preferably 25% to 60% by weight, more preferably 30% to 50% by weight.
10. The process of claim 1, wherein the hydrogenation reaction is carried out at a temperature of 40 ℃ to 120 ℃.
11. The process according to claim 1, wherein the hydrogenation reaction is carried out for a period of 20min to 5h.
12. 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.
13. The process of claim 7, wherein hydrogen is introduced from the bottom of the hydrogenation reactor or from a conduit into a net bag containing catalyst.
14. The process of claim 1, further comprising the step of recycling the mother liquor after crystallization separation to the maleic anhydride hydrolysis unit.
15. The process of claim 1 further comprising the step of condensing the water vapor at the gas outlet and unreacted hydrogen to recover hydrogen.
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