CN116023351A - Preparation method and system of succinic anhydride - Google Patents
Preparation method and system of succinic anhydride Download PDFInfo
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- CN116023351A CN116023351A CN202111260538.2A CN202111260538A CN116023351A CN 116023351 A CN116023351 A CN 116023351A CN 202111260538 A CN202111260538 A CN 202111260538A CN 116023351 A CN116023351 A CN 116023351A
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- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229940014800 succinic anhydride Drugs 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 164
- 239000007788 liquid Substances 0.000 claims abstract description 92
- 238000006243 chemical reaction Methods 0.000 claims abstract description 74
- 239000012071 phase Substances 0.000 claims abstract description 74
- 239000007791 liquid phase Substances 0.000 claims abstract description 71
- 239000007789 gas Substances 0.000 claims abstract description 62
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 238000004064 recycling Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 24
- 239000007795 chemical reaction product Substances 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 7
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000002737 fuel gas Substances 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 42
- 230000002349 favourable effect Effects 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 25
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000005265 energy consumption Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- PTVMKIXADNJEOT-UHFFFAOYSA-N N.[Ni].[Cu] Chemical compound N.[Ni].[Cu] PTVMKIXADNJEOT-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000010933 acylation Effects 0.000 description 1
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- 229920000180 alkyd Polymers 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- KGFLRTPDVLYMOL-UHFFFAOYSA-N cerium(3+) nickel(2+) dinitrate Chemical compound [N+](=O)([O-])[O-].[Ce+3].[N+](=O)([O-])[O-].[Ni+2] KGFLRTPDVLYMOL-UHFFFAOYSA-N 0.000 description 1
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- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation method of succinic anhydride and a system for preparing succinic anhydride. The method of the present invention preferably comprises: (1) The maleic anhydride solution is subjected to heat exchange through a raw material heat exchanger to reach the reaction temperature, enters a first-stage hydrogenation reactor from the upper part of the reactor, and the circulating hydrogen and the supplementary fresh hydrogen are mixed and enter from the top of the first-stage reactor; (2) The first-stage hydrogenation product is cooled to the reaction temperature through a heat exchanger, then is subjected to gas-liquid separation, the gas phase enters the reactor from the top of the second-stage reactor, and the liquid phase enters the second-stage reactor from the upper part of the reactor; (3) After gas-liquid separation, gas phase is recycled to the first-stage reactor for recycling, liquid phase part is sent to a subsequent rectification system, part of the liquid phase part is recycled and mixed with maleic anhydride solution, and the mixture enters the first-stage hydrogenation reactor from the upper part of the reactor. The method has mild reaction operation conditions and low temperature rise of the reaction bed layer, and is favorable for improving the selectivity of the catalyst and prolonging the service life of the catalyst.
Description
Technical Field
The invention relates to a preparation method of succinic anhydride and a system for preparing succinic anhydride.
Background
Succinic anhydride molecular formula: c (C) 4 H 4 O 3 Can generate hydrolysis, alcoholysis, esterification, halogenation, acylation and other reactions, is an important organic synthesis intermediate, and is widely used in the fields of medicines, food flavoring agents, pesticides, fine chemical engineering, alkyd resins and the like.
At present, the method for industrially producing succinic anhydride can be divided into two methods: namely a succinic acid dehydration method and a maleic anhydride hydrogenation method. The maleic anhydride hydrogenation method is divided into an electrochemical reduction method and a maleic anhydride direct hydrogenation method, and the electrochemical reduction method has the defects of high energy consumption, easy breakage of an ion membrane, complex process operation conditions and the like.
The direct maleic anhydride hydrogenation method is a method with the highest conversion rate and purity of succinic anhydride, and improves a plurality of problems of a biological fermentation method and a succinic anhydride dehydration method in technological process, operation conditions and production cost, but the maleic anhydride hydrogenation is a strong exothermic reaction (AH= -128 KJ/mol), the adiabatic temperature rise of the reaction is large, organic matters are easily initiated to polymerize and coke on the surface of a catalyst, the activity of the catalyst is reduced, and meanwhile, the temperature of a catalyst bed layer is easily caused to be rapidly increased, so that the phenomenon of temperature runaway occurs. Therefore, development of a maleic anhydride hydrogenation process is needed to effectively remove the heat released by the reaction.
CN101891718A discloses a continuous production process for preparing succinic anhydride by hydrogenating maleic anhydride, wherein maleic anhydride and solvent are dissolved and then react in a trickle bed reactor, and the finished succinic anhydride is obtained after gas-liquid separation and the separated solvent is recovered. Compared with the intermittent stirred tank process, the method has the great advantage of effectively improving the production efficiency, but the reaction pressure of the production process is higher (the reaction pressure is 2.0-8.0 MPa), the reaction energy consumption is higher, only a single trickle bed reactor is adopted, the heat removal effect is poor, and the strong exothermic effect of the reaction for preparing succinic anhydride by hydrogenating maleic anhydride can not be effectively solved.
Disclosure of Invention
In order to solve the problems of large heat release, difficult heat transfer, large investment in production process, high energy consumption and the like in the prior art in the process of preparing succinic anhydride by taking maleic anhydride as a raw material through hydrogenation, a novel preparation method and a novel preparation system for succinic anhydride are provided.
According to a first aspect of the present invention, there is provided a process for the preparation of succinic anhydride, which comprises carrying out a two-stage hydrogenation reaction,
(1) The maleic anhydride solution is subjected to heat exchange through a raw material heat exchanger until the reaction temperature is reached, the maleic anhydride solution enters a first-stage hydrogenation reactor from a liquid phase feed inlet at the upper part of the first-stage hydrogenation reactor to contact hydrogen for hydrogenation, and hydrogen enters the first-stage hydrogenation reactor from a gas phase inlet at the top of the first-stage hydrogenation reactor;
(2) Cooling the first-stage hydrogenation product in sequence, separating gas from liquid, allowing all gas phases separated from gas phase feed inlets at the top of the second-stage hydrogenation reactor to enter the second-stage hydrogenation reactor, allowing liquid phases separated from gas phases to enter the second-stage hydrogenation reactor from liquid phase feed inlets at the upper part of the second-stage reactor, reacting with hydrogen to obtain a second-stage hydrogenation product, and separating gas from liquid to obtain gas phases and liquid phase materials;
(3) And recycling part or all of gas phase obtained by separating the second-stage hydrogenation product to the first-stage hydrogenation reactor to be used as recycle hydrogen, and optionally recycling part of liquid phase material obtained by separating the second-stage hydrogenation product to the first-stage hydrogenation reactor to be used as raw material.
According to a second aspect of the present invention there is provided a system for preparing succinic anhydride, the system comprising:
along the material flow direction, a raw material heat exchanger, a first-stage hydrogenation reactor, a second-stage gas-liquid separator, a first-stage reaction product cooler and a first-stage gas-liquid separator which are sequentially connected in series are sequentially connected at the discharge port end at the bottom of the first-stage hydrogenation reactor;
the first-stage hydrogenation reactor comprises a top gas-phase feed inlet, an upper liquid-phase feed inlet and a bottom discharge outlet;
the second-stage hydrogenation reactor is communicated with the first-stage gas-liquid separator in series, and comprises a top gas-phase feed inlet, an upper liquid-phase feed inlet and a bottom discharge outlet, wherein the top gas-phase feed inlet is communicated with a top gas-phase outlet of the first-stage gas-liquid separator through a pipeline, and the upper liquid-phase feed inlet is communicated with a bottom liquid-phase outlet of the first-stage gas-liquid separator through a pipeline;
and the second-stage gas-liquid separator is communicated with a discharge hole at the bottom of the second-stage hydrogenation reactor in series.
According to the method disclosed by the invention, the raw materials are preheated to the reaction temperature, after the first-stage reaction, the gas phase is completely fed into the second-stage reactor after the gas-liquid separation after the temperature reduction, so that the reaction heat generated by the second-stage reaction can be effectively removed. The process and the method have the characteristics of simple flow, investment saving, strong applicability, easy control and the like.
According to a preferred embodiment of the invention, the method of the invention comprises:
(1) The maleic anhydride solution is subjected to heat exchange through a raw material heat exchanger to reach the reaction temperature, enters a first-stage hydrogenation reactor from the upper part of the reactor, and the circulating hydrogen and the supplementary fresh hydrogen are mixed and enter from the top of the first-stage reactor;
(2) The first-stage hydrogenation product is cooled to the reaction temperature through a heat exchanger, then is subjected to gas-liquid separation, the gas phase enters the reactor from the top of the second-stage reactor, and the liquid phase enters the second-stage reactor from the upper part of the reactor;
(3) After gas-liquid separation, gas phase is recycled to the first-stage reactor for recycling, liquid phase part is sent to a subsequent rectification system, part of the liquid phase part is recycled and mixed with maleic anhydride solution, and the mixture enters the first-stage hydrogenation reactor from the upper part of the reactor.
In summary, the method of the invention has the following characteristics: the method adopts the two-stage hydrogenation reactor, the raw materials are preheated to the reaction temperature, the materials at the outlet part of the two-stage reactor are extracted and recycled to the first-stage reactor, after the first-stage reaction, the gas phase and the liquid phase respectively enter the reactor after the gas-liquid separation by cooling, so that the method has the advantages of effectively removing the reaction heat generated by the second-stage reaction, along with high catalyst effective utilization rate, investment saving and the like. The method has mild reaction operation conditions and low temperature rise of the reaction bed layer, and is favorable for improving the selectivity of the catalyst and prolonging the service life of the catalyst.
Drawings
Fig. 1 is a schematic flow diagram according to a preferred embodiment of the present invention.
Fig. 2 is a schematic flow chart according to another preferred embodiment of the present invention.
Description of the reference numerals
1 a raw material heat exchanger; 2 a first-stage hydrogenation reactor; 3 a first stage reaction product cooler; 4, a first-stage gas-liquid separator; a 5-stage hydrogenation reactor; a second-stage gas-liquid separator; 7 a two-stage cooler; 8, a third gas-liquid separator; 11 maleic anhydride solution; 12 reaction products; 13 are supplemented with hydrogen.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
The present invention is described in detail below with reference to the specific drawings and examples, and it is necessary to point out that the following examples are given for further illustration of the present invention only and are not to be construed as limiting the scope of the present invention, since numerous insubstantial modifications and adaptations of the invention to those skilled in the art will still fall within the scope of the present invention.
The invention provides a preparation method of succinic anhydride, which comprises the steps of carrying out two-stage hydrogenation reaction,
(1) The maleic anhydride solution 11 is subjected to heat exchange through a raw material heat exchanger 1 until the reaction temperature is reached, and enters the first-stage hydrogenation reactor 2 from a liquid-phase feed inlet at the upper part of the first-stage hydrogenation reactor 2 to be contacted with hydrogen for hydrogenation, and hydrogen (comprising supplementary hydrogen (or fresh hydrogen) 13 or mixed hydrogen of the supplementary hydrogen and circulating hydrogen) enters the first-stage hydrogenation reactor 2 from a gas-phase inlet at the top part of the first-stage hydrogenation reactor 2;
(2) The first-stage hydrogenation products are sequentially cooled, gas-liquid separated, gas phases with gas-liquid separation are all fed into the second-stage hydrogenation reactor 5 from a gas phase feed inlet at the top of the second-stage hydrogenation reactor 5, and liquid phases with gas-liquid separation are fed into the second-stage hydrogenation reactor from a liquid phase feed inlet at the upper part of the second-stage reactor, and react with hydrogen to obtain second-stage hydrogenation products, and gas-liquid separation is carried out to obtain gas phases and liquid phase materials;
(3) Part or all of gas phase obtained by separating the second-stage hydrogenation product is recycled to the first-stage hydrogenation reactor to be used as recycle hydrogen, optionally part of liquid phase material obtained by separating the second-stage hydrogenation product is recycled to the first-stage hydrogenation reactor to be used as raw material, and the rest of liquid phase material is used as a reaction product 12 to enter a subsequent separation system. The method adopts the two-stage hydrogenation reactor, the raw materials are preheated to the reaction temperature, the materials at the outlet part of the two-stage reactor are extracted and recycled to the first-stage reactor, after the first-stage reaction, the gas phase and the liquid phase respectively enter the reactor after the gas-liquid separation by cooling, so that the method has the advantages of effectively removing the reaction heat generated by the second-stage reaction, along with high catalyst effective utilization rate, investment saving and the like. The method has mild reaction operation conditions and low temperature rise of the reaction bed layer, and is favorable for improving the selectivity of the catalyst and prolonging the service life of the catalyst.
According to a preferred embodiment of the present invention, in the step (2), the gas phase after gas-liquid separation is all fed into the two-stage hydrogenation reactor from the top, and the liquid phase is all fed into the hydrogenation reactor from the upper part of the two-stage reactor, and after two-stage hydrogenation reaction, maleic anhydride is all converted into succinic anhydride.
According to a preferred embodiment of the invention, in the step (2), after the gas-liquid separation of the second-stage hydrogenation reaction product, the gas-phase material is cooled by a heat exchanger, the cooling temperature is preferably 30-80 ℃, the cooled material is subjected to gas-liquid separation, the gas phase is recycled to the first-stage reactor for recycling, and the liquid phase is returned to the previous gas-liquid separator.
According to a preferred embodiment of the present invention, in the step (2), after the gas-liquid separation of the second-stage hydrogenation product, about 0.5% to 2% by volume of the material is preferably removed from the fuel gas by gas phase extraction, and the rest is recycled to the first-stage hydrogenation reactor, and after being mixed with the additional fresh hydrogen, the mixture enters the first-stage hydrogenation reactor.
According to a preferred embodiment of the present invention, in the step (2), the liquid phase after gas-liquid separation is preferably 10% -80% by volume, preferably 30% -70% by volume, of the liquid phase reaction product is sent to a subsequent separation system, and the remaining liquid phase reaction product is returned to a first-stage hydrogenation reactor for recycling.
According to a preferred embodiment of the present invention, optionally, in the step (1) and the step (2), the gas phase and the liquid phase are contacted with the catalyst after passing through the distributor when entering the first-stage reactor and the second-stage reactor.
According to a preferred embodiment of the invention, from 10 to 80% by weight of the liquid phase material of the two-stage hydrogenation is fed as reaction product (or liquid phase product) to a subsequent separation system, the remainder being returned to step (1) for use as feed. Therefore, the reaction heat generated by the second-stage reaction can be effectively removed, and the effective utilization rate of the catalyst can be improved.
According to a preferred embodiment of the invention, 0.5 to 2% by volume of the gas phase material of the two-stage hydrogenation is taken as fuel gas and the remainder is used as the recycle hydrogen. Therefore, the reaction heat generated by the second-stage reaction can be effectively removed, and the effective utilization rate of the catalyst can be improved.
According to a preferred embodiment of the present invention, in step (2), the operating conditions of the two-stage hydrogenation reactor comprise: the temperature is 30-120deg.C, preferably 40-100deg.C, such as 40deg.C, 41 deg.C, 42 deg.C, 43 deg.C, 44 deg.C, 45 deg.C, 46 deg.C, 47 deg.C, 48 deg.C, 49 deg.C, 50 deg.C, etc., and so on, and each reaction temperature is applicable to the present invention; and/or a pressure of 0.1 to 10MPa, preferably 0.5 to 5MPa; and/or space velocity of 0.5-5h -1 . Thereby effectively removing heat and improving the effective utilization rate of the catalyst.
According to a preferred embodiment of the invention, in step (1), the molar ratio of hydrogen to maleic anhydride is from 5 to 100, preferably from 10 to 40. In the invention, the hydrogen in the step (1) is fresh hydrogen or mixed hydrogen of the fresh hydrogen and circulated hydrogen. The hydrogen formula is a formula of a total hydrogen amount, and the maleic anhydride formula is a formula of a total maleic anhydride amount.
According to a preferred embodiment of the present invention, in the step (1), the formulation of the maleic anhydride solution is not particularly limited, and is generally a mixture of maleic anhydride and a solvent, and the type of solvent is not particularly limited, and according to a preferred embodiment of the present invention, the solvent is one or more of acetic anhydride, gamma-butyrolactone, dioxane, tetrahydrofuran, aromatic hydrocarbon, ethyl acetate, four-carbon dibasic acid ester, ethanol, isopropanol, hexane, cyclohexane, propylene oxide, ketone and ether.
By adopting the method provided by the invention, the maleic anhydride concentration in the incoming maleic anhydride solution can be not too low, the solvent consumption is reduced, and the energy consumption for subsequent solvent recovery is reduced. According to a preferred embodiment of the invention, in step (1), the maleic anhydride concentration of the maleic anhydride solution is from 1 to 90% by weight, preferably from 10 to 40% by weight.
According to a preferred embodiment of the present invention, in step (1), the operating conditions of the one-stage hydrogenation reactor comprise: the temperature is 30-100deg.C, preferably 40-80deg.C, such as 40deg.C, 41 deg.C, 42 deg.C, 43 deg.C, 44 deg.C, 45 deg.C, 46 deg.C, 47 deg.C, 48 deg.C, 49 deg.C, 50 deg.C, etc., in sequenceBy analogy, each reaction temperature is suitable for the present invention; and/or the reaction pressure is 0.1 to 10MPa, preferably 0.5 to 5MPa; and/or, airspeed of 0.5 to 5 hours -1 . Therefore, the utilization rate of the catalyst can be effectively improved, and the reaction heat can be effectively removed.
According to a preferred embodiment of the invention, the maleic anhydride conversion is preferably from 30 to 90% after the end of the one-stage hydrogenation reactor. Therefore, the total conversion rate and the selectivity can be improved to the maximum extent, and the whole hydrogenation reaction can effectively remove heat.
According to a preferred embodiment of the invention, the method further comprises:
cooling a gas phase obtained by gas-liquid separation of the second-stage hydrogenation product, and then performing third gas-liquid separation, wherein part or all of the obtained gas phase is used as circulating hydrogen and returned to the first-stage hydrogenation reactor; optionally, the liquid phase obtained by the third gas-liquid separation is returned to the two-stage gas-liquid separator for gas-liquid separation. Therefore, the utilization rate of the catalyst can be effectively improved, and the reaction heat can be effectively removed.
According to a preferred embodiment of the present invention, the gas phase obtained by gas-liquid separation of the two-stage hydrogenation product is cooled to a temperature of 30 to 80 ℃. Therefore, the utilization rate of the catalyst can be effectively improved, and the reaction heat can be effectively removed.
The present invention is mainly directed to process design, and hydrogenation catalysts such as a first-stage hydrogenation reactor and a second-stage hydrogenation reactor, wherein the catalyst to be packed is not limited, and any hydrogenation catalyst can be used, such as the catalysts described in chinese patent applications 20201118431. X, CN 202011120495.3.
The method has mild reaction operation conditions and low temperature rise of the reaction bed layer, and is favorable for improving the selectivity of the catalyst and prolonging the service life of the catalyst.
In accordance with the present invention, there is provided a system for preparing succinic anhydride, the system comprising:
along the material flow direction, a raw material heat exchanger 1, a first-stage hydrogenation reactor 2, a second-stage hydrogenation reactor 5, a second-stage gas-liquid separator 6, a first-stage reaction product cooler 3 and a first-stage gas-liquid separator 4 which are sequentially connected in series at the discharge port end at the bottom of the first-stage hydrogenation reactor 2;
the first-stage hydrogenation reactor 2 comprises a top gas-phase feed inlet, an upper liquid-phase feed inlet and a bottom discharge outlet;
the second-stage hydrogenation reactor 5 is communicated with the first-stage gas-liquid separator 4 in series, the second-stage hydrogenation reactor 5 comprises a top gas-phase feed inlet, an upper liquid-phase feed inlet and a bottom discharge outlet, the top gas-phase feed inlet is communicated with a top gas-phase outlet of the first-stage gas-liquid separator 4 through a pipeline, and the upper liquid-phase feed inlet is communicated with a bottom liquid-phase outlet of the first-stage gas-liquid separator 4 through a pipeline;
and the second-stage gas-liquid separator 6 is communicated with a discharge hole at the bottom of the second-stage hydrogenation reactor 5 in series.
According to a preferred embodiment of the invention, the top gas phase outlet of the two-stage gas-liquid separator 6 is in communication with the top gas phase feed of the one-stage hydrogenation reactor 2 via a pipeline.
According to a preferred embodiment of the present invention, the bottom liquid phase outlet of the two-stage gas-liquid separator 6 is in communication with the upper liquid phase feed inlet of the one-stage hydrogenation reactor 2 via a pipeline.
According to a preferred embodiment of the invention, a second-stage cooler 7 and a third gas-liquid separator 8 are sequentially arranged in series at the top gas phase outlet end of the second-stage gas-liquid separator 6, and the gas phase outlet of the third gas-liquid separator 8 is communicated with the top gas phase feed inlet of the first-stage hydrogenation reactor 2 through a pipeline; the bottom liquid phase outlet of the third gas-liquid separator 8 is communicated with the liquid phase feed inlet of the second-stage gas-liquid separator 6.
According to a preferred embodiment of the present invention, the upper middle part of the first-stage hydrogenation reactor 2 and the second-stage hydrogenation reactor 5 is provided with a raw material distributor so as to make the gas-liquid two-phase mixture more uniform and then contact with the catalyst, and the shape and structure of the raw material distributor are specially required, and all the existing components capable of enhancing the gas-liquid mixture can be used in the present invention, which is not described in detail herein.
The system according to the invention may comprise, in addition to the devices listed in the figures, pumps, heat exchangers, tanks, compressors, etc., as desired and as required by the person skilled in the art.
According to a preferred embodiment of the present invention, the following examples are carried out using the flow shown in fig. 1 or fig. 2,
in fig. 1 and 2, 1 a feed heat exchanger; 2 a first-stage hydrogenation reactor; 3 a first stage reaction product cooler; 4, a first-stage gas-liquid separator; a 5-stage hydrogenation reactor; a second-stage gas-liquid separator; 7 a two-stage cooler; 8, a third gas-liquid separator; 11 maleic anhydride solution; 12 reaction products; 13 are supplemented with hydrogen.
The method of the invention comprises the following steps:
(1) The maleic anhydride solution 11 is subjected to heat exchange through a raw material heat exchanger 1 until the reaction temperature is reached, and enters the first-stage hydrogenation reactor 2 from a liquid-phase feed inlet at the upper part of the first-stage hydrogenation reactor 2 to be contacted with hydrogen for hydrogenation, and hydrogen (comprising supplementary hydrogen (or fresh hydrogen) 13 or mixed hydrogen of the supplementary hydrogen and circulating hydrogen) enters the first-stage hydrogenation reactor 2 from a gas-phase inlet at the top part of the first-stage hydrogenation reactor 2;
(2) Cooling and cooling the first-stage hydrogenation product in a first-stage reaction product cooler 3 in sequence, separating gas from liquid in a first-stage gas-liquid separator 4, enabling all gas phases subjected to gas-liquid separation to enter a second-stage hydrogenation reactor 5 from a gas phase feed inlet at the top of the second-stage hydrogenation reactor 5, enabling liquid phases subjected to gas-liquid separation to enter the second-stage hydrogenation reactor from a liquid phase feed inlet at the upper part of the second-stage hydrogenation reactor, reacting to obtain a second-stage hydrogenation product, and separating gas from liquid in a second-stage gas-liquid separator 6 to obtain gas phases and liquid phase materials;
(3) Optionally, part or all of gas phase obtained by separating the second-stage hydrogenation product is recycled to the first-stage hydrogenation reactor to be used as recycle hydrogen, part of liquid phase material obtained by separating the second-stage hydrogenation product is recycled to the first-stage hydrogenation reactor to be used as raw material, and the rest of liquid phase material is used as a reaction product 12 to enter a subsequent separation system.
Or as shown in fig. 2, in the step (2), after the gas-liquid separation of the second-stage hydrogenation reaction product by the second-stage gas-liquid separator 6, the gas-phase material is cooled by the second-stage cooler 7, the cooling temperature is preferably 30-80 ℃, the cooled material enters the third gas-liquid separator 8 for gas-liquid separation, the gas phase is circulated to the first-stage hydrogenation reactor for recycling, and the liquid phase is returned to the previous gas-liquid separator.
The maleic anhydride hydrogenation reaction process and method of the invention have the following characteristics:
(1) The invention adopts two sections of hydrogenation reactors, and extracts the material at the outlet of the two sections of reactors to circulate to the first section of reactor, and the material does not contain maleic anhydride, so that the maleic anhydride content in the feed of the first section of reaction can be effectively diluted, and the reaction heat generated by the first section of reaction is taken away.
(2) After the first-stage reaction, the gas phase is completely fed into the second-stage reactor after the temperature reduction gas-liquid separation, so that the reaction heat generated by the second-stage reaction can be effectively removed.
(3) After the first-stage reactor, the invention sets gas-liquid separation, the gas phase and the liquid phase respectively enter the reactor, and a gas-liquid phase distribution device can be selected, so that the materials entering the reactor are more fully contacted, the gas-liquid solid contact is good, the effective utilization rate of the catalyst is high, and the investment is saved.
(4) The invention has mild reaction operation condition, can react at about 40 ℃, greatly reduces the reaction temperature, has low temperature rise of the reaction bed layer, and is favorable for improving the selectivity of the catalyst and prolonging the service life of the catalyst.
The following examples employed the following catalysts:
chinese patent application cn20201118431. X-example 1
(1) 50.00g of basic nickel carbonate (nickel content: 45% by weight) and 9.16g of Cu (NO) were weighed out 3 ) 2 ·3H 2 Mixing 49.91g of ethylenediamine tetraacetic acid, 500g of deionized water and 100g of 25 wt% ammonia water, introducing ammonia gas, regulating the pH value of the solution to 10.5, and stirring at 45 ℃ until all solids are dissolved to obtain a nickel-copper ammonia complex solution;
(2) Weighing 458.31g of silica sol and mixing the silica sol with the nickel-copper ammonia complex solution obtained in the step (1) to obtain a mixed solution;
(3) Aging the mixed solution for 14 hours at the temperature of 60 ℃ under stirring, and drying for 12 hours at the temperature of 120 ℃ to obtain a catalyst precursor;
(4) Will contain 11.41g of Ce (NO) 3 ) 3 ·6H 2 Saturated impregnation of the catalyst precursor with a cerium nitrate solution of O to obtainTo the matrix catalyst;
(5) Drying the matrix catalyst at 115 ℃ for 12 hours, then roasting at 400 ℃ for 4 hours, and forming to obtain the catalyst S1.
The catalyst S1 comprises, based on the total weight of the catalyst S1: 19 wt% NiO, 2 wt% CuO, 3 wt% CeO 2 And 76% by weight of SiO 2 。
Chinese patent application CN 202011120495.3-example 1
(1) 10.90g of Ni (NO 3) 3.6H was weighed out 2 O and 5.04g of Ce (NO) 3 ) 3 ·6H 2 Cerium oxide, dissolved in water and fixed to a volume of 50.0ml, and then 50g of SiO as a carrier 2 Immersing (specific surface area 300m2/g, water absorption 1.0 mL/g) in nickel nitrate-cerium nitrate mixed solution, stirring uniformly, standing and aging for 4 hours, then drying at 120 ℃ for 12 hours, and finally roasting at 450 ℃ in air for 4 hours to obtain a composite oxide carrier E;
(2) The composite oxide carrier E is added into 100ml of ruthenium metal solution with exothermic Ru content of 0.02g/L, ammonia water with mass concentration of 25% is added dropwise under stirring, the pH value of the solution is regulated and maintained at 9 and 55 ℃ for reaction for 6 hours, then the solution is filtered, then dried at 110 ℃ for 12 hours, and finally baked in air at 500 ℃ for 4 hours, thus obtaining the finished catalyst S1.
The catalyst S1 contains: siO with the catalyst carrier 2 Wherein the mass fraction of Ni in the catalyst is 7% of the mass of the carrier, ceO 2 The mass fraction of (2) is 4% of the mass of the carrier, and the mass fraction of Ru is 0.4% of the mass of the carrier.
Example 1
The maleic anhydride hydrogenation reaction method shown in figure 1 is adopted, the solvent adopts gamma-butyrolactone, the maleic anhydride content in the maleic anhydride solution is 10 weight percent, the maleic anhydride solution is continuously introduced into a first-stage hydrogenation reactor, the molar ratio of hydrogen to maleic anhydride is 12, and the space velocity of the first-stage hydrogenation reactor is 2.5h -1 The reaction temperature is 40 ℃ and the reaction pressure is 1.5MPa. Cooling the first-stage hydrogenation reaction product to 40 ℃, separating gas from liquid, respectively feeding the gas phase and the liquid phase into a second-stage hydrogenation reactor, and the space velocity of the second-stage hydrogenation reactor is 1h -1 The reaction temperature is 45 ℃ and the reaction pressure is 1.3MPa. And (3) after the second-stage hydrogenation reaction product passes through a gas-liquid separator, 1% by volume of gas phase is extracted, the rest gas phase and the supplementary fresh hydrogen are sent into a first-stage hydrogenation reactor together, 65% by volume of liquid phase is sent to a subsequent separation system, 35% by volume of liquid phase returns to the first-stage hydrogenation reactor, and after being mixed with maleic anhydride solution, the mixture is subjected to heat exchange to 40 ℃ and enters the first-stage hydrogenation reactor. The catalysts filled in the first-stage hydrogenation reactor and the second-stage hydrogenation reactor are Ni active component catalysts, and the specific composition is shown in the Chinese patent CN20201118431. X-example 1.
The maleic anhydride conversion rate of the first-stage hydrogenation reactor is 45%, the total maleic anhydride conversion rate is 99.5% after two-stage reaction, and the total succinic anhydride selectivity is 98.9%.
Example 2
The maleic anhydride hydrogenation reaction method shown in figure 2 is adopted, dioxane is adopted as the solvent, the maleic anhydride content in the maleic anhydride solution is 18 weight percent, the maleic anhydride solution is continuously introduced into a first-stage hydrogenation reactor, the molar ratio of hydrogen to maleic anhydride is 30, and the space velocity of the first-stage hydrogenation reactor is 1.8h -1 The reaction temperature is 40 ℃ and the reaction pressure is 1.3MPa. Cooling the first-stage hydrogenation reaction product to 45 ℃, separating gas from liquid, respectively feeding the gas phase and the liquid phase into a second-stage hydrogenation reactor, and controlling the space velocity of the second-stage hydrogenation reactor to be 0.6h -1 The reaction temperature is 48 ℃ and the reaction pressure is 1.2MPa. The second-stage hydrogenation reaction product is cooled to 40 ℃ again after passing through a gas-liquid separator, and then is sent into a first-stage hydrogenation reactor together with the supplementary fresh hydrogen after passing through the gas-liquid separator, 50% liquid phase is sent to a subsequent separation system, 50% liquid phase returns to the first-stage hydrogenation reactor, is mixed with maleic anhydride solution, and then is subjected to heat exchange to 40 ℃ and enters the first-stage hydrogenation reactor.
The catalysts filled in the first-stage hydrogenation reactor and the second-stage hydrogenation reactor are Ni active component catalysts, and the specific composition is shown in Chinese patent CN 202011120495.3-example 1.
The maleic anhydride conversion rate of the first-stage hydrogenation reactor is 40%, the total maleic anhydride conversion rate is 99.8% after two-stage reaction, and the total succinic anhydride selectivity is 99.6%.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (10)
1. A preparation method of succinic anhydride is characterized by comprising the steps of carrying out a two-stage hydrogenation reaction,
(1) The maleic anhydride solution is subjected to heat exchange through a raw material heat exchanger until the reaction temperature is reached, the maleic anhydride solution enters a first-stage hydrogenation reactor from a liquid phase feed inlet at the upper part of the first-stage hydrogenation reactor to contact hydrogen for hydrogenation, and hydrogen enters the first-stage hydrogenation reactor from a gas phase inlet at the top of the first-stage hydrogenation reactor;
(2) Cooling the first-stage hydrogenation product in sequence, separating gas from liquid, allowing all gas phases separated from gas phase feed inlets at the top of the second-stage hydrogenation reactor to enter the second-stage hydrogenation reactor, allowing liquid phases separated from gas phases to enter the second-stage hydrogenation reactor from liquid phase feed inlets at the upper part of the second-stage reactor, reacting with hydrogen to obtain a second-stage hydrogenation product, and separating gas from liquid to obtain gas phases and liquid phase materials;
(3) And recycling part or all of gas phase obtained by separating the second-stage hydrogenation product to the first-stage hydrogenation reactor to be used as recycle hydrogen, and optionally recycling part of liquid phase material obtained by separating the second-stage hydrogenation product to the first-stage hydrogenation reactor to be used as raw material.
2. The process according to claim 1, wherein 10 to 80% by volume, preferably 30 to 70% by volume of the liquid phase material of the two-stage hydrogenation is sent as liquid phase product to a subsequent separation system, and the remainder is returned to step (1) for use as raw material;
and the gas phase material of the second-stage hydrogenation reaction is extracted to be 0.5-2% by volume and used as fuel gas, and the rest is used as the circulating hydrogen.
3. The production process according to claim 1 or 2, wherein in step (2), the operating conditions of the two-stage hydrogenation reactor include:
the temperature is 30-120deg.C, preferably 40-100deg.C; and/or a pressure of 0.1 to 10MPa, preferably 0.5 to 5MPa; and/or space velocity of 0.5-5h -1 。
4. A process according to any one of claims 1 to 3, wherein in step (1),
the molar ratio of hydrogen to maleic anhydride is 5-100, preferably 10-40; and/or
The maleic anhydride solution is a mixture of maleic anhydride and a solvent, wherein the solvent is one or more of acetic anhydride, gamma-butyrolactone, dioxane, tetrahydrofuran, aromatic hydrocarbon, ethyl acetate, four-carbon dibasic acid ester, ethanol, isopropanol, hexane, cyclohexane, propylene oxide, ketone and ether; and/or
The maleic anhydride concentration of the maleic anhydride solution is 1 to 90 wt%, preferably 10 to 40 wt%; and/or.
5. The process according to any one of claim 1 to 4, wherein in the step (1),
the operating conditions of the stage hydrogenation reactor include: the temperature is 30-100deg.C, preferably 40-80deg.C; and/or the reaction pressure is 0.1 to 10MPa, preferably 0.5 to 5MPa; and/or, airspeed of 0.5 to 5 hours -1 。
6. The production method according to any one of claims 1 to 5, wherein the method further comprises:
cooling a gas phase obtained by gas-liquid separation of the second-stage hydrogenation product, and then performing third gas-liquid separation, wherein part or all of the obtained gas phase is used as circulating hydrogen and returned to the first-stage hydrogenation reactor; optionally, the liquid phase obtained by the third gas-liquid separation is returned to the two-stage gas-liquid separator for gas-liquid separation.
7. The process according to claim 6, wherein the gas phase obtained by separating the two-stage hydrogenation product from the gas phase is cooled at a temperature of 30 to 80 ℃.
8. A system for producing succinic anhydride, the system comprising:
along the material flow direction, a raw material heat exchanger (1), a first-stage hydrogenation reactor (2), a second-stage hydrogenation reactor (5), a second-stage gas-liquid separator (6) and a first-stage reaction product cooler (3) and a first-stage gas-liquid separator (4) which are sequentially connected in series at the discharge port end at the bottom of the first-stage hydrogenation reactor (2) are sequentially connected in series;
the first-stage hydrogenation reactor (2) comprises a top gas-phase feed inlet, an upper liquid-phase feed inlet and a bottom discharge outlet;
the second-stage hydrogenation reactor (5) is communicated with the first-stage gas-liquid separator (4) in series, the second-stage hydrogenation reactor (5) comprises a top gas-phase feed inlet, an upper liquid-phase feed inlet and a bottom discharge outlet, the top gas-phase feed inlet is communicated with a top gas-phase outlet of the first-stage gas-liquid separator (4) through a pipeline, and the upper liquid-phase feed inlet is communicated with a bottom liquid-phase outlet of the first-stage gas-liquid separator (4) through a pipeline;
the second-stage gas-liquid separator (6) is communicated with a discharge hole at the bottom of the second-stage hydrogenation reactor (5) in series.
9. The system according to claim 8,
the top gas phase outlet of the two-stage gas-liquid separator (6) is communicated with the top gas phase feed inlet of the first-stage hydrogenation reactor (2) through a pipeline; and/or
The bottom liquid phase outlet of the two-stage gas-liquid separator (6) is communicated with the upper liquid phase feed inlet of the first-stage hydrogenation reactor (2) through a pipeline.
10. The system according to claim 8 or 9, wherein a second-stage cooler (7) and a third gas-liquid separator (8) are sequentially arranged in series at the top gas-phase outlet end of the second-stage gas-liquid separator (6), and the gas-phase outlet of the third gas-liquid separator (8) is communicated with the top gas-phase feed inlet of the first-stage hydrogenation reactor (2) through a pipeline; the bottom liquid phase outlet of the third gas-liquid separator (8) is communicated with the liquid phase feed inlet of the second-stage gas-liquid separator (6).
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389751A (en) * | 2011-08-17 | 2012-03-28 | 徐志刚 | Fixed bed reactor and method for preparing butanedioic anhydride through maleic anhydride solution hydrogenation |
| CN103570650A (en) * | 2013-11-13 | 2014-02-12 | 山西大学 | Technological process for continuously producing succinic anhydride and co-producing succinic acid through maleic anhydride hydrogenation |
| CN103566837A (en) * | 2013-11-13 | 2014-02-12 | 山西大学 | External circular reaction device suitable for hydrogenation exothermic reaction |
| CN105801536A (en) * | 2016-04-07 | 2016-07-27 | 上海华谊（集团）公司 | Method for preparing succinic anhydride from maleic anhydride through liquid-phase selective hydrogenation |
| CN107253938A (en) * | 2017-08-17 | 2017-10-17 | 冯岩 | Cis-butenedioic anhydride direct hydrogenation prepares the production technology of high purity butylene dicarboxylic anhydride |
| CN111689845A (en) * | 2020-03-18 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Process for producing succinic acid by maleic anhydride aqueous phase hydrogenation |
| CN111689849A (en) * | 2020-03-18 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Method for producing succinic acid by liquid-phase two-stage hydrogenation |
-
2021
- 2021-10-27 CN CN202111260538.2A patent/CN116023351A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102389751A (en) * | 2011-08-17 | 2012-03-28 | 徐志刚 | Fixed bed reactor and method for preparing butanedioic anhydride through maleic anhydride solution hydrogenation |
| CN103570650A (en) * | 2013-11-13 | 2014-02-12 | 山西大学 | Technological process for continuously producing succinic anhydride and co-producing succinic acid through maleic anhydride hydrogenation |
| CN103566837A (en) * | 2013-11-13 | 2014-02-12 | 山西大学 | External circular reaction device suitable for hydrogenation exothermic reaction |
| CN105801536A (en) * | 2016-04-07 | 2016-07-27 | 上海华谊（集团）公司 | Method for preparing succinic anhydride from maleic anhydride through liquid-phase selective hydrogenation |
| CN107253938A (en) * | 2017-08-17 | 2017-10-17 | 冯岩 | Cis-butenedioic anhydride direct hydrogenation prepares the production technology of high purity butylene dicarboxylic anhydride |
| CN111689845A (en) * | 2020-03-18 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Process for producing succinic acid by maleic anhydride aqueous phase hydrogenation |
| CN111689849A (en) * | 2020-03-18 | 2020-09-22 | 中国科学院山西煤炭化学研究所 | Method for producing succinic acid by liquid-phase two-stage hydrogenation |
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