CN115611832B - Process for preparing succinic anhydride by maleic anhydride hydrogenation - Google Patents
Process for preparing succinic anhydride by maleic anhydride hydrogenation Download PDFInfo
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- CN115611832B CN115611832B CN202211270851.9A CN202211270851A CN115611832B CN 115611832 B CN115611832 B CN 115611832B CN 202211270851 A CN202211270851 A CN 202211270851A CN 115611832 B CN115611832 B CN 115611832B
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- 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 55
- 229940014800 succinic anhydride Drugs 0.000 title claims abstract description 55
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 48
- 239000006227 byproduct Substances 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 37
- 239000000047 product Substances 0.000 claims abstract description 30
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000000926 separation method Methods 0.000 claims abstract description 26
- 230000005587 bubbling Effects 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- -1 butyl lactone Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 26
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 12
- 239000012071 phase Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 238000011084 recovery Methods 0.000 claims description 7
- 229920000180 alkyd Polymers 0.000 claims description 5
- 150000008064 anhydrides Chemical class 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000005265 energy consumption Methods 0.000 abstract description 8
- 238000012423 maintenance Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 9
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 8
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 4
- 239000000543 intermediate Substances 0.000 description 4
- 239000001384 succinic acid Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229920006238 degradable plastic Polymers 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/60—Two oxygen atoms, e.g. succinic anhydride
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
- B01D3/4211—Regulation; Control of columns
- B01D3/4227—Head- and bottom stream
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0446—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical
- B01J8/0449—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds
- B01J8/0457—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the flow within the beds being predominantly vertical in two or more cylindrical beds the beds being placed in separate reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0492—Feeding reactive fluids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
Abstract
The invention discloses a process for preparing succinic anhydride by hydrogenating maleic anhydride, which solves the problems of high equipment investment and operation cost, high energy consumption and further improvement of product quality in the prior art. The technical scheme includes that mixed solution of solvent gamma butyl lactone and maleic anhydride is sequentially sent into three hydrogenation reactors connected in series to carry out selective hydrogenation reaction in the presence of a catalyst, then, cyclic hydrogen separation is carried out through a hydrogen thermal separation tank, byproducts are removed through a byproduct removal tower, the solvent is removed through a solvent removal tower, and medical-grade succinic anhydride is obtained at the tower top after rectification of a succinic anhydride rectifying tower, and industrial-grade succinic anhydride is obtained at the tower bottom; the bottom section of the hydrogenation reactor is a bubbling fixed bed section, the middle section is a tubular heat-taking section, and the upper section is a bubbling fixed bed section. The invention has the advantages of simple process, high product yield, good quality, small occupied space of equipment, easy overhaul and maintenance and low investment and operation cost.
Description
Technical Field
The invention relates to a process for preparing succinic anhydride by maleic anhydride hydrogenation.
Background
In the field of degradable plastics, PBS is paid attention to and favored by its excellent degradability, mechanical properties close to PP, excellent mechanical processability, heat resistance exceeding 100 ℃ and better light stability. The raw materials for producing PBS are 1, 4-butanediol and succinic acid or succinic anhydride, the production technology of the 1, 4-butanediol is mature and stable, and the production technology of the succinic anhydride is a limiting technology for restricting the development of the PBS industry.
The existing succinic acid production technology comprises an electrochemical method, a biological fermentation method, a paraffin oxidation method and a maleic anhydride hydrogenation method. The electrochemical method has mature process, but has the defects of high electricity consumption, serious equipment corrosion, large investment and large occupied area; the biological fermentation method has the advantages of low raw material cost and low energy consumption, but has the defects of low product yield, difficult product purification, high wastewater yield and the like; paraffin oxidation process has mature technology, but complex product, difficult separation and low product yield. The maleic anhydride hydrogenation method is widely focused by research institutions at home and abroad, and results of related experiments are made, so that the maleic anhydride hydrogenation method is considered as the most promising technology for producing PBS raw materials.
The maleic anhydride hydrogenation method is divided into a maleic anhydride direct hydrogenation process and a maleic anhydride hydrogenation process with a solvent, and the direct hydrogenation method has the advantages of large reaction heat release, difficult accurate control of reaction temperature, relatively more byproducts, difficult separation and low yield of target products. The maleic anhydride hydrogenation method with solvent has the advantages of convenient raw material storage and transportation, easy control of reaction temperature, difficult formation of hot spots on the bed, less side reaction and high product yield. The maleic anhydride hydrogenation method with solvent is hereinafter referred to as maleic anhydride hydrogenation method.
The solvent used in the maleic anhydride hydrogenation method can be tetrahydrofuran or gamma-butyrolactone. Tetrahydrofuran has a low boiling point, and the explosion risk of the medium is higher than that of gamma-butyl lactone, but under the condition of low temperature, the diffusion speed of hydrogen is faster, thereby being beneficial to the hydrogenation reaction. But tetrahydrofuran has lower solubility for succinic anhydride product than gamma-butyrolactone, which requires a larger solvent ratio to meet the reaction process requirement. THF will not be advantageous in terms of energy consumption when the apparatus is enlarged, but it will be more advantageous if a crystallization separation process is used as solvent. When gamma-butyrolactone is used as a solvent, the higher concentration of ingredients can be allowed because of the higher solubility of the gamma-butyrolactone to the raw material maleic anhydride and the succinic anhydride of the product, and the higher concentration of ingredients means that the energy consumption of the fractionation part of the product is lower. Thus, when the device is enlarged, gamma-butyrolactone is superior to tetrahydrofuran as a solvent. However, after the concentration of ingredients is increased, the reaction temperature rise is larger, and if the reaction temperature rise cannot be effectively controlled, byproducts are increased, which brings difficulty to the design of a reaction system. Currently available industrial plants are designed with feed concentrations below 20% wt, because of the inability to control effectively in order to prevent excessive temperature rise.
The existing technology for preparing succinic anhydride by maleic anhydride hydrogenation still has the following problems:
(1) The existing technology adopts a larger circulation ratio, namely more reaction products are circulated to the inlet of the reactor, the concentration of maleic anhydride entering the reactor is more than 3-5 wt%, if the concentration of maleic anhydride is high, the temperature rise of the reactor is larger, thus the selectivity is unfavorable, in addition, the larger circulation ratio also increases the loss of solvent, as the solvent can react in trace amount to generate byproducts such as tetrahydrofuran, 1, 4-butanediol, and the like. If an isothermal reactor with good control effect is adopted, the catalyst is arranged in the pipe of the isothermal reactor, and a cooling medium is arranged outside the pipe, so that the problems of huge equipment volume (about 3-5 times of a fixed bed reactor) and low space utilization rate (less than 50%) of the reactor are caused. In addition, with the enlargement of the apparatus, the uniformity of heat transfer is difficult to be ensured during the enlargement of the isothermal reactor.
(2) The existing technology does not extract the byproduct tetrahydrofuran due to small scale of the device, which causes the conditions that the tail gas does not reach the standard and the solvent loss is increased.
(3) The temperature of the bottom of the light component removing tower in the prior art is 120-160 ℃, and the condition of color change of the solvent and increased consumption of raw materials exists in actual production.
(4) The highest purity of succinic anhydride in the prior art is 99.7%, and the yellowing condition of the product still exists in the polymerization process.
Therefore, on the premise that gamma-butyrolactone is used as a solvent, how to further improve the concentration of maleic anhydride in the feed, reduce the solvent circulation ratio, reduce the equipment investment and the running cost and improve the product quality is a technical problem which needs to be solved by the technicians in the field.
Disclosure of Invention
The invention aims to solve the technical problems and provide a process for preparing succinic anhydride by hydrogenating maleic anhydride, which has the advantages of simple process, high product yield, good quality, small occupied space of equipment, easy overhaul and maintenance and low investment and operation cost.
The technical scheme includes that mixed solution of solvent gamma butyl lactone and maleic anhydride is sequentially sent into three hydrogenation reactors connected in series to carry out selective hydrogenation reaction in the presence of a catalyst, then, cyclic hydrogen separation is carried out through a hydrogen thermal separation tank, byproducts are removed through a byproduct removal tower, the solvent is removed through a solvent removal tower, and medical-grade succinic anhydride is obtained at the tower top after rectification of a succinic anhydride rectifying tower, and industrial-grade succinic anhydride is obtained at the tower bottom;
the bottom section of the hydrogenation reactor is a bubbling fixed bed section, the middle section is a tube type heat-taking section, a catalyst is filled in a tube, the upper section is a bubbling fixed bed section, mixed liquid enters and exits from the bottom, hydrogen is introduced into the middle section and the bottom section, the reaction temperature of each section is controlled to be 15-25 ℃, the total temperature of each hydrogenation reactor is controlled to be 15-30 ℃, and a hot water cooler is arranged between two adjacent hydrogenation reactors.
Controlling the reaction pressure of each hydrogenation reactor to be 5-7MPaG, the hydrogen-oil ratio to be 30-100 and the solvent ratio to be 70-75%wt.
The inlet temperature of the first hydrogenation reactor is controlled to be 55 ℃, the outlet temperature is controlled to be 85 ℃, the inlet temperature of the second hydrogenation reactor and the third hydrogenation reactor is controlled to be 60 ℃, and the outlet temperature is controlled to be 85 ℃.
The height-to-diameter ratio of the bed layer of the hydrogenation reactor is 3-6:1.
And (3) circularly separating hydrogen from the reaction products after hydrogenation reaction in the three hydrogenation reactors by using a hydrogen thermal separation tank, wherein one part of separated liquid phase is used as circulating liquid to be returned to the hydrogenation reactor together with the mixed liquid, the reaction circulation ratio is 0-2:1, and the other part of separated liquid phase is sent to a byproduct removal tower.
The concentration of maleic anhydride in the mixed solution is 25-30 wt%.
The gas phase separated by the hydrogen thermal separation tank is cooled and then enters the hydrogen cold separation tank for further separation, the separated liquid is recycled as solvent, and the gas phase is recycled after being pressurized by the recycle hydrogen compressor.
The operation pressure of the byproduct removal tower is 40-45kPaA, and the bottom temperature is 180-190 ℃.
The operating pressure of the solvent removal tower is 5-10kPaA, and the bottom temperature is 185-195 ℃.
The byproduct obtained from the tower top of the byproduct removal tower is sent to a byproduct recovery tower for rectification and purification, a tetrahydrofuran product is obtained from the tower top, and mixed alkyd substances are led out from the tower bottom; and the tail gas discharged from the top of the desolventizing removal tower and the succinic anhydride rectifying tower is sent into a tail gas absorption tower to recover the anhydride component carried in the tail gas, and then is purified and discharged.
The byproduct obtained from the tower top of the byproduct removal tower is sent to a byproduct recovery tower for rectification and purification, a tetrahydrofuran product is obtained from the tower top, and mixed alkyd substances are led out from the tower bottom; and the tail gas discharged from the top of the desolventizing removal tower and the succinic anhydride rectifying tower is sent into a tail gas absorption tower to recover the anhydride component carried in the tail gas, and then is purified and discharged.
In order to solve the problems existing in the background art, the inventors make the following improvements:
(1) The hydrogenation reactor adopts a special middle heat-taking type bubbling reactor, namely, the bottom section is a bubbling fixed bed section, the middle section is a tubular heat-taking section, and the upper section is a bubbling fixed bed section. Compared with the traditional fixed bed reactor, the structure can well control the reaction temperature rise. Compared with a tubular isothermal reactor, the reactor has smaller volume, more uniform heat transfer and greatly reduced manufacturing cost.
The mixed solution enters from bottom to top in a hydrogenation reactor, and the maleic anhydride is selectively hydrogenated to generate succinic anhydride in the presence of a catalyst and hydrogen, so that the reaction process is exothermic. The main and side reaction rates are increased when the temperature is increased, and the selectivity of the main product is reduced. The temperature control of the reactor is carried out in two modes, firstly, the temperature of the inlet of the reactor and the temperature of the outlet of the intermediate heat-taking section are regulated through the hot water flow of the intermediate heat-taking section and the hot water flow of the feeding section; and secondly, the reaction temperature rise is controlled by controlling the injection intensity of the hydrogen, the reaction effect is good if the injection flow of the hydrogen is large, and the bed temperature rise is high, otherwise, the temperature rise is low. Under the conditions of the two control modes and the flow mode of the lower inlet and the upper outlet of the reactor, the reaction temperature and the temperature rise can be well controlled, thereby inhibiting the occurrence of side reaction and improving the yield of the main product.
(2) Due to good temperature control effect, by adopting three hydrogenation reactors in series and skillfully controlling the three hydrogenation reactors to gradually and slightly heat up for reaction, unreacted maleic anhydride can be completely converted, the maleic anhydride conversion rate is ensured to reach or approach to 100 percent, the raw material conversion rate and the product yield are ensured, and the higher concentration (25-30 percent by weight) of the fed maleic anhydride can be allowed, so that the solvent circulation ratio is reduced, the energy consumption in the recovery process is reduced, and various problems caused by large circulation ratio are solved.
(3) The byproduct removal tower is preferably provided with a filler section, has higher severity, controls the operating pressure to be 40-45kPaA, and controls the bottom temperature to be 180-190 ℃ to remove the byproducts including light components such as propionic acid, propanol, butyric acid and butanol in the reaction product from the solvent, thereby purifying the solvent, avoiding the reaction with raw material maleic anhydride to generate esters and other compounds when the solvent circulates, and solving the problems of solvent discoloration and increased raw material consumption caused by insufficient extraction of the light components in the actual production.
(4) The solvent removal column is preferably provided with a packing section having a higher severity and operating pressure of 5-10kPaA and a column bottom temperature of 185-195 ℃. The trace 1, 4-butanediol generated in the reaction process is distilled out from the succinic anhydride, so that a succinic acid product (99.9%wt) with higher purity can be obtained, the condition that the product turns yellow in the polymerization process is avoided, and the quality requirement of PBS (poly (butylene succinate)) polymer grade succinic anhydride raw materials is met.
(5) And a byproduct removal tower is additionally arranged, a solvent and succinic anhydride contained in the vacuumized tail gas are recovered, the tail gas is purified in a tail gas absorption tower by adopting the solvent, the absorption liquid returns to the byproduct removal tower, and a tetrahydrofuran product with higher purity is obtained at the top of a rectifying and purifying tower through the byproduct recovery tower, and the purpose of purifying the tail gas and recovering byproducts is achieved by mixing alkyd substances at the bottom of the tower.
The invention has simple process, meets the requirements of large-scale and continuous production of devices, can allow higher concentration of ingredients, effectively reduces the energy consumption of the fractionation process, and has low equipment investment and operation cost, small occupied area, high product conversion rate and yield, good quality and environmental friendliness.
Drawings
FIG. 1 is a process flow diagram of the present invention.
FIG. 2 is a schematic diagram of a hydrogenation reactor.
In fig. 1, R01A, R01B and R01C are hydrogenation reactors; t01 is a byproduct removal tower, T02 is a solvent removal tower, T03 is a succinic anhydride rectifying tower, T04 is a tail gas absorption tower and T05 is a byproduct recovery tower; e01 and E02A, E02B are hot water coolers and E03 is a circulating hydrogen cooler; v01 is a solvent buffer tank, V02 is a reaction feeding buffer tank, V03 is a hydrogen thermal separation tank, V04 is a hydrogen cold separation tank and V05 is a circulating hydrogen separation tank; c01 is a recycle hydrogen compressor; p01 is a hydrogenation feed pump, and P02 is a hydrogenation circulating pump; z01 and Z03 are succinic anhydride slicing machines, and Z02 and Z04 are succinic anhydride packaging machines;
in fig. 2, 1 is a bottom section, 2 is a middle section, and 3 is an upper section.
Detailed Description
The process of the invention is further explained below with reference to the accompanying drawings:
the starting material in this example is a mixture of solvent gamma-butyrolactone and maleic anhydride, with a maleic anhydride content of 25% wt, a feed flow of 27.6t/h, a feed temperature of 60℃and a feed pressure of 5-7.0MPaG.
Referring to fig. 1, after solvent in a solvent buffer tank V01 is sent into a feed buffer tank V02 to be mixed with maleic anhydride to prepare mixed solution with 25 wt% of maleic anhydride content, the mixed solution is pressurized by a hydrogenation feed pump P01 and subjected to heat exchange by a hot water cooler E01, and then enters three hydrogenation reactors R01A, R01B and R01C connected in series, selective hydrogenation reaction is carried out under the action of a catalyst to generate succinic anhydride, and the reaction temperature rise is controlled by the bubbling intensity of hydrogen and an intermediate heat-taking heat exchanger.
Referring to fig. 2, in the hydrogenation reactor R01A, the bottom section 1 is a bubbling fixed bed section, the middle section 2 is a tubular heat-taking section, the upper section 3 is a bubbling fixed bed section, the mixed solution firstly enters the bubbling fixed bed section of the bottom section 1 from the bottom to react, then enters the middle section 2 to react while controlling the temperature, finally enters the bubbling fixed bed section of the upper section 2 to continue to react, and finally is discharged from the top. While introducing hydrogen gas into the bottom of the upper section 3 and the bottom section 1 and controlling the reaction temperature of each section to be 15-25 ℃. The height-to-diameter ratio of the bed layer of the hydrogenation reactor is 3-6:1, wherein the height-to-diameter ratio refers to the common height of two bubbling fixed bed sections and a tubular heat-taking section of the hydrogenation reactor divided by the diameter.
Three hydrogenation reactors R01A, R01A and R01C are connected in series in sequence, and a hot water cooler E02A, E02B is arranged between two adjacent hydrogenation reactors to control the reaction temperature. Wherein the total temperature of each hydrogenation reactor is controlled at 15-30 ℃ and the reaction pressure of each hydrogenation reactor is controlled at 5-7MPaG, the hydrogen-oil ratio is 30-100, and the solvent ratio is 70-75%.
The inlet temperature of the first hydrogenation reactor is controlled to be 55 ℃, the outlet temperature is controlled to be 85 ℃, the inlet temperature of the second hydrogenation reactor and the third hydrogenation reactor is controlled to be 60 ℃, and the outlet temperature is controlled to be 85 ℃.
The reaction products after three hydrogenation reactors enter a reaction feeding buffer tank V02 for buffering and then enter a hydrogen thermal separation tank V03 for hydrogen separation, separated gas phases are cooled by a circulating hydrogen cooler E03 and then enter a hydrogen cold separation tank V04 for further separation, separated liquid is recycled as solvent, the gas phases are treated by a circulating hydrogen separation tank V05 and then used as circulating hydrogen, and the gas phases are pressurized by a circulating hydrogen compressor C01 and continuously fed with fresh hydrogen to be returned to the hydrogenation reactor.
After being mixed, a part of the separated liquid phase and the liquid separated in the gas phase is taken as circulating liquid, pressurized by a hydrogenation circulating pump P02 and then sent back to a hydrogenation reactor together with the mixed liquid through a hot water cooler E01 (the reaction circulating ratio is controlled according to the outlet temperature of the reactor, when the outlet temperature of the reactor is controlled within a required range, the reaction circulating ratio can be zero, otherwise, the circulating ratio is adaptively increased), the other part of the mixed liquid is sent to a byproduct removal tower T01 to remove byproducts, then the solvent removal tower T02 to remove solvents and a succinic anhydride rectifying tower T03 to rectify the mixed liquid, the medical succinic anhydride obtained at the top of the tower is sent to a succinic anhydride slicer Z01 and a succinic anhydride packaging machine Z02 to be sliced and packaged, and the industrial succinic anhydride obtained at the bottom of the tower is sent to the succinic anhydride slicer Z03 and the succinic anhydride packaging machine Z04 to be sliced and packaged;
the byproduct obtained from the top of the byproduct removal tower T01 is sent to a byproduct recovery tower T05 for rectification and purification, tetrahydrofuran products are obtained from the top of the tower, and mixed alkyd substances are led out from the bottom of the tower; tail gas discharged from the tops of the desolventizing removal tower T02 and the succinic anhydride rectifying tower T03 is sent to a tail gas absorption tower T04 to recover anhydride components carried in the tail gas, then the tail gas is purified and discharged, and the separated anhydride is returned to a byproduct removal tower T01; the top gas-liquid separation of the desolventizing tower T02 is carried out to obtain a liquid phase which is returned to the solvent buffer tank V01.
Wherein the operation pressure of the byproduct removal tower is 40-45kPaA, and the bottom temperature is 180-190 ℃. The operating pressure of the solvent removal tower is 5-10kPaA, and the bottom temperature is 185-195 ℃.
The succinic anhydride (pharmaceutical grade and industrial grade) is used as a reference, the unit consumption of maleic anhydride is 0.974t/t, the unit consumption of hydrogen is 253Nm3/t, the unit consumption of solvent is 26.83kg/t, and the energy consumption cost of public engineering is 600-1000 yuan/t. Thus, the pharmaceutical grade succinic acid product with the purity of about 6.25t/h and the industrial grade succinic anhydride product with the purity of 0.83t/h are obtained, and the purity of the product is more than 98 percent. There is also a small amount of tetrahydrofuran product. The medical succinic anhydride can be used as PBS polymeric raw material. The obtained industrial succinic anhydride can meet the requirements of general users. The produced high-purity succinic anhydride can also be used as a raw material of certain intermediates in the pharmaceutical industry.
The method can be used for producing high-purity succinic anhydride, has good product quality, complete process flow, low investment, small occupied area, low operation energy consumption and environmental protection, does not generate a large amount of waste water, waste gas and waste solids, and solves the technical problem of the process for preparing succinic anhydride by maleic anhydride hydrogenation.
Claims (9)
1. A process for preparing succinic anhydride by hydrogenating maleic anhydride is characterized by comprising the steps of sequentially feeding mixed solution of solvent gamma butyrolactone and maleic anhydride into three hydrogenation reactors connected in series to carry out selective hydrogenation reaction in the presence of a catalyst, then carrying out cyclic hydrogen separation by a hydrogen thermal separation tank, removing byproducts by a byproduct removal tower, removing solvent by a desolventizing removal tower, rectifying by a succinic anhydride rectifying tower, and obtaining medical succinic anhydride at the tower top, wherein industrial succinic anhydride is obtained at the tower bottom;
the bottom section of the hydrogenation reactor is a bubbling fixed bed section, the middle section is a tubular heat-taking section, a catalyst is filled in a tubular, the upper section is a bubbling fixed bed section, mixed liquid enters and exits from the bottom, hydrogen is introduced into the middle section and the bottom section, the reaction temperature of each section is controlled to be 15-25 ℃, the total temperature of each hydrogenation reactor is controlled to be 15-30 ℃, and a hot water cooler is arranged between two adjacent hydrogenation reactors;
wherein the operation pressure of the byproduct removal tower is 40-45kPaA, and the bottom temperature is 180-190 ℃.
2. The process for preparing succinic anhydride by hydrogenating maleic anhydride according to claim 1, wherein the reaction pressure of each hydrogenation reactor is controlled to be 5-7MPaG, the hydrogen-oil ratio is 30-100, and the solvent ratio is 70-75% wt.
3. The process for producing succinic anhydride by hydrogenating maleic anhydride according to claim 1, wherein the inlet temperature of the first hydrogenation reactor is controlled to be 55 ℃, the outlet temperature is controlled to be 85 ℃, the inlet temperatures of the second and third hydrogenation reactors are controlled to be 60 ℃, and the outlet temperatures are controlled to be 85 ℃.
4. The process for preparing succinic anhydride by hydrogenating maleic anhydride according to claim 1, wherein the height-to-diameter ratio of the bed layer of the hydrogenation reactor is 3-6:1.
5. The process for producing succinic anhydride by hydrogenating maleic anhydride according to any one of claims 1 to 4, wherein the reaction product after the hydrogenation reaction in the three hydrogenation reactors is separated by circulating hydrogen in a hydrogen thermal separation tank, a part of the separated liquid phase is returned to the hydrogenation reactor as a circulating liquid together with the mixed liquid, the reaction circulation ratio is 0 to 2:1, and the other part is fed to a by-product removal column.
6. The process for producing succinic anhydride by hydrogenating maleic anhydride according to claim 5, wherein the concentration of maleic anhydride in the mixed solution is 25-30% by weight.
7. The process for preparing succinic anhydride by hydrogenating maleic anhydride according to claim 5, wherein the gas phase separated by the hydrogen thermal separation tank is cooled and then enters the hydrogen cold separation tank for further separation, the separated liquid is recycled as solvent, and the gas phase is recycled after being pressurized by the recycle hydrogen compressor.
8. The process for producing succinic anhydride by hydrogenating maleic anhydride according to claim 1, wherein the operation pressure of the solvent removal column is 5 to 10kPaA and the bottom temperature is 185 to 195 ℃.
9. The process for preparing succinic anhydride by hydrogenating maleic anhydride according to claim 1, wherein the byproduct obtained from the top of the byproduct removal tower is sent to a byproduct recovery tower for rectification and purification, tetrahydrofuran product is obtained from the top of the tower, and mixed alkyd substances are led out from the bottom of the tower; and the tail gas discharged from the top of the desolventizing removal tower and the succinic anhydride rectifying tower is sent into a tail gas absorption tower to recover the anhydride component carried in the tail gas, and then is purified and discharged.
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| CN101417220A (en) * | 2008-11-14 | 2009-04-29 | 浙江大学 | Method and device for improving flow character of gas liquid bubble column with row tubes |
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| CN112661625A (en) * | 2021-03-16 | 2021-04-16 | 中化学科学技术研究有限公司 | Preparation process of succinic acid |
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| CN101417220A (en) * | 2008-11-14 | 2009-04-29 | 浙江大学 | Method and device for improving flow character of gas liquid bubble column with row tubes |
| CN101480595A (en) * | 2009-01-08 | 2009-07-15 | 浙江大学 | Slurry bubble column reactor with needle type fin column tube bundle |
| 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 |
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