CN117920057A - Hydrogenation reaction system and maleic anhydride hydrogenation method - Google Patents
Hydrogenation reaction system and maleic anhydride hydrogenation method Download PDFInfo
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- CN117920057A CN117920057A CN202211301016.7A CN202211301016A CN117920057A CN 117920057 A CN117920057 A CN 117920057A CN 202211301016 A CN202211301016 A CN 202211301016A CN 117920057 A CN117920057 A CN 117920057A
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- maleic anhydride
- hydrogenation
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- hydrogenation reaction
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 166
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 118
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 52
- 239000001257 hydrogen Substances 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 25
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229940014800 succinic anhydride Drugs 0.000 claims abstract description 19
- 238000000926 separation method Methods 0.000 claims abstract description 18
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 44
- 239000003054 catalyst Substances 0.000 claims description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 34
- 239000002994 raw material Substances 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 25
- 150000002431 hydrogen Chemical class 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000007791 liquid phase Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 230000004323 axial length Effects 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000000084 colloidal system Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- 238000005194 fractionation Methods 0.000 claims description 4
- 238000010907 mechanical stirring Methods 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 239000012071 phase Substances 0.000 claims description 4
- 230000003068 static effect Effects 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011344 liquid material Substances 0.000 claims description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- DKMROQRQHGEIOW-UHFFFAOYSA-N Diethyl succinate Chemical compound CCOC(=O)CCC(=O)OCC DKMROQRQHGEIOW-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 2
- 241000219793 Trifolium Species 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 239000000047 product Substances 0.000 description 15
- 239000007795 chemical reaction product Substances 0.000 description 11
- 238000007086 side reaction Methods 0.000 description 7
- 238000009472 formulation Methods 0.000 description 5
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a hydrogenation reaction system and a maleic anhydride hydrogenation method. The hydrogenation reaction system comprises a reactor I and a reactor II; the reactor I comprises a cylinder I and a central tube I, wherein the wall of the central tube I is provided with an opening, and the cylinder I is communicated with the central tube I through the opening; the reactor II comprises a cylinder II and a built-in central tube II, wherein the wall of the central tube II is provided with a hole, and the cylinder II is communicated with the central tube II through the hole. The maleic anhydride hydrogenation method comprises the steps that a mixed material of maleic anhydride solution and hydrogen sequentially passes through a reactor I and a reactor II to carry out hydrogenation reaction, and a succinic anhydride product is obtained through gas-liquid separation. The system can effectively control the reaction rate and the temperature rise in the maleic anhydride hydrogenation reaction process, solves the problems of concentrated heat release and easy generation of local hot spots in the maleic anhydride hydrogenation reaction process, and improves the conversion rate and the selectivity in the maleic anhydride hydrogenation process.
Description
Technical Field
The invention belongs to the technical field of succinic anhydride production, and particularly relates to a hydrogenation reaction system and a maleic anhydride hydrogenation method.
Background
At present, the production method of succinic anhydride is mainly divided into a succinic anhydride dehydration method, a biological fermentation method and a maleic anhydride catalytic hydrogenation method, wherein the maleic anhydride catalytic hydrogenation method is the method with the highest conversion rate and the best product quality for producing succinic anhydride, and is most suitable for large-scale industrialization, but the succinic anhydride produced by maleic anhydride hydrogenation is the strong exothermic reaction (delta H=128 kJ/mol), and the reaction heat is not easily removed in time by adopting the conventional trickle bed hydrogenation and the conventional liquid phase hydrogenation industry and reactor structure, so that the temperature of the reaction process can not be controlled, the problems of local hot spot, serious side reaction, hardening of the catalyst bed layer and the like are caused, the conversion rate and the selectivity of the reaction process are difficult to be compatible, and higher selectivity is more difficult to achieve.
CN103570650a proposes a technological process for continuously producing succinic anhydride and co-producing succinic acid by maleic anhydride hydrogenation, the method adopts a two-stage hydrogenation reactor, the first-stage hydrogenation reactor is a fixed bed reactor for feeding hydrogen and reaction liquid downwards and discharging upwards, the second-stage hydrogenation reactor is a trickle bed reactor for feeding hydrogen and reaction liquid upwards and discharging downwards, and an external circulation heat removal mode is adopted to remove reaction heat, so as to control the average operation temperature of the whole reactor and equalize the temperature in the reactor. In the method, a primary reactor adopts a parallel flow upward flow mode of hydrogen and reaction liquid, and based on the specificity of large heat release of maleic anhydride hydrogenation reaction, the conventional technology cannot ensure uniform material mixing and uniform distribution, and cannot ensure uniform reaction and solve the problem of local hot spots; the secondary reactor adopts a parallel-flow downward trickle bed reactor flow mode, so that the timely taking away of the reaction heat can not be ensured, and the problem of local hot spots can be solved.
CN 105801536B proposes a method for preparing succinic anhydride by maleic anhydride liquid phase selective hydrogenation, the liquid phase hydrogenation reaction adopts a two-stage low-temperature low-pressure reaction process method to prepare succinic anhydride, two reactors are adopted, a first-stage reactor and a second-stage reactor are respectively adopted, and the first-stage reactor and the second-stage reactor are used in series; the maleic anhydride, the solvent and the hydrogen enter a first-stage reactor to carry out partial catalytic selective hydrogenation, after the reaction, the residual maleic anhydride, the generated succinic anhydride and the solvent mixed liquid material enter a second-stage reactor to carry out complete catalytic selective hydrogenation, and the succinic anhydride product is obtained after gas-liquid separation and rectification of the product of the second-stage reactor. In the method, the two-stage reactor adopts a liquid-phase hydrogenation method of hydrogen and reaction liquid, and based on the specificity of large heat release of maleic anhydride hydrogenation reaction, the conventional liquid-phase hydrogenation mixing and reaction technology cannot ensure uniform material mixing and uniform distribution, and cannot ensure uniform reaction and solve the problem of local hot spots.
Disclosure of Invention
Aiming at the defects of the prior art, the invention discloses a hydrogenation reaction system and a maleic anhydride hydrogenation method. The system can effectively control the reaction rate and the temperature rise in the maleic anhydride hydrogenation reaction process, solves the problems of concentrated heat release and easy generation of local hot spots in the maleic anhydride hydrogenation reaction process, and improves the conversion rate and the selectivity in the maleic anhydride hydrogenation process.
The hydrogenation reaction system comprises a reactor I and a reactor II;
The reactor I comprises a cylinder I and a built-in central tube I, which are coaxially arranged, wherein the wall of the central tube I is provided with an opening, the cylinder I and the central tube I are communicated through the opening, and an annular area between the cylinder I and the central tube I is a reaction area I; the bottom of the central tube I is provided with a feed inlet I, and the top of the cylinder I is provided with a discharge outlet I; the size of the central tube I can be the same as or different from that of the feeding port I;
The reactor II comprises a cylinder II and a built-in central tube II, which are coaxially arranged, wherein an opening is formed in the wall of the central tube II, the cylinder II is communicated with the central tube II through the opening, and an annular area between the cylinder II and the central tube II is a reaction area II; the bottom of the cylinder II is provided with a feed inlet II, and the top of the central tube II is provided with a discharge outlet II; the size of the central tube I can be the same as or different from that of the feeding port I; the feed inlet I is communicated with a feed pipeline, and the discharge outlet I is communicated with the feed inlet II through the pipeline.
In the hydrogenation reaction system, the height-diameter ratio of the reactor I is 2-20, preferably 3-8, and the height-diameter ratio of the reactor II is 0.5-5, preferably 0.5-3.0; the volume ratio of the reactor I to the reactor II is 1:1.1 to 1:10, preferably 1:1.5 to 1:5.
In the hydrogenation reaction system, the diameter ratio of the central tube to the cylinder is 1:2-1:200.
In the hydrogenation reaction system, a partial area of the surface of the central tube I is provided with holes, and the hole area is from the bottom of the central tube I to an area of 1/2-4/5 of the axial length of the central tube I (the bottom is an axial length starting point); the surface opening size of the central tube I is generally 1 mm-100 mm; the surface open area of the central tube I is not smaller than the sectional area of the feed inlet I; the surface part area of the central tube II is provided with holes, and the hole area is from the top of the central tube II to 1/2 to 4/5 area of the axial length of the central tube II (the top is the starting point of the axial length); the surface opening size of the central tube II is generally 1 mm-100 mm; the surface open area of the central tube II is not smaller than the sectional area of the discharge hole II; generally, the central tubes I and II are provided with the same open area.
In the hydrogenation reaction system, the top of the outer shell of the reactor (the reactor I and the reactor II) is an upper seal head, the bottom of the outer shell is a lower seal head, and central pipes (central pipes I and II) are fixedly welded along the axial direction of the reactor at the central position of the inner wall of the upper seal head and the central position of the inner wall of the lower seal head.
In the hydrogenation reaction system, the reactor I and the reactor II are filled with hydrogenation catalysts commonly used in the field; the catalyst types can be set according to the needs and can be the same or different; the number of catalyst beds can be set as desired.
The hydrogenation reaction system of the invention further comprises raw material mixing equipment for mixing liquid phase raw materials with hydrogen, such as equipment with liquid-liquid and/or gas-liquid mixing functions such as a static mixer, a dissolved air pump, mechanical stirring equipment, a colloid mill, a micro-pore plate nano/micro-hydrogen dispersing component, a micro-bubble generator, a ceramic membrane nano/micro-hydrogen dispersing component, a micro-channel mixer and the like. The raw material mixing equipment is generally arranged in front of a feed inlet of the reactor. Such as maleic anhydride hydrogenation, and hydrogen.
The hydrogenation reaction system of the invention further comprises a heat-taking device for taking heat from the discharge of the reactor I and exchanging heat from the feed of the reactor II to the reaction temperature required by the materials, such as a heat exchanger, a water cooler, etc.
The hydrogenation reaction system of the invention further comprises a hydrogen supplementing pipeline which is generally directly connected with the raw material mixing equipment and is used for providing hydrogen needed by the hydrogenation reaction in the reactor II.
The hydrogenation reaction system of the invention further comprises a gas-liquid separation device for gas-liquid separation of the effluents of the reactors I and II, which is generally completed by a gas-liquid separation tank, the top of which is separated into gas and liquid phase products at the bottom of the separation tank.
The maleic anhydride hydrogenation method provided by the invention comprises the following steps:
(1) The mixed material of maleic anhydride solution and hydrogen enters a central tube I of a reactor I as a first mixed feed through a feed inlet I, and is diffused into a cylinder I filled with hydrogenation catalyst from an opening on the wall of the central tube I, a first-stage hydrogenation reaction occurs from bottom to top, and a first-stage hydrogenation reaction effluent leaves the reactor I from a discharge port I;
(2) The mixture of the primary hydrogenation reaction effluent and the supplementary hydrogen is taken as a second mixed feed, enters a cylinder body II filled with hydrogenation catalyst from a feed inlet II of a reactor II, a secondary hydrogenation reaction occurs from bottom to top, the reacted secondary hydrogenation reaction effluent is diffused into a central tube II through an opening on the wall of the central tube II, leaves the reactor II through a discharge outlet II, and is subjected to gas-liquid separation to obtain succinic anhydride products.
In the method of the invention, the first mixed feed in the step (1) is a liquid phase material taking hydrogen as a disperse phase and maleic anhydride solution as a continuous phase; the dispersion size of the hydrogen is generally from 100nm to 1000. Mu.m, preferably from 50 μm to 600. Mu.m; one or more of mixing devices such as a static mixer, a dissolved air pump, mechanical stirring equipment, a colloid mill, a micro-pore plate nano/micron hydrogen dispersing component, a micro-bubble generator, a ceramic membrane nano/micron hydrogen dispersing component, a micro-channel mixer and the like are generally adopted.
In the method, the solvent in the step (1) is selected from one or more of benzene, toluene, xylene, acetone, tetrahydrofuran, gamma-butyrolactone, first-class acetone, cyclohexanone, ethyl acetate, diethyl succinate or ethylene glycol monomethyl ether; the concentration of maleic anhydride solution is generally 0.03 to 0.3g/mL, preferably 0.05 to 0.15g/mL.
In the process of the invention, the hydrogen is generally hydrogen having a purity of more than 90 (v)%, preferably 99.9% pure hydrogen.
In the method of the invention, the outer surfaces of the central pipes I and II are wrapped with one or more layers of steel wire meshes for preventing the catalyst particles from leaking along the openings on the surfaces of the central pipes, and the pore diameters of the wire meshes are generally smaller than the nominal diameter of the smallest section of the catalyst particles.
In the process of the invention, the ratio of the volume flow of hydrogen (Nm 3/h) to the fresh feed (m 3/h) (sum of maleic anhydride and solvent) in the reactors (I and II) is 5:1 to 100:1, preferably 10:1 to 60:1.
In the method of the invention, the hydrogenation reaction conditions of the reactor I are as follows: the reaction temperature is 40-200 ℃, preferably 50-90 ℃; the reaction pressure is generally 0.5 to 10.0MPa, preferably 1 to 5.0MPa; the liquid hourly space velocity is generally from 1 to 20.0h -1, preferably from 3.0 to 10.0h -1.
In the method of the invention, the hydrogenation reaction conditions of the reactor II are as follows: the reaction temperature is generally 40 to 100 ℃, preferably 50 to 70 ℃; the reaction pressure is generally 0.5 to 10.0MPa, preferably 1 to 5.0MPa; the liquid hourly space velocity is generally from 0.1 to 5.0h -1, preferably from 0.5 to 3.0h -1.
In the method of the invention, the sum of the maleic anhydride hydrogenation conversion rates of the reactor I and the reactor II is 100%, wherein the maleic anhydride hydrogenation conversion rate of the reactor I is generally 10% -99%, preferably 50% -95%, the maleic anhydride hydrogenation conversion rate of the reactor II is generally 1% -90%, preferably 5% -50%, and the maleic anhydride hydrogenation conversion rate of the reactor I is higher than the maleic anhydride hydrogenation conversion rate of the reactor II.
In the method of the invention, the hydrogenation catalyst is preferably a supported nickel-based catalyst, wherein the catalyst carrier can be one or more of SiO 2、Al2O3、SiO2- Al2O3、TiO2, active carbon or molecular sieve; the catalyst may be in the form of one of sphere, bar, clover, toothed sphere, etc., preferably a sphere or toothed sphere catalyst.
In the method, the liquid materials obtained by gas-liquid separation can be partially recycled to the reactors I and II, and partial materials can be recycled to the subsequent succinic anhydride product fractionation unit or not recycled to the subsequent succinic anhydride product fractionation unit; if the reaction products are partly recycled, the recycled material recycled to the reactor I represents from 5 to 80% by weight, preferably from 10 to 30% by weight, of the fresh material at the inlet of the reactor I; the recycle to reactor II is 1 to 30wt%, preferably 5 to 20wt%, of the fresh feed to reactor I.
In the method, the materials in the reactor I are materials in the earlier stage of maleic anhydride hydrogenation reaction, and the problems of concentrated heat release, local hot spots and the like are very easy to cause on the basis of high maleic anhydride concentration and high reaction rate, so that on one hand, the problems of local catalyst coking and serious side reaction occur in the reactor, and on the other hand, the problems of uneven reaction at the upper part and the lower part along the axis position in the reactor, namely, the concentration of the lower part of reaction heat occur; based on the fact that the materials in the reactor II are materials in the later period of reaction, the maleic anhydride concentration is low, the reaction rate is low, and the mass transfer driving force is small, so that the problems of long local residence time, multiple side reactions and the like are more likely to occur when the maleic anhydride is completely converted by using a slightly low space velocity. According to the invention, in the structure of the reactor I, the reactor containing the central tube I is arranged, and reaction materials diffuse into the catalyst bed layer from the openings on the surface of the central tube I, so that on one hand, the residence time of the materials on the surface of the catalyst at different positions can be controlled by controlling parameters such as the opening area, the opening position and the like of the central tube I, and the reaction process is effectively controlled; on the other hand, after the materials are diffused to the catalyst through the central tube I, the materials flow radially and axially in the reactor I at the same time, so that the reaction is more uniform, local hot spots are reduced, and uniform reaction heat is facilitated; in addition, the reactor I adopts a high space velocity condition and an up-flow micro-expansion bed flow mode, which is beneficial to alleviating the problems of local hot spots, catalyst coking and the like and is more beneficial to long-period high-efficiency operation. In the structure of the reactor II, the reactor with the central tube II is arranged, and reaction materials are diffused from the catalyst bed layer into the central tube II through a central hole formed in the outer part of the central tube II and leave the central tube II, so that the material residence time of the materials on the surface of the catalyst at different positions in the reactor II can be controlled by controlling parameters such as the open pore area and the open pore height of the central tube II, the complete efficient conversion of maleic anhydride can be realized, and the deep side reaction can be effectively controlled; on the other hand, the materials are gradually diffused to the central tube II through the catalyst bed layer and then leave the reactor, and the materials simultaneously flow radially and axially in the reactor II, so that the radial and axial reaction degree and the temperature distribution in the reactor II are very uniform, and the side reaction is reduced. And (3) injection: the early stage of the reaction refers to the stage in which the concentration of maleic anhydride in the maleic anhydride solution material in the reactor is greater than or equal to the concentration of succinic anhydride, and the later stage of the reaction refers to the stage in which the concentration of maleic anhydride in the maleic anhydride solution material in the reactor is less than the concentration of succinic anhydride.
Drawings
FIG. 1 is a schematic diagram of a hydrogenation reaction system and a maleic anhydride hydrogenation process according to the present invention.
Wherein 1 is maleic anhydride solution, 2 is hydrogen, 3 is mixer, 4 is maleic anhydride hydrogenation reaction system feed, 5 is reactor I,6 is center tube I,7 is annular region I,8 is opening on center tube I, 9 is catalyst bed I,10 is reactor I's reaction discharge, 11 is heat collector, 12 is hydrogen, 13 is mixer, 14 is reactor II's reaction feed, 15 is reactor II,16 is center tube II,17 is annular region II,18 is center tube II,19 is catalyst bed II,20 is reactor II's reaction discharge, 21 is heat collector, 22 is gas-liquid separator feed, 23 is gas-liquid separator, 24 is separated gas, 25 is separated hydrogenation product.
Detailed Description
The invention will now be described in more detail with reference to the accompanying drawings and examples, which are not intended to limit the invention thereto.
Taking the attached figure 1 as an example, the application process of the hydrogenation reaction system and the maleic anhydride hydrogenation method of the invention is as follows:
The maleic anhydride solution 1 and the hydrogen 2 are uniformly mixed by a mixer 3 to form a reaction feed 4, and the reaction feed is firstly introduced into a maleic anhydride hydrogenation reaction system. Firstly, the maleic anhydride enters a central tube I6 from the bottom of a reactor I5, then diffuses into an annular area I7 from an opening 8 on the central tube I, the maleic anhydride hydrogenation reaction occurs in a catalyst bed I9 from bottom to top, after the reaction is completed, the maleic anhydride hydrogenation reaction diffuses into the central tube I6, a reaction discharge 10 serving as the reactor I leaves the reactor, is cooled to a proper temperature by a heat collector 11, enters a mixer 13 together with hydrogen 12 to be uniformly mixed, a feed serving as a reactor II 15 enters a catalyst bed II 19, the maleic anhydride hydrogenation reaction occurs in the catalyst bed I19 from bottom to top, after the reaction is completed, the maleic anhydride hydrogenation reaction diffuses into a central tube II18, a reaction discharge 20 serving as the reactor II leaves the reactor, is cooled to a proper temperature by a heat collector 21, enters a gas-liquid separator 23, and gas 24 and liquid products 25 are separated.
The method is applied to the maleic anhydride hydrogenation reaction process. Maleic anhydride starting material and gamma-butyrolactone solvent were commercially available, the specific properties are shown in tables 1 and 2, respectively, and the catalyst properties are shown in table 3.
TABLE 1 maleic anhydride raw material Properties
TABLE 2 solvent Properties of gamma butyrolactone
TABLE 3 physical and chemical indicators of catalyst
Comparative example 1
The conventional fixed bed hydrogenation process is adopted, and maleic anhydride is subjected to maleic anhydride hydrogenation reaction in the first reactor and the second reactor in sequence in a mode of connecting two up-flow hydrogenation reactors in series. Firstly, maleic anhydride raw materials are dissolved in gamma-butyrolactone solvent and uniformly mixed to prepare maleic anhydride solution, the maleic anhydride solution is regulated to the temperature of an inlet of a reactor and then mixed with hydrogen, the maleic anhydride solution enters from the bottom of an up-flow hydrogenation reactor, hydrogenation reaction is carried out through a catalyst bed layer from bottom to top, the obtained hydrogenation product enters from the bottom of a second up-flow hydrogenation reactor after being regulated to be mixed with supplementary hydrogen, hydrogenation reaction is carried out through the catalyst bed layer from bottom to top, the maleic anhydride solution leaves the reactor after the hydrogenation reaction is finished, gas-liquid separation is carried out through a separator, and separated materials are partially circulated, and the other part of the material enters a separation unit.
The operating conditions of the first hydrogenation reactor were as follows:
the reactor inlet temperature was 50 ℃;
The reaction pressure is 6.0-6.5 MPaG;
The height-diameter ratio of the reactor is as follows: 2.5
Volume space velocity: 2.5h -1
Maleic anhydride formulation concentration: 10g/mL
The volume ratio of hydrogen (Nm 3/h) to fresh raw material (m 3/h) (solution of maleic anhydride dissolved in gamma-butyrolactone solvent) was 100:1, a step of;
The mass ratio of the recycle amount of the reaction product entering the primary reaction to the fresh raw materials: 30%;
The second hydrogenation reactor was operated as follows:
the reactor inlet temperature was 50 ℃;
The reaction pressure is 6.0-6.5 MPaG;
volume space velocity: 1.0h -1;
The height-diameter ratio of the reactor is as follows: 2.5;
The volume ratio of hydrogen (Nm 3/h) to fresh raw material (m 3/h) (solution of maleic anhydride dissolved in gamma-butyrolactone solvent) was 300:1, a step of;
the mass ratio of the recycle amount of the reaction product entering the secondary reaction to the fresh raw materials: 30%;
Under the reaction conditions, maleic anhydride and gamma-butyrolactone solvents shown in table 1 and table 2 are taken as raw materials, and enter a first reactor and a second reactor to continuously carry out hydrogenation reaction to obtain hydrogenation products, and the reaction results are shown in table 4.
Comparative example 2
The maleic anhydride hydrogenation process is carried out by adopting a conventional mode of connecting an up-flow fixed bed and a down-flow trickle bed in series, and maleic anhydride is subjected to maleic anhydride hydrogenation reaction in the first reactor and the second reactor in sequence. Firstly, maleic anhydride raw materials are dissolved in gamma-butyrolactone solvent and uniformly mixed to prepare maleic anhydride solution, the maleic anhydride solution is regulated to the temperature of an inlet of a reactor and then mixed with hydrogen, the maleic anhydride solution enters from the bottom of an up-flow hydrogenation reactor, hydrogenation reaction is carried out through a catalyst bed layer from bottom to top, the obtained hydrogenation product enters from the top of a down-flow hydrogenation reactor after being regulated to be mixed with supplementary hydrogen, hydrogenation reaction is carried out through the catalyst bed layer from top to bottom, the maleic anhydride solution leaves the reactor after the hydrogenation reaction is completed, gas-liquid separation is carried out through a separator, and separated materials are partially circulated, and the other part of the material enters a separation unit.
The operating conditions of the first hydrogenation reactor were as follows:
the reactor inlet temperature was 50 ℃;
The reaction pressure is 6.0-6.5 MPaG;
the height-diameter ratio of the reactor is as follows: 3.0
Volume space velocity: 3.0h -1
Maleic anhydride formulation concentration: 10g/mL
The volume ratio of hydrogen (Nm 3/h) to fresh feed (m 3/h) (solution of maleic anhydride in gamma-butyrolactone solvent) was 150:1, a step of;
The mass ratio of the recycle amount of the reaction product entering the primary reaction to the fresh raw materials: 30%;
The second hydrogenation reactor was operated as follows:
the reactor inlet temperature was 50 ℃;
The reaction pressure is 6.0-6.5 MPaG;
volume space velocity: 1.0h -1;
The height-diameter ratio of the reactor is as follows: 2.5;
The volume ratio of hydrogen (Nm 3/h) to fresh raw material (m 3/h) (solution of maleic anhydride dissolved in gamma-butyrolactone solvent) was 300:1, a step of;
the mass ratio of the recycle amount of the reaction product entering the secondary reaction to the fresh raw materials: 30%;
Under the reaction conditions, maleic anhydride and gamma-butyrolactone solvents shown in table 1 and table 2 are taken as raw materials, and enter a first reactor and a second reactor to continuously carry out hydrogenation reaction to obtain hydrogenation products, and the reaction results are shown in table 4.
Example 1
With the process according to the invention, a reactor I and a reactor II are provided. Firstly, uniformly mixing a pre-prepared 15% maleic anhydride (gamma-butyrolactone solvent) solution and hydrogen, and then entering a maleic anhydride hydrogenation system, and sequentially carrying out hydrogenation reaction through a reactor I and a reactor II; when the reaction feed enters the reactor I, the reaction feed is diffused into an annular space I through an opening on the surface of a central tube I arranged in the reactor I, hydrogenation reaction is carried out in a catalyst bed layer arranged in the annular space I, reaction effluent leaves from the annular space I, is uniformly mixed with supplementary hydrogen after heat taking and temperature adjustment, then enters a catalyst bed layer in an annular space II to carry out hydrogenation reaction, and the reaction effluent enters a central tube II through an opening on the surface of the central tube II and leaves the reactor II to carry out gas-liquid separation; after the reaction effluent is subjected to gas-liquid separation, the separated gas is led out of the reaction system, and the separated liquid part enters a subsequent separation unit and is partially circulated back to the maleic anhydride hydrogenation reactor.
Reaction conditions for reactor I:
The reaction temperature is 50-90 ℃;
the reaction pressure is 3.0-4.0 MPaG;
Volume space velocity: 8.0h -1;
Ratio of height to diameter: 8.0;
The volume ratio of hydrogen (Nm 3/h) to fresh raw material (m 3/h) (solution of maleic anhydride dissolved in gamma-butyrolactone solvent) was 60:1, a step of;
The recycle amount of the reaction product entering the sub-reactor I is compared with the mass ratio of fresh raw materials: 20% of a base;
maleic anhydride formulation concentration: 12g/mL
Reaction conditions for reactor II:
The reaction temperature is 50-90 ℃;
the reaction pressure is 3.0-4.0 MPaG;
volume space velocity: 0.7h -1;
Reactor II aspect ratio: 2.5;
the volume ratio of hydrogen (Nm 3/h) to fresh feed (m 3/h) (solution of maleic anhydride in gamma-butyrolactone solvent) was 20:1, a step of;
the recycle amount of the reaction product entering the sub-reactor II is compared with the mass ratio of fresh raw materials: 30%;
Under the reaction conditions, maleic anhydride and gamma-butyrolactone solvents shown in table 1 and table 2 are taken as raw materials, and enter a maleic anhydride hydrogenation system and a hydrogenation method for hydrogenation reaction to obtain hydrogenation products, and the reaction results are shown in table 4.
Example 2
The reaction system and method were the same as in example 1. The reaction conditions differ from the examples as follows:
Reaction conditions for reactor I:
the reaction temperature is 50-80 ℃;
the reaction pressure is 3.0-4.0 MPaG;
Volume space velocity: 6.0h -1;
reactor I aspect ratio: 3.0;
The volume ratio of hydrogen (Nm 3/h) to fresh feed (m 3/h) (solution of maleic anhydride in gamma-butyrolactone solvent) was 45:1, a step of;
the recycle amount of the reaction product entering the sub-reactor I is compared with the mass ratio of fresh raw materials: 25%;
maleic anhydride formulation concentration: 12g/mL
Reaction conditions for reactor II:
The reaction temperature is 50-90 ℃;
the reaction pressure is 3.0-4.0 MPaG;
volume space velocity: 1.0h -1;
reactor II aspect ratio: 1.0;
The volume ratio of hydrogen (Nm 3/h) to fresh feed (m 3/h) (solution of maleic anhydride in gamma-butyrolactone solvent) was 25:1, a step of;
the recycle amount of the reaction product entering the reactor II is compared with the mass ratio of fresh raw materials: 20% of a base;
Under the reaction conditions, maleic anhydride and gamma-butyrolactone solvents shown in table 1 and table 2 are taken as raw materials, and enter a maleic anhydride hydrogenation system and a hydrogenation method for hydrogenation reaction to obtain hydrogenation products, and the reaction results are shown in table 4.
Example 3
The reaction system and method were the same as in example 1. The reaction conditions differ from the examples as follows:
Reaction conditions for reactor I:
The reaction temperature is 50-90 ℃;
the reaction pressure is 3.0-4.0 MPaG;
volume space velocity: 4.0h -1;
reactor I aspect ratio: 3.0;
The volume ratio of hydrogen (Nm 3/h) to fresh feed (m 3/h) (solution of maleic anhydride in gamma-butyrolactone solvent) was 30:1, a step of;
The recycle amount of the reaction product entering the sub-reactor I is compared with the mass ratio of fresh raw materials: 10%;
maleic anhydride formulation concentration: 12g/mL
Reaction conditions for reactor II:
The reaction temperature is 50-90 ℃;
the reaction pressure is 3.0-4.0 MPaG;
Volume space velocity: 1.5h -1;
reactor II aspect ratio: 1.0;
The volume ratio of hydrogen (Nm 3/h) to fresh feed (m 3/h) (solution of maleic anhydride in gamma-butyrolactone solvent) was 30:1, a step of;
the recycle amount of the reaction product entering the reactor II is compared with the mass ratio of fresh raw materials: 15%;
Under the reaction conditions, maleic anhydride and gamma-butyrolactone solvents shown in table 1 and table 2 are taken as raw materials, and enter a maleic anhydride hydrogenation system and a hydrogenation method for hydrogenation reaction to obtain hydrogenation products, and the reaction results are shown in table 4.
TABLE 4 reaction results
As can be seen from the effects of the embodiment and the comparative example, by adopting the hydrogenation system and the maleic anhydride hydrogenation method, reaction feed sequentially passes through the reactor I and the reactor II which comprise the central tube to carry out hydrogenation reaction, wherein materials in the reactor I are all maleic anhydride hydrogenation early-stage materials, and the reaction materials are diffused to a catalyst bed layer through openings on the surface of the central tube I, namely, the residence time of the materials on the surface of the catalyst at different positions is controlled by controlling parameters such as the opening area, the opening position and the like of the central tube I, so that the reaction process at the early stage of the reaction is effectively controlled, the reaction heat is uniform, and side reactions are reduced; the materials in the reactor II are the rest reaction materials in the later period of maleic anhydride hydrogenation reaction, the concentration of maleic anhydride is low, the reaction rate is low, the central tube II arranged in the reactor II is adopted, and the reaction materials are diffused away from the catalyst bed layer through the central tube II, so that the material residence time of the materials on the surface of the catalyst at different positions in the reactor II can be controlled by controlling the parameters such as the open pore area and the open pore height of the central tube II, the complete efficient conversion of maleic anhydride is realized, and the deep side reaction can be effectively controlled.
Claims (23)
1. A hydrogenation reaction system, characterized in that: comprises a reactor I and a reactor II;
The reactor I comprises a cylinder I and a built-in central tube I, which are coaxially arranged, wherein the wall of the central tube I is provided with an opening, the cylinder I and the central tube I are communicated through the opening, and an annular area between the cylinder I and the central tube I is a reaction area I; the bottom of the central tube I is provided with a feed inlet I, and the top of the cylinder I is provided with a discharge outlet I;
The reactor II comprises a cylinder II and a built-in central tube II, which are coaxially arranged, wherein an opening is formed in the wall of the central tube II, the cylinder II is communicated with the central tube II through the opening, and an annular area between the cylinder II and the central tube II is a reaction area II; the bottom of the cylinder II is provided with a feed inlet II, and the top of the central tube II is provided with a discharge outlet II; the feed inlet I is communicated with a feed pipeline, and the discharge outlet I is communicated with the feed inlet II through the pipeline.
2. The hydrogenation reaction system according to claim 1, wherein: the height-diameter ratio of the reactor I is 2-20, preferably 3-8, and the height-diameter ratio of the reactor II is 0.5-5, preferably 0.5-3.0; the volume ratio of the reactor I to the reactor II is 1:1.1 to 1:10, preferably 1:1.5 to 1:5.
3. The hydrogenation reaction system according to claim 1, wherein: the diameter ratio of the central tube to the cylinder is 1:2-1:200.
4. The hydrogenation reaction system according to claim 1, wherein: the surface part area of the central tube I is provided with holes, and the hole area is from the bottom of the central tube I to the area of 1/2-4/5 of the axial length of the central tube I; the surface opening size of the central tube I is 1 mm-100 mm; the surface open area of the central tube I is not smaller than the sectional area of the feed inlet I.
5. The hydrogenation reaction system according to claim 1, wherein: the surface part area of the central tube II is provided with holes, and the hole area is from the top of the central tube II to the area of 1/2-4/5 of the axial length of the central tube II; the surface opening size of the central tube II is 1 mm-100 mm; the surface open area of the central tube II is not smaller than the sectional area of the discharge hole II.
6. The hydrogenation reaction system according to claim 1, wherein: the open area of the central tube I is the same as that of the central tube II.
7. The hydrogenation reaction system according to claim 1, wherein: the top of the reactor shell is an upper seal head, the bottom of the reactor shell is a lower seal head, and the central position of the inner wall of the upper seal head and the central position of the inner wall of the lower seal head are fixedly welded with a central tube along the axial direction of the reactor.
8. The hydrogenation reaction system according to claim 1, wherein: the hydrogenation reaction system comprises a raw material mixing device for mixing liquid phase raw materials with hydrogen, and is selected from one or more of a static mixer, a dissolved air pump, a mechanical stirring device, a colloid mill, a micro-pore plate nano/micro-hydrogen dispersing component, a micro-bubble generator, a ceramic membrane nano/micro-hydrogen dispersing component or a micro-channel mixer.
9. The hydrogenation reaction system according to claim 1, wherein: the hydrogenation reaction system comprises a heat-taking device for taking heat from the discharge of the reactor I and exchanging heat from the feed of the reactor II to the reaction temperature required by the materials.
10. The hydrogenation reaction system according to claim 1, wherein: the hydrogenation reaction system comprises a hydrogen supplementing pipeline which is directly connected with the raw material mixing equipment and is used for providing hydrogen needed by hydrogenation reaction in the reactor II.
11. The hydrogenation reaction system according to claim 1, wherein: the hydrogenation reaction system comprises a gas-liquid separation device for separating the gas and liquid of the effluent of the reactors I and II.
12. A maleic anhydride hydrogenation method is characterized by comprising the following steps: (1) The mixed material of maleic anhydride solution and hydrogen enters a central tube I of a reactor I as a first mixed feed through a feed inlet I, and is diffused into a cylinder I filled with hydrogenation catalyst from an opening on the wall of the central tube I, a first-stage hydrogenation reaction occurs from bottom to top, and a first-stage hydrogenation reaction effluent leaves the reactor I from a discharge port I; (2) The mixture of the primary hydrogenation reaction effluent and the supplementary hydrogen is taken as a second mixed feed, enters a cylinder body II filled with hydrogenation catalyst from a feed inlet II of a reactor II, a secondary hydrogenation reaction occurs from bottom to top, the reacted secondary hydrogenation reaction effluent is diffused into a central tube II through an opening on the wall of the central tube II, leaves the reactor II through a discharge outlet II, and is subjected to gas-liquid separation to obtain succinic anhydride products.
13. The maleic anhydride hydrogenation method according to claim 12, characterized in that: the first mixed feed in the step (1) is a liquid phase material taking hydrogen as a disperse phase and maleic anhydride solution as a continuous phase; the dispersion size of the hydrogen gas is 100nm to 1000. Mu.m, preferably 50 μm to 600. Mu.m.
14. The maleic anhydride hydrogenation method according to claim 12, characterized in that: the first mixed feeding adopts one or more of a static mixer, a dissolved air pump, a mechanical stirring device, a colloid mill, a micro-pore plate nano/micro hydrogen dispersing component, a micro-bubble generator, a ceramic membrane nano/micro hydrogen dispersing component and a micro-channel mixer.
15. The maleic anhydride hydrogenation method according to claim 12, characterized in that: the solvent in the step (1) is selected from one or more of benzene, toluene, xylene, acetone, tetrahydrofuran, gamma-butyrolactone, first-class acetone, cyclohexanone, ethyl acetate, diethyl succinate or ethylene glycol monomethyl ether; the concentration of maleic anhydride solution is 0.03-0.3 g/mL.
16. The maleic anhydride hydrogenation method according to claim 12, characterized in that: the hydrogen gas adopts hydrogen gas with purity of more than 90v percent.
17. The maleic anhydride hydrogenation method according to claim 12, characterized in that: the ratio of the volume flow rates of the hydrogen Nm 3/h in the reactor I and the reactor II to the maleic anhydride solution m 3/h in the step (1) was 5:1 to 100:1, preferably 10:1 to 50:1.
18. The maleic anhydride hydrogenation method according to claim 12, characterized in that: the hydrogenation reaction conditions of the reactor I are as follows: the reaction temperature is 40-200 ℃, preferably 50-90 ℃; the reaction pressure is 0.5-10.0 MPa, preferably 1-5.0 MPa; the liquid hourly space velocity is 1 to 20.0h -1, preferably 3.0 to 10.0h -1.
19. The maleic anhydride hydrogenation method according to claim 12, characterized in that: the hydrogenation reaction conditions of the reactor II are as follows: the reaction temperature is 40-100 ℃, preferably 50-70 ℃; the reaction pressure is 0.5-10.0 MPa, preferably 1-5.0 MPa; the liquid hourly space velocity is 0.1 to 5.0h -1, preferably 0.5 to 3.0h -1.
20. The maleic anhydride hydrogenation method according to claim 12, characterized in that: the sum of the maleic anhydride hydrogenation conversion rates of the reactor I and the reactor II is 100%, wherein the maleic anhydride hydrogenation conversion rate of the reactor I is 10% -99%, preferably 50% -95%, the maleic anhydride hydrogenation conversion rate of the reactor II is 1% -90%, preferably 5% -50%, and the maleic anhydride hydrogenation conversion rate of the reactor I is higher than the maleic anhydride hydrogenation conversion rate of the reactor II.
21. The maleic anhydride hydrogenation method according to claim 12, characterized in that: the hydrogenation catalyst is a supported nickel-based catalyst, wherein the catalyst carrier is one or more of SiO 2、Al2O3、SiO2- Al2O3、TiO2, activated carbon or molecular sieve; the catalyst is one of sphere, bar, clover and tooth sphere.
22. The maleic anhydride hydrogenation method according to claim 12, characterized in that: and part of liquid materials obtained by gas-liquid separation is recycled to the reactors I and II, and part of the materials enter a subsequent succinic anhydride product fractionation unit or enter the subsequent succinic anhydride product fractionation unit.
23. The maleic anhydride hydrogenation method according to claim 22, characterized in that: the recycle material recycled to the reactor I accounts for 5 to 80wt%, preferably 10 to 30wt%, of the fresh material at the inlet of the reactor I; the recycle to reactor II is 1 to 30wt%, preferably 5 to 20wt%, of the fresh feed to reactor I.
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