CN216987591U - Reaction device for preparing ethylene glycol by hydrogenation of ethanedioic acid ester - Google Patents
Reaction device for preparing ethylene glycol by hydrogenation of ethanedioic acid ester Download PDFInfo
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- CN216987591U CN216987591U CN202023099553.7U CN202023099553U CN216987591U CN 216987591 U CN216987591 U CN 216987591U CN 202023099553 U CN202023099553 U CN 202023099553U CN 216987591 U CN216987591 U CN 216987591U
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- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 88
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 title claims description 22
- -1 ethanedioic acid ester Chemical class 0.000 title description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 81
- 239000002245 particle Substances 0.000 claims description 31
- 239000007787 solid Substances 0.000 claims description 31
- 238000000926 separation method Methods 0.000 claims description 21
- 239000000428 dust Substances 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000004744 fabric Substances 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 229920000620 organic polymer Polymers 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 56
- 238000012546 transfer Methods 0.000 abstract description 9
- 238000005265 energy consumption Methods 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 150000002148 esters Chemical class 0.000 abstract 1
- 239000012495 reaction gas Substances 0.000 description 21
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- LOMVENUNSWAXEN-UHFFFAOYSA-N Methyl oxalate Chemical compound COC(=O)C(=O)OC LOMVENUNSWAXEN-UHFFFAOYSA-N 0.000 description 8
- 239000003245 coal Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 125000004494 ethyl ester group Chemical group 0.000 description 3
- 230000005484 gravity Effects 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 238000010517 secondary reaction Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229940083957 1,2-butanediol Drugs 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- QYMFNZIUDRQRSA-UHFFFAOYSA-N dimethyl butanedioate;dimethyl hexanedioate;dimethyl pentanedioate Chemical compound COC(=O)CCC(=O)OC.COC(=O)CCCC(=O)OC.COC(=O)CCCCC(=O)OC QYMFNZIUDRQRSA-UHFFFAOYSA-N 0.000 description 1
- LOMVENUNSWAXEN-NUQCWPJISA-N dimethyl oxalate Chemical group CO[14C](=O)[14C](=O)OC LOMVENUNSWAXEN-NUQCWPJISA-N 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- CBOIHMRHGLHBPB-UHFFFAOYSA-N hydroxymethyl Chemical compound O[CH2] CBOIHMRHGLHBPB-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
The utility model relates to a reaction device for preparing ethylene glycol by hydrogenating oxalate, which comprises a fluidized bed reactor (100), a fixed bed reactor (200), a filter (300) and a water vapor bag (400), wherein the bottom of the fluidized bed reactor (100) is connected with a raw material gas inlet pipe (1), the top of the fluidized bed reactor (100) is connected with the filter (300), the filter (300) is connected with the fixed bed reactor (200), and the water vapor bag (400) is connected with the fluidized bed reactor (100) through a circulating pipeline. Compared with the prior art, the oxalic ester and the hydrogen react in the fluidized bed reactor and the fixed bed reactor twice in sequence, the fluidized bed is utilized to realize good heat transfer and temperature control, the medium conversion efficiency is obtained, and the fixed bed reactors are combined in series, so that the high capacity of a single reactor system can be realized, the investment, the energy consumption and the total cost of unit yield are reduced, and the competitiveness of the single reactor system with a petrochemical route is improved.
Description
Technical Field
The utility model relates to a device and a process for producing ethylene glycol by a coal chemical industry route, in particular to a method for producing ethylene glycol by hydrogenating dimethyl oxalate or diethyl ester, which adopts a combination of a fluidized bed and a fixed bed reactor and is suitable for large-scale production of ethylene glycol.
Background
Ethylene glycol is an important basic organic chemical raw material, and is mainly used as a polycondensation monomer of polyester. Due to the rapid growth of the polyester industry, the global capacity of ethylene glycol approaches 4000 million tons/year. The traditional production route is an ethylene-ethylene oxide-based petroleum route, the production in China can not meet the demand, the import quantity is large, the import dependence of nearly ten years is always more than 70%, and the development of the polyester industry in China is severely restricted.
The resource characteristics of China are that coal is rich in oil, little in gas and poor in quality, and the development of the coal chemical industry route for producing ethylene glycol has strategic and practical significance. The production of ethylene glycol by the coal chemical industry route comprises three reaction steps: (1) coupling: CO and nitrous acid ester (methyl ester or ethyl ester) are coupled to generate ethanedioic acid ester and coproduce NO, (2) hydrogenation: hydrogenation of ethanediol to ethanediol and coproduction of methanol (ethanol), esterification: NO and methyl (ethyl) alcohol are oxidized and esterified to produce methyl (ethyl) nitrite and water. Three reactions constitute a cycle of NO and methanol (ethanol), the overall reaction being:
2CO+4H2+0.5O2=(CH2OH)2+H2O
clearly, this reaction is very close to that of methanol, and therefore, the coal chemical route has significant resource advantages over the traditional ethylene-ethylene oxide route.
The coal chemical industry route of ethylene glycol has been the American combined carbon chemistry and the Utility model of the chemical company of Japan department respectively in the 80 s of the last century, scientists in China started basic research in the 90 s, especially entered the present century, and a plurality of units in China have carried out technical development, and industrialization, rapid development in the last decade, and the established + under-built + proposed capacity will reach 1500 ten thousand tons/year. However, in recent years, due to the low price of petroleum, the ethylene glycol route in the coal chemical industry has large area loss due to the small capacity, large investment and high energy consumption of a single set, and is difficult to compete with the petroleum route.
Therefore, the technical development direction of the ethylene glycol in the coal chemical industry is how to reduce the investment, improve the production capacity of a single set (namely a single reactor), reduce the investment, reduce the energy consumption and improve the competitive capacity with the petroleum route.
The problem with the current art is that the reaction temperature window is narrow in hydrogenation reactions. Generally, the higher the reaction temperature, the better, but the reaction temperature cannot be high, 1,2 butanediol which is difficult to separate is generated after the reaction is high, and the high temperature also causes sintering deactivation of the copper-based catalyst, so the feasible operation temperature range is narrow. On the other hand, the reactor adopts a heat exchange type tube array fixed bed reactor, is limited by heat transfer capacity, has small tube diameter, and limits the production capacity, and the capacity of a single set of reactor is about 5 ten thousand tons per year generally.
Different reactors have their own disadvantages according to the principles of chemical reaction engineering. In a gas-solid reaction system, a fluidized bed reactor is adopted to better solve the problem of heat transfer, but the reaction efficiency of the fluidized bed reaction is not as high as that of a fixed bed, and different specific embodiments are provided for different reactions by combining the characteristics of the reactions.
For the hydrogenation reaction of oxalate, patent document 201110045352 (fluidized bed catalyst in which oxalate is used to catalyze ethylene glycol) discloses a copper catalyst modified by using cerium and niobium as auxiliary agents, which is used in a fluidized bed reactor; 201110045364 (method for producing ethylene glycol by oxalate through fluidized bed catalytic reaction) adopts a fluidized bed reactor, and the catalyst is modified by bismuth and tungsten. Although the literature states that 100% conversion of oxalate can be achieved, it is difficult to achieve in practice because the fluidized bed reactor is characterized by non-uniformity of gas-solid flow, especially the presence of back-mixing due to large bubbles, and the conversion efficiency is difficult to achieve to a high level, and even impossible to achieve 100% (even theoretically, unless the catalyst loading is infinite), and apparently is not applicable, and thus, no further development or industrial application has been found so far.
SUMMERY OF THE UTILITY MODEL
The utility model aims to overcome the problems of low production capacity, limitation of large-scale production and difficult improvement of conversion efficiency in the prior art, and provides a reaction device technology for preparing ethylene glycol by hydrogenation of oxalate, which has the advantages of simple structure, high yield and high conversion efficiency and is particularly suitable for the requirement of large-scale production.
The purpose of the utility model can be realized by the following technical scheme: the utility model provides a reaction unit of oxalate hydrogenation system ethylene glycol, includes fluidized bed reactor (100), fixed bed reactor (200), filter (300) and vapor package (400), fluidized bed reactor (100) bottom connect feed gas intake pipe (1), filter (300) are connected at the top, fixed bed reactor (200) is connected in filter (300), vapor package (400) connect fluidized bed reactor (100) through circulating line, combined the advantage that fluidized bed reactor heat transfer capacity is high and fixed bed reactor conversion is high, can realize good temperature control and reactor steady operation simultaneously.
The fluidized bed reactor and the fixed bed reactor are connected with a filter through a dust-containing gas pipeline and a clean gas pipeline to realize gas-solid separation of fine particle catalysts, so that the catalysts are thoroughly recovered, the waste is reduced, the blockage of subsequent fixed bed reaction is eliminated, and stable and safe operation is ensured.
The fluidized bed reactor comprises a bottom gas distribution area, a middle reaction area and a top gas-solid separation area, wherein a gas distributor a is arranged in the gas distribution area, a catalyst a and a heat exchange tube are filled in the middle reaction area, and a gas-solid separator is arranged in the gas-solid separation area, so that the temperature of the reactor is controlled by heat transfer while reaction is ensured, the uniform distribution of reaction gas is ensured, and the reaction operation is stabilized.
The heat exchange tube and the steam bag form a circulation loop through a water inlet pipeline and a water outlet pipeline; a plurality of heat exchange tubes which are connected in parallel are uniformly arranged in the reaction area, and the catalyst is filled between the heat exchange tubes, so that the excess heat released by the reaction can be used for producing steam while the reaction is carried out.
The particle size of the catalyst a is between 20 and 1000 microns, preferably between 50 and 500 microns.
The fixed bed reactor is filled with a catalyst b and a gas distributor b, and the particle size of the catalyst b is between 2 and 10 millimeters, preferably between 4 and 8 millimeters, so that the resistance is reduced, and the high reaction efficiency is ensured.
The fixed bed reactor is an adiabatic reactor, has simple structure and high efficiency, reduces investment, and the catalyst b is spherical, cylindrical, annular or porous cylindrical, preferably annular, has low gas resistance and reduces energy consumption.
The filter is internally provided with a filter pipe which is a microporous metal sintering pipe, a ceramic pipe, a glass fiber cloth bag or an organic polymer fiber cloth bag, is provided with three interfaces, is respectively connected with the top of the upstream fluidized bed reactor through a dust-containing gas pipeline, is connected with the downstream fixed bed reactor through a clean gas pipeline, and is connected with the lower part of the fluidized bed reactor through a catalyst particle backflow pipeline, so that the catalyst is ensured to be rapidly and continuously recovered, the reaction gas is purified, and the blockage of the downstream fixed bed reactor is reduced.
The reaction process for preparing the ethylene glycol by hydrogenating the oxalate by adopting the device comprises the following steps:
1. first-order reaction: raw material gas enters a lower cavity of the fluidized bed reactor (100) through a raw material gas inlet pipe (1), is uniformly distributed through a gas distributor a (102), enters a fluidized section containing a catalyst a (101), and contacts with the catalyst a (101) to generate a catalytic reaction for preparing ethylene glycol through hydrogenation of oxalate, so that ethylene glycol is generated and methanol or ethanol is co-produced;
2. heat transfer: the heat released by the hydrogenation reaction in the fluidized bed reactor raises the temperature of the reaction gas to a set temperature, namely the temperature of the fluidized bed reactor, and removes redundant reaction heat through the heat exchange between the reaction gas and a heat exchange tube, and forms water circulation with a water vapor bag through an inlet water pipeline and an outlet water pipeline to produce steam in a steam drum;
3. gas-solid separation: the reaction gas obtained by hydrogenation reaction in the fluidized bed reactor enters an upper gas-solid separation zone for gas-solid separation, the catalyst particles with larger particle size carried by the reaction gas are separated by gravity settling, the catalyst particles with smaller particle size are separated by a gas-solid separator by cyclone separation, the catalyst with fine particle size is conveyed to a filter outside the reactor by a dust-containing gas pipeline for thorough filtration and separation, the fine particle catalyst obtained by filtration returns to the fluidized section of the fluidized bed reactor for recycling through a catalyst return pipeline, the obtained clean reaction gas enters a downstream fixed bed reactor through a clean pipeline,
4. and (3) secondary reaction: the clean reaction gas is reacted for the second time in the fixed bed reactor, so that high conversion efficiency is realized.
1, the volume of feed gas entering a fluidized bed reactor (100) in the step 1 consists of 1-5% of oxalate, and the balance of hydrogen and the like; wherein the ethanedioic acid ester is dimethyl oxalate or diethyl oxalate; the raw material gas is a configured mixed gas.
The top pressure of the fluidized bed reactor is 1.5-5.5Mpa, because the reaction is not facilitated by too high and too low, the top temperature is 160-200 ℃, preferably 170-190 ℃, the reaction speed is low when the temperature is too low, and the negative reaction occurs when the temperature is too high; moreover, the fixed bed reactor is operated in an adiabatic way, so that the reaction temperature is continuously increased, and the conversion efficiency is favorably improved;
the conversion rate of dimethyl oxalate or ethyl ester of the fluidized bed reactor is 80-90%, and the total conversion rate of dimethyl oxalate or ethyl ester of the two reactors is 95-99%.
The catalyst adopted by the fluidized bed reactor and the fixed bed reactor is a common catalyst for preparing the glycol by hydrogenating the prior oxalate, is a copper-based catalyst, and the carrier is inert silicon dioxide.
Compared with the prior art, the utility model has the following advantages:
1. the utility model has carried on the series connection with the fixed bed the fluidized bed, utilized the fluidized bed and advantage that the fixed bed reacts respectively, overcome their own disadvantage, the heat release of this reaction is not high, it is a system of medium and small heat release, the catalyst stability is very good, the reaction rate is not calculated very high, the utility model utilizes the fluidized bed to realize good heat transfer and temperature control at first, can improve the flow rate of the unit volume reaction mass, thus improve the production capacity, namely propose a high-yield reaction unit, get the medium conversion efficiency, connect in series and combine a fixed bed reactor, can realize the high capacity of the single set of reactor system, reduce investment, energy consumption and total cost of the unit output, improve its competitiveness with petrochemical route; can produce carbonic acid dibasic ester as a byproduct to a larger extent and further improve the economic benefit of the device.
2. Because the gas at the outlet of the fluidized bed reactor carries more catalyst dust, the subsequent fixed bed reactor can be blocked by the simple series fixed bed, and therefore, the filter is arranged between the two reactors, and the service life of the device is prolonged.
Drawings
FIG. 1 is a schematic view of a reaction apparatus for preparing ethylene glycol by hydrogenation of oxalate according to the present invention.
The labels in the figure are: the catalyst comprises a fluidized bed reactor 100, a catalyst a101, a gas distributor a102, a heat exchange pipe 103, a gas-solid separator 104, a fixed bed reactor 200, a catalyst b201, a gas distributor b202, a filter 300 and a water vapor bag 400;
a raw material gas inlet pipe 1, a dust-containing gas pipeline 2, a clean gas pipeline 3, a catalyst particle backflow pipeline 4, a total water inlet pipeline 6, a steam product pipeline 7, a water inlet pipeline 8 and a water outlet pipeline 9.
Detailed Description
The utility model is described in detail below with reference to the figures and specific embodiments.
Example 1:
as shown in FIG. 1, this example corresponds to a production energy of 10 ten thousand tons of ethylene glycolThe reaction device for preparing the ethylene glycol by hydrogenating the dimethyl oxalate comprises a fluidized bed reactor 100 and a fixed bed reactor 200, wherein the fluidized bed reactor 100 is positioned at the upstream of the fixed bed reactor 200, namely the fixed bed reactor is connected in series after the fluidized bed reaction, the diameter of the fluidized bed reactor is 1.8 meters, the height of the fluidized bed reactor is 15 meters, and the diameter of the fixed bed reaction is 1.3 meters, and the height of the fixed bed reaction is 6 meters; meanwhile, a filter 300 is connected between the fluidized bed reactor 100 and the fixed bed reactor 200 through a dust-containing gas pipeline 2 and a clean gas pipeline 3 for realizing gas-solid separation, and the filter is made of a stainless steel metal particle sintering microporous tube and can effectively filter and separate fine particle catalysts; the fluidized bed reactor 100 comprises a bottom gas distribution zone, a middle reaction zone and a top gas-solid separation zone, wherein a gas distributor a102 is arranged in the gas distribution zone, a catalyst a101 is filled in the middle reaction zone, and the catalyst filling amount is 5m3The particle size of the catalyst a101 is 50-350 micrometers, a plurality of heat exchange tubes 103 connected in parallel are uniformly arranged in the reaction area, the catalyst a101 is filled in the heat exchange tubes 103 among the heat exchange tubes, the gas distributor a102 is a perforated plate type distributor, the heat exchange tubes are of a stainless steel tube type, and the total area is 100m2The diameter of the heat exchange tube is 50mm, the length of the heat exchange tube is 6 meters, and 100 heat exchange tubes are connected in parallel; a gas-solid separator 104 is arranged in the gas-solid separation zone, and the gas-solid separator 104 is a cyclone separator. The heat exchange tube 103 forms a circulation loop with the steam packet 400 through a water inlet pipeline 8 and a water outlet pipeline 9, and can produce 2.8 tons/hr of steam;
the fixed bed reactor 200 is filled with a catalyst b201 and a gas distributor b202, and the particles of the catalyst b201 are circular catalysts with the diameter of 6 mm, the thickness of the circular wall is 1.5 mm, the height of the circular wall is 6 mm, and the filling amount is 5m3(ii) a The fixed bed reactor 200 is an adiabatic reactor, and the catalyst b201 is annular; the filter 300 is provided with a filter tube, which is a microporous metal sintered tube, and has three ports, and the filter is connected with the top of the upstream fluidized bed reactor 100 through a dust-containing gas pipeline 2, connected with the downstream fixed bed reactor 200 through a clean gas pipeline 3, and connected with the lower part of the fluidized bed reactor 100 through a catalyst particle backflow pipeline 4, and the recovered fine particle catalystAnd refluxing to the fluidized bed for reaction.
The reaction process for preparing the ethylene glycol by hydrogenating the dimethyl oxalate according to the device comprises the following steps of:
(1) first-order reaction: the raw material gas enters a lower cavity of a fluidized bed reactor 100 through a raw material gas inlet pipe 1, is uniformly distributed through a gas distributor a102, enters a fluidized section containing a catalyst a101, contacts with the catalyst a101 to generate dimethyl oxalate hydrogenation reaction for preparing ethylene glycol, generates ethylene glycol and coproduces methanol, wherein the volume component of the raw material gas is dimethyl oxalate which is 2%, and the rest components are hydrogen;
(2) heat transfer: the heat released by the hydrogenation reaction in the fluidized bed reactor 100 raises the temperature of the reaction gas from 40 ℃ to 175 ℃ of the fluidized bed reactor 100 on one hand, and removes the redundant reaction heat through the heat exchange between the reaction gas and the heat exchange tube 103 on the other hand, and forms a water circulation with the water vapor bag 400 through the inlet water line 8 and the outlet water line 9, steam is produced in the water vapor bag 400, the steam yield is 2.5 tons/hr, the steam is discharged from the steam product line 7, and the fresh desalted and deoxidized soft water total water inlet line 6 is added into the water vapor bag to maintain the liquid level of the water vapor bag to be stable;
(3) gas-solid separation: the reaction gas obtained by hydrogenation reaction in the fluidized bed reactor 100 enters an upper gas-solid separation zone for gas-solid separation, the catalyst particles with larger particle size carried by the reaction gas are separated by gravity settling, the catalyst particles with smaller particle size are separated by cyclone separation through a gas-solid separator 104, the catalyst with fine particle size is conveyed to a filter 300 by a dust-containing gas pipeline 2 for thorough filtration, the fine particle catalyst obtained by filtration returns to the fluidized section of the fluidized bed reactor 100 through a catalyst return pipeline 4 for recycling, the obtained clean reaction gas enters a downstream fixed bed reactor 200 through a clean gas pipeline 3, and the solid content in the clean reaction gas is 3mg/Nm3;
(4) And (3) secondary reaction: the product gas from step (3) leaves the filter 300 and enters the fixed bed reactor 200 through the clean gas line 3 for the second hydrogenation reaction, achieving high conversion efficiency.
In addition, the top pressure of the fluidized bed reactor 100 was 2.0Mpa, the top temperature was 175 ℃, and the fixed bed reactor 200 was operated adiabatically; the conversion of dimethyl oxalate in the fluidized bed reactor 100 was 84%, the total conversion of nitrite in both reactors was 99%, and the selectivity to ethylene glycol was 97.5%.
Example 2:
as shown in fig. 1, the reaction apparatus for preparing ethylene glycol by hydrogenation of diethyl oxalate in this example corresponds to the production capacity of 30 ten thousand tons of ethylene glycol, and includes a fluidized bed reactor 100 and a fixed bed reactor 200, and the fluidized bed reactor 100 is located upstream of the fixed bed reactor 200, i.e. a fixed bed reactor is connected in series after the fluidized bed reaction, the fluidized bed reactor has a diameter of 3.25 meters and a height of 15 meters, and the fixed bed reaction has a diameter of 2.25 meters and a height of 6 meters; meanwhile, a filter 300 is connected between the fluidized bed reactor 100 and the fixed bed reactor 200 through a dust-containing gas pipeline 2 and a clean gas pipeline 3 for realizing gas-solid separation, and the filter is made of a stainless steel metal particle sintering microporous tube and can effectively filter and separate fine particle catalysts; the fluidized bed reactor 100 comprises a catalyst a101, and the loading amount of the catalyst a is 15m3A gas distributor 102, a heat exchange tube 103 and a gas-solid separator 104, wherein the particle size of the catalyst a101 is 50-350 microns, the gas distributor a102 is a perforated plate distributor, the heat exchange tube is in a stainless steel tube type, and the total area is 300m2The diameter of the heat exchange tube is 50mm, the length of the heat exchange tube is 6 meters, and 300 heat exchange tubes are connected in parallel; the fixed bed reactor 200 is filled with a catalyst b201 and a gas distributor b202, and the particles of the catalyst b201 are circular ring-shaped catalysts with the diameter of 6 mm, the ring wall thickness is 1.5 mm, the ring height is 6 mm, and the loading is 15m3(ii) a The fluidized bed reactor also comprises a water vapor bag 400, wherein the water vapor bag 400 is connected with the heat exchange tube 103 in the fluidized bed reactor 100 through a water inlet pipeline 8 and a water outlet pipeline 9 and can produce 8.5 tons/hr of steam; the fixed bed reactor 200 is an adiabatic reactor, and the catalyst b201 is annular; the filter 300 is internally provided with a filter pipe which is a microporous metal sintered pipe, and is provided with three interfaces which respectively pass through the dust-containing gas pipeline 2 and the upstream fluidized bed reactor 100Is connected with the downstream fixed bed reactor 200 through a clean gas line 3, and is connected with the lower part of the fluidized bed reactor 100 through a catalyst particle reflux line 4, and the recovered fine particle catalyst is refluxed to the fluidized bed for reaction.
The reaction process for preparing the ethylene glycol by hydrogenating diethyl oxalate according to the device comprises the following steps:
(1) first-order reaction: raw material gas enters a lower cavity of a fluidized bed reactor 100 through a raw material gas inlet pipe 1, is uniformly distributed through a gas distributor a102, enters a fluidized section containing a catalyst a101, contacts with the catalyst a101 to generate a reaction for preparing ethylene glycol by diethyl oxalate hydrogenation, generates ethylene glycol and co-produces ethanol, and has the volume composition of diethyl oxalate of 3.3 percent and the balance of hydrogen;
(2) heat transfer: the heat released by the hydrogenation reaction raises the temperature of the reaction gas from 40 ℃ to 190 ℃ in the fluidized bed reactor 100 on one hand, and removes the redundant reaction heat through the heat exchange of the reaction gas and the heat exchange tube 103 on the other hand, and forms a water circulation with the water vapor bag 400 through the inlet water line 8 and the outlet water line 9, steam is produced in the water vapor bag 400, the steam yield is 8.5 tons/hr, the steam is discharged from the steam product line 7, and the fresh desalted, deoxidized and softened water total water inlet line 6 is added into the water vapor bag to maintain the liquid level of the water vapor bag to be stable;
(3) gas-solid separation: the reaction gas obtained from the hydrogenation reaction in the step 2 enters the upper space of the fluidized bed reactor 100, the catalyst particles with larger particle size carried by the reaction gas are separated by gravity settling, the catalyst particles with smaller particle size are separated by cyclone separation through a gas-solid separator 104, the catalyst with fine particle size is conveyed to a filter 300 through a dust-containing gas pipeline 2 for thorough filtration, the fine particle catalyst obtained by filtration returns to the fluidized section of the fluidized bed reactor 100 through a catalyst return pipeline 4 for recycling, the obtained clean reaction gas enters the downstream fixed bed reactor 200 through a clean gas pipeline 3, and the solid content in the clean reaction gas is 2.5mg/Nm3;
(4) And (3) secondary reaction: the product gas from step (3) leaves the filter 300 and enters the fixed bed reactor 200 through the clean gas line 3 for the second hydrogenation reaction, achieving high conversion efficiency.
In addition, the top pressure of the fluidized bed reactor 100 is 2.5Mpa, the top temperature is 190 ℃, and the fixed bed reactor 200 is operated adiabatically; the conversion of diethyl oxalate in fluidized bed reactor 100 was 88%, the total diethyl oxalate conversion for both reactors was 98.5%, and the selectivity to ethylene glycol was 98.5%.
Example 3
The particle size of the catalyst a is 20-250 microns, and the particle size of the catalyst b is spherical with the diameter of 2 mm.
The top pressure of the fluidized bed reactor 100 was 5.5MPa, and the top temperature was 200 ℃ as in example 1.
The conversion of diethyl oxalate in the fluidized bed reactor 100 was 90%, the total conversion of diethyl oxalate in both reactors was 99.3%, and the selectivity to ethylene glycol was 96.5%.
Example 4
The particle size of the catalyst a is between 850-1000 microns, and the particle size of the catalyst b is 10 mm cylindrical.
The top pressure of the fluidized bed reactor 100 was 1.5MPa, and the top temperature was 160 ℃ as in example 1.
The conversion of diethyl oxalate in the fluidized bed reactor 100 was 89.5%, the total conversion of diethyl oxalate in both reactors was 98.7%, and the selectivity to ethylene glycol was 97.6%.
Claims (6)
1. The reaction device for preparing the ethylene glycol by hydrogenating the oxalate is characterized by comprising a fluidized bed reactor (100), a fixed bed reactor (200), a filter (300) and a water vapor bag (400), wherein the bottom of the fluidized bed reactor (100) is connected with a raw material gas inlet pipe (1), the top of the fluidized bed reactor (100) is connected with the filter (300), the filter (300) is connected with the fixed bed reactor (200), and the water vapor bag (400) is connected with the fluidized bed reactor (100) through a circulating pipeline;
the fluidized bed reactor (100) comprises a bottom gas distribution zone, a middle reaction zone and a top gas-solid separation zone, wherein a gas distributor a (102) is arranged in the gas distribution zone, a catalyst a (101) and a heat exchange tube (103) are filled in the middle reaction zone, and a gas-solid separator (104) is arranged in the gas-solid separation zone;
the heat exchange tube (103) and the steam packet (400) form a circulation loop through a water inlet pipeline (8) and a water outlet pipeline (9); a plurality of heat exchange tubes (103) which are connected in parallel are uniformly arranged in the reaction zone, and a catalyst a (101) is filled among the heat exchange tubes;
the particle size of the catalyst a (101) is between 20 and 1000 microns;
the fixed bed reactor (200) is filled with a catalyst b (201) and a gas distributor b (202), and the particle size of the catalyst b (201) is 2-10 mm;
the catalyst adopted by the fluidized bed reactor and the fixed bed reactor is a copper-based catalyst, and the carrier is inert silicon dioxide.
2. The reaction device for preparing ethylene glycol by hydrogenating oxalate according to claim 1, wherein the particle size of the catalyst a (101) is 50 to 500 μm.
3. The reaction unit for preparing ethylene glycol by hydrogenating oxalate according to claim 1, wherein the particle size of the catalyst b (201) is 4-8 mm.
4. The reaction device for preparing ethylene glycol by hydrogenating oxalate according to claim 1, wherein the fixed bed reactor (200) is an adiabatic reactor, and the catalyst b (201) is spherical, cylindrical, annular or porous cylindrical.
5. The reaction unit for preparing ethylene glycol by hydrogenating oxalate according to claim 4, wherein the catalyst b (201) is ring-shaped.
6. The reaction device for preparing ethylene glycol through hydrogenation of oxalate according to claim 1, wherein the filter (300) is internally provided with a filter tube which is a microporous metal sintered tube, a ceramic tube, a glass fiber cloth bag or an organic polymer fiber cloth bag and is provided with three ports, the three ports are respectively connected with the top of the upstream fluidized bed reactor (100) through a dust-containing gas pipeline (2), connected with the downstream fixed bed reactor (200) through a clean gas pipeline (3), and connected with the lower part of the fluidized bed reactor (100) through a catalyst particle return pipeline (4).
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