CN113856567A - Ethylene carbonate hydrogenation reactor and application thereof - Google Patents
Ethylene carbonate hydrogenation reactor and application thereof Download PDFInfo
- Publication number
- CN113856567A CN113856567A CN202111305330.8A CN202111305330A CN113856567A CN 113856567 A CN113856567 A CN 113856567A CN 202111305330 A CN202111305330 A CN 202111305330A CN 113856567 A CN113856567 A CN 113856567A
- Authority
- CN
- China
- Prior art keywords
- ethylene carbonate
- reactor
- reaction
- interlayer
- reaction bed
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 title claims abstract description 157
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 51
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 175
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 168
- 238000006243 chemical reaction Methods 0.000 claims abstract description 161
- 239000010410 layer Substances 0.000 claims abstract description 130
- 239000011229 interlayer Substances 0.000 claims abstract description 72
- 239000003507 refrigerant Substances 0.000 claims abstract description 59
- 239000001257 hydrogen Substances 0.000 claims abstract description 46
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 46
- 239000007789 gas Substances 0.000 claims abstract description 44
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims description 44
- 239000000047 product Substances 0.000 claims description 32
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 25
- 229910052802 copper Inorganic materials 0.000 claims description 25
- 239000010949 copper Substances 0.000 claims description 25
- 239000002245 particle Substances 0.000 claims description 22
- 238000013461 design Methods 0.000 claims description 18
- 238000007599 discharging Methods 0.000 claims description 13
- 239000000945 filler Substances 0.000 claims description 12
- 238000005457 optimization Methods 0.000 claims description 11
- 230000003197 catalytic effect Effects 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 9
- 238000009904 heterogeneous catalytic hydrogenation reaction Methods 0.000 claims description 8
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 238000013178 mathematical model Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000002068 genetic effect Effects 0.000 claims description 3
- 238000012546 transfer Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000004364 calculation method Methods 0.000 claims description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 14
- 239000003921 oil Substances 0.000 description 8
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 239000001569 carbon dioxide Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000002679 ablation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 ethylene carbonate ester Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0496—Heating or cooling the reactor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
-
- G—PHYSICS
- G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
- G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
- G16C10/00—Computational theoretical chemistry, i.e. ICT specially adapted for theoretical aspects of quantum chemistry, molecular mechanics, molecular dynamics or the like
-
- G—PHYSICS
- G16—INFORMATION AND COMMUNICATION TECHNOLOGY [ICT] SPECIALLY ADAPTED FOR SPECIFIC APPLICATION FIELDS
- G16C—COMPUTATIONAL CHEMISTRY; CHEMOINFORMATICS; COMPUTATIONAL MATERIALS SCIENCE
- G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
- G16C20/10—Analysis or design of chemical reactions, syntheses or processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Computing Systems (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Theoretical Computer Science (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Bioinformatics & Computational Biology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a ethylene carbonate hydrogenation reactor and application thereof, wherein a multi-section heat exchange fixed bed reactor comprises a reactor shell, an upper end socket, a lower end socket, a main feeding pipe, a main distributor, a reaction bed layer, an interlayer heat exchange pipe, a refrigerant inlet, a refrigerant outlet and a product gas guide pipe; a feed pipe, an interlayer distributor and an interlayer heat exchange pipe are arranged among the reaction bed layers; when the method is applied, premixed high-temperature ethylene carbonate gas and hydrogen are dispersed and then enter a first reaction bed layer, and supplemented ethylene carbonate gas is introduced through an interlayer feeding pipe, is mixed and dispersed with the first-stage product mixed gas, and then is subjected to step-by-step reaction. Compared with the prior art, the method optimizes and selects the structure and the operation parameters of the reactor, realizes the maximization of the yield of the total alcohol or glycol product, reduces the hydrogen-ester ratio of the operation, and greatly improves the process economy; solves the problems of low yield of target products and high hydrogen-ester ratio in the process of the industrial process of the ethylene carbonate hydrogenation coproduction of methanol and ethylene glycol.
Description
Technical Field
The invention relates to the field of chemicals prepared from carbon dioxide, in particular to a hydrogenation reactor for ethylene carbonate and application thereof.
Background
The increasing global carbon dioxide emission brings serious environmental risks of aggravated greenhouse effect, seawater acidification, glacier ablation and the like, so that the policy targets of 2030 carbon peak reaching and 2060 carbon neutralization are put forward in China. The carbon dioxide green utilization technology for producing chemicals by taking carbon dioxide as a carbon source is developed, which is beneficial to reducing the carbon footprint of chemical production, reducing the consumption of fossil fuels and slowing down the increase of atmospheric carbon dioxide concentration. The method prepares ethylene carbonate by the reaction of carbon dioxide and ethylene oxide, and produces ethylene glycol and methanol products with high added values by the hydrogenation of ethylene carbonate, is a green chemical process route with 100 percent of atom utilization rate, and is concerned under the background of 'carbon peak reaching and carbon neutralization'. At present, the fixed bed reaction process for producing ethylene carbonate by using carbon dioxide and ethylene oxide realizes industrial demonstration operation; the hydrogenation of ethylene carbonate is still in the industrial test stage.
Chinese patent CN110975939A discloses a ruthenium-based complex homogeneous catalyst for the coproduction of methanol and ethylene glycol by the hydrogenation of ethylene carbonate; chinese patents CN110947382A, CN107754802A, CN110586094A, and CN110227545A disclose several copper-based heterogeneous catalyst systems suitable for the co-production of methanol and ethylene glycol by the hydrogenation of ethylene carbonate. These reports focus on catalytic materials and do not address problems of industrial reactor design, product separation and system optimization for large-scale industrial applications. Chinese patents CN210906088U and CN112387219A disclose two adiabatic fixed bed reactor designs for ethylene carbonate hydrogenation, mainly solving the problems of ethylene carbonate liquid phase feeding and distribution, but do not optimize the reactor design and operation conditions with respect to the characteristics of reaction kinetics.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an ethylene carbonate hydrogenation reactor and application thereof, and by means of sectional optimization control of bed temperature, the yield of different products can be maximized, the hydrogen-ester ratio is reduced, and the requirements of large-scale production are met.
In the conception process of the technical scheme, the applicant makes the following analysis:
the copper-based catalyst has the advantages of low price, high space-time yield, simple product separation and the like, and has great industrial application potential. In the heterogeneous hydrogenation reaction of ethylene carbonate based on a copper-based catalyst, firstly, ethylene carbonate is gasified and mixed with hydrogen, and the mixture passes through a copper-based catalyst bed layer to react under the conditions of 180-220 ℃, 2-6MPa and 60-200 hydrogen-ester ratio to generate methanol and ethylene glycol. The main reaction equation is as follows (in the formula, ethylene carbonate ester is EC for short, ethylene glycol is EG for short, methanol is MeOH for short, and ethanol is EtOH for short):
①EC+3H2→EG+MeOH
②EC+H2→EG+CO
in this process, a side reaction represented by the following formula is also accompanied:
③EG+H2→EtOH+H2O
the reaction system has the following characteristics: 1) the reaction is moderate and exothermic; 2) the activation energy of the side reaction is high, and the selectivity of the main reaction is obviously reduced at high temperature; 3) the high hydrogen-ester ratio and high pressure are favorable for improving the conversion rate of the ethylene carbonate; 4) ethylene carbonate is easily condensed (boiling point 248 ℃ under 1 atm). Because the selectivity of the heterogeneous hydrogenation reaction of the ethylene carbonate is sensitive to the temperature, when the ethylene carbonate is produced industrially, if a conventional multi-section heat-insulating fixed bed reactor is adopted, the inlet temperature and the outlet temperature of each section are low and too high, the side reaction is promoted, and the product yield is reduced; if an isothermal tubular fixed bed hydrogenation reactor is adopted, the average temperature of the bed layer is lower, which is not beneficial to high conversion rate and can also cause the yield of the product to be reduced. On the other hand, the suitable production temperatures of the main products, ethylene glycol and methanol, are different and cannot be satisfied simultaneously. In addition, in order to meet the high hydrogen-ester ratio condition that the copper-based catalyst is suitable for working, the single-pass conversion rate of hydrogen is low, a large amount of unreacted hydrogen needs to be recycled, and the energy consumption of the process is obviously increased.
The purpose of the invention can be realized by the following technical scheme:
the first purpose of the invention is to protect an ethylene carbonate hydrogenation reactor, which can adopt a specific reactor structure and can work in at least two operation modes including methanol, ethylene glycol total yield maximization and ethylene glycol yield maximization through the optimized selection of reactor structure parameters and reactor operation parameters. The reactor comprises a reactor upper end enclosure, a reactor lower end enclosure and a reactor shell arranged between the reactor upper end enclosure and the reactor lower end enclosure;
the reactor upper end socket is provided with a main feeding pipe and a charging port, and the reactor lower end socket is provided with a discharging pipe and a discharging port;
the outer wall of the reactor shell is provided with at least one stage of interlayer feeding pipe comprising a first interlayer feeding pipe, at least one stage of refrigerant inlet comprising a first refrigerant inlet, at least one stage of refrigerant outlet comprising a first refrigerant outlet and a manhole;
the reactor is characterized in that a main distributor, at least one-stage interlayer distributor comprising a first interlayer distributor, at least two-stage reaction beds comprising a first reaction bed and a second reaction bed, at least one-stage interlayer heat exchange tube comprising a first interlayer heat exchange tube and a product gas guide tube are arranged in the inner cavity of the reactor shell.
Further, the main feeding pipe and the discharging pipe are arranged vertically downwards, and the central axes of the main feeding pipe and the discharging pipe are collinear or parallel with the central axis of the reactor shell;
the direction of the interlayer feeding pipe, the refrigerant inlet and the refrigerant outlet is vertical to the outer wall of the reactor shell.
Further, the inlet of the main distributor is connected with a main feeding pipe, and the outlet of the main distributor is arranged above the first reaction bed layer;
the inlet of the first interlayer distributor is connected with the first interlayer feeding pipe, the outlet of the first interlayer distributor is arranged above the second reaction bed layer, and the like is carried out if a subsequent layer exists;
and the inlet of the product gas guide pipe is arranged below the last stage of the reaction bed layer, and the outlet of the product gas guide pipe is connected with the discharge pipe.
Furthermore, each reaction bed layer comprises a packing layer, a catalytic layer and a support sieve plate from top to bottom, wherein the packing layer is filled with metal or ceramic filler, and the catalytic layer is filled with supported copper-based catalyst particles.
Furthermore, the space between the main distributor and the interlayer distributor and the corresponding reaction bed layer and the thickness of the corresponding packing layer in the reaction bed layer can ensure that the gas-phase feed is uniformly distributed on the section of the catalyst layer.
Furthermore, interlayer heat exchange tubes are embedded in at least one layer of reaction bed layer, inlets of the interlayer heat exchange tubes are connected with corresponding refrigerant inlets, and outlets of the interlayer heat exchange tubes are connected with corresponding refrigerant outlets;
preferably, the interlayer heat exchange tube is a straight tube or a spiral coil; the straight tubes are vertically downward parallel to the central axis of the reactor shell in the direction of the inside of the reaction bed layer, the tube diameter is 2-5cm, and the number of the tubes is 10-200; the spiral coil is arranged in the reaction bed layer and spirally downwards surrounds the central axis of the reactor shell, the pipe diameter is 2-5cm, and the screw pitch is 10-20 cm.
Further, the optimized values of the structural parameters and the operating parameters of the ethylene carbonate hydrogenation reactor are determined by an operation mode;
the operation mode comprises the maximization of the total yield of methanol and glycol and the maximization of the yield of glycol;
the reactor structure parameters comprise the specific bed number of the ethylene carbonate hydrogenation reactor and the height of each stage of reaction bed;
the operating parameters comprise the operating pressure of each stage of reaction bed layer, the mass airspeed of each section of ethylene carbonate, the molar ratio of each section of hydrogen to ethylene carbonate, the pressure of each section of refrigerant, the flow rate of each section of refrigerant and the flow direction of each section of refrigerant.
Further, the optimized values of the structural parameters and the operational parameters of the ethylene carbonate hydrogenation reactor are determined by the following method:
s1, establishing a reactor mathematical model, including:
reactor design equation:
wherein F is the molar flow, V is the volume of the reaction bed, r is the reaction rate, n is the number of reactor bed layers, i is the component participating in the reaction, and 0 represents the inlet position;
reactor energy balance equation:
wherein T is the bed temperature, TmIs the average temperature of the heat exchange medium, H is the enthalpy, U is the total heat transfer coefficient, cpIs molar constant pressure heat capacity;
the reaction kinetics equation:
wherein A is a pre-exponential factor, Ea is activation energy, R is an ideal gas constant, T is temperature, P isiIs a dimensionless partial pressure of component i, alphaiThe reaction number of the component i is shown, and j represents the reaction number;
the hydrogenation of ethylene carbonate on a supported copper-based catalyst corresponds to the following three macroscopic reactions:
①EC+3H2→EG+MeOH
②EC+H2→EG+CO
③EG+H2→EtOH+H2O
wherein EC represents ethylene carbonate, MeOH represents methanol, EG represents ethylene glycol, EtOH represents ethanol, the reaction kinetics parameters assume the following values: a. the1＝1～20mol/h,Ea1＝20～40kJ/mol,α1,EC＝0.5～1,A2＝1～20mol/h,Ea2＝20～40kJ/mol,α2,EC＝0.8～1.5,A3＝103～109mol/h,Ea3＝30～120kJ/mol,α3,EG＝0；
S2, establishing an objective function for maximizing methanol and glycol total alcohol yield, glycol yield or other production targets, determining the limit of each design variable and operation variable as a constraint function, and establishing an expression corresponding to the optimization problem as follows:
wherein, Y (x) is an objective function, and when the yield of the total alcohol of the methanol and the glycol is maximized as a production target, Y (x) is YMeOH(x)+YEG(x) (ii) a When the production target is the maximum yield of ethylene glycol, Y (x) is YEG(x) (ii) a x is a decision variable vector comprising various design variables and operation variables; gk(x) Constraint functions for values of each design variable and operation variable;
and S3, performing optimization calculation by adopting a heuristic algorithm to obtain an optimal value of the decision variable.
Further, the heuristic algorithm in S3 includes a genetic algorithm, a swarm intelligence algorithm, or another heuristic algorithm, wherein the process of obtaining the preferred value of the decision variable includes:
(v) randomly selecting a decision variable as an optimized initial seed in a constraint function range to perform population initialization;
(vi) sequentially inputting seeds in the population into a reactor mathematical model to obtain a target function value;
(vii) selecting an optimal group of solutions from the population as a new population, and updating the population according to a certain rule;
(viii) and (5) iterating according to the step (ii) (iii) until an iteration termination condition is met.
Further, the number of the reaction bed layers is 1-4, the temperature of each reaction bed layer is 185-205 ℃, and the mass space velocity of ethylene carbonate in each section is 0.4-2.8 h-1The molar ratio of the hydrogen to the ethylene carbonate at each stage is 220: 1-150: 1, and the pressure is 2.5-3.5 MPa;
and/or the supported copper-based catalyst filled in the catalyst layer is cylindrical or honeycomb-shaped particles, the particle size is 2-8 mm, and the copper loading is 25-50%;
and/or the refrigerant is pressurized hot water of 0.5-1.5 MPa, pressurized steam of 0.5-1.5 MPa or heat conducting oil of 150-200 ℃, and the flow direction of the refrigerant is parallel flow or countercurrent flow.
A second object of the present solution is to protect the use of a reactor for hydrogenating ethylene carbonate, comprising one or more of the following steps:
the premixed high-temperature ethylene carbonate gas and hydrogen enter the reactor shell from the main feeding pipe and are dispersed in the space above the first reaction bed layer through the main distributor;
after passing through a first filler layer, the ethylene carbonate and hydrogen mixed gas is further fully and uniformly mixed, enters a first catalyst layer filled with catalyst particles, and generates ethylene carbonate heterogeneous hydrogenation reaction on the surfaces of copper-based catalyst particles to generate a first-stage product mixed gas containing reaction products of ethylene glycol and methanol, and unreacted ethylene carbonate and hydrogen;
the first-stage product mixed gas enters a space between a first reaction bed layer and a second reaction bed layer in the reaction shell, is mixed with ethylene carbonate gas which is introduced through a first interlayer feeding pipe and dispersed through a first interlayer distributor, and is dispersed in a space above the second reaction bed layer;
after entering a second filler layer, the ethylene carbonate and hydrogen mixed gas is further fully and uniformly mixed and enters a second catalyst layer filled with catalyst particles, and the heterogeneous hydrogenation reaction of ethylene carbonate occurs on the surfaces of copper-based catalyst particles to generate a second-stage product mixed gas containing reaction products of ethylene glycol and methanol, unreacted ethylene carbonate and hydrogen, and so on, wherein the product mixed gas containing ethylene glycol, methanol, hydrogen and a very small amount of ethylene carbonate flowing out of the last-stage reaction bed layer leaves a ethylene carbonate hydrogenation reactor through a product gas guide pipe and a discharge pipe;
and each stage of refrigerant is introduced into the corresponding interlayer heat exchange tube from the corresponding refrigerant inlet, performs heat exchange with the corresponding reaction bed layer, and is discharged from the corresponding refrigerant outlet.
Compared with the prior art, the invention has the following technical advantages:
1) the multi-section fixed bed reactor provided by the invention has low manufacturing and maintenance cost, meets the requirement of large-scale production, can independently control the temperature of a multi-section reaction bed layer in sections, and realizes various different operation modes such as maximization of the total yield of methanol and glycol, maximization of the yield of glycol and the like;
2) according to the reactor optimization design method provided by the invention, a heuristic algorithm is adopted to optimize and select structural parameters and operation parameters such as the height of each section of reaction bed layer, the feeding composition and flow rate of each section of interlayer, the length of each section of interlayer heat exchange tube, the composition and flow rate of each section of refrigerant and the like of a multi-section fixed bed reactor, so that the reactor can adjust the reaction of ethylene carbonate and hydrogen to be consistent with the reaction kinetics matching according to different requirements such as maximized methanol, total yield of ethylene glycol or yield of ethylene glycol in actual production, the hydrogen-ester ratio of operation is reduced, and the economical efficiency and the application range of the process are greatly improved;
3) the optimized designed multistage fixed bed reactor is utilized to carry out the hydrogenation of the ethylene carbonate to coproduce methanol and ethylene glycol, and the conversion rate of the ethylene carbonate at the outlet of the reactor is more than 98 percent, the selectivity of the ethylene glycol is more than 95 percent, or the selectivity of the total alcohol is more than 84 percent.
Drawings
FIG. 1 is a schematic front view of a vinyl carbonate hydrogenation reactor for co-producing methanol and ethylene glycol according to the present invention.
Fig. 2 is a schematic top view of a reactor for hydrogenating ethylene carbonate to co-produce methanol and ethylene glycol according to the present invention.
Fig. 3 is a schematic structural diagram of a certain stage of reaction bed of an ethylene carbonate hydrogenation reactor equipped with a cooling straight pipe in the patent of the invention.
Fig. 4 is a schematic diagram of a certain stage of reaction bed of an ethylene carbonate hydrogenation reactor equipped with a cooling coil according to the patent of the invention.
In the figure: the reactor comprises a reactor shell 1, a reactor upper end socket 2, a reactor lower end socket 3, a main feeding pipe 4, a main distributor 5, a packing layer 6, a catalytic layer 7, a packing layer supporting sieve plate 8, a catalytic layer supporting sieve plate 9, a first reaction bed layer 10, a second reaction bed layer 11, a first interlayer feeding pipe 12, a first interlayer distributor 13, a heat exchange pipe 14, a refrigerant inlet 15, a refrigerant outlet 16, a product gas flow guide pipe 17 and a discharging pipe 18.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. In the technical scheme, the features such as component model, material name, connection structure, control method, algorithm and the like which are not explicitly described are all regarded as common technical features disclosed in the prior art.
The ethylene carbonate hydrogenation reactor in the technical scheme adopts a specific reactor structure, and can work in at least two operation modes including the maximization of the total yield of methanol and ethylene glycol and the maximization of the yield of ethylene glycol by the optimization selection of the reactor structure parameters and the reactor operation parameters.
Specifically, the ethylene carbonate hydrogenation reactor in the technical scheme comprises a reactor upper end enclosure, a reactor lower end enclosure and a reactor shell arranged between the reactor upper end enclosure and the reactor lower end enclosure; the reactor upper end socket is provided with a main feeding pipe and a charging port, and the reactor lower end socket is provided with a discharging pipe and a discharging port; the reactor shell is characterized in that the outer wall of the reactor shell is provided with at least one stage of interlayer feeding pipe comprising a first interlayer feeding pipe, at least one stage of refrigerant inlet comprising a first refrigerant inlet, at least one stage of refrigerant outlet comprising a first refrigerant outlet and a manhole.
Specifically, a main distributor, at least one-stage interlayer distributor comprising a first interlayer distributor, at least two-stage reaction beds comprising a first reaction bed and a second reaction bed, at least one-stage interlayer heat exchange tube comprising a first interlayer heat exchange tube, and a product gas guide tube are arranged in an inner cavity of a reactor shell in the technical scheme. The main feeding pipe and the discharging pipe are arranged vertically downwards, and the central axes of the main feeding pipe and the discharging pipe are collinear or parallel with the central axis of the reactor shell; the direction of the interlayer feeding pipe, the refrigerant inlet and the refrigerant outlet is vertical to the outer wall of the reactor shell. The inlet of the main distributor is connected with the main feeding pipe, and the outlet of the main distributor is arranged above the first reaction bed layer; the inlet of the first interlayer distributor is connected with the first interlayer feeding pipe, the outlet of the first interlayer distributor is arranged above the second reaction bed, and the rest is arranged in the same way if the subsequent layers exist; and the inlet of the product gas guide pipe is arranged below the last stage of the reaction bed layer, and the outlet of the product gas guide pipe is connected with the discharge pipe.
Specifically, each reaction bed layer in the technical scheme comprises a packing layer, a catalytic layer and a support sieve plate from top to bottom, wherein the packing layer is filled with metal or ceramic packing, and the catalytic layer is filled with supported copper-based catalyst particles. An interlayer heat exchange tube is embedded in at least one layer of reaction bed layer, the inlet of the interlayer heat exchange tube is connected with the corresponding refrigerant inlet, and the outlet of the interlayer heat exchange tube is connected with the corresponding refrigerant outlet; the interlayer heat exchange tubes are straight tubes or spiral coils, the straight tubes are parallel to the direction inside the reaction bed layer and vertically downward to the central axis of the reactor shell, and the spiral coils are arranged around the direction inside the reaction bed layer and spirally downward to the central axis of the reactor shell.
In the process of optimally designing the ethylene carbonate hydrogenation reactor, the structural parameters and the operating parameters of the reactor can be optimally determined according to the maximization of the total yield of methanol and ethylene glycol, the maximization of the yield of ethylene glycol or other specific production requirements, and specifically comprise the number of bed layers, the height of each stage of reaction bed layers, the operating pressure, the mass airspeed of each stage of ethylene carbonate, the molar ratio of each stage of hydrogen to ethylene carbonate, the pressure of each stage of refrigerant, the flow rate of each stage of refrigerant, the flow direction of each stage of refrigerant and the like, so that the segmented control of the temperature of each stage of bed layers is realized. The optimization of the structural parameters and the operating parameters of the reactor is carried out according to the following steps:
s1, establishing a reactor mathematical model including a reactor design equation,
wherein F is the molar flow, V is the volume of the reaction bed, r is the reaction rate, n is the number of reactor bed layers, i is the component participating in the reaction, and 0 represents the inlet position;
the energy balance equation of the reactor is shown in the specification,
wherein T is the bed temperature, TmIs the average temperature of the heat exchange medium, H is the enthalpy, U is the total heat transfer coefficient, cpIs molar constant pressure heat capacity;
the equation of the reaction kinetics is shown in the specification,
wherein A is a pre-exponential factor, Ea is activation energy, R is an ideal gas constant, T is temperature, P isiIs a dimensionless partial pressure of component i, alphaiThe reaction number of the component i is shown, and j represents the reaction number;
for the hydrogenation of ethylene carbonate on a supported copper-based catalyst, the macroscopic reactions shown in the first to the third and the reaction kinetic parameters are consideredThe following values were used: a. the1＝1～20mol/h,Ea1＝20～40kJ/mol,α1,EC＝0.5～1,A2＝1～20mol/h,Ea2＝20～40kJ/mol,α2,EC＝0.8～1.5,A3＝103～109mol/h,Ea3＝30～120kJ/mol,α3,EG＝0；
S2, establishing an objective function for maximizing methanol and glycol total alcohol yield, glycol yield or other production targets, determining the limits of various design variables and operation variables as constraint functions, establishing an optimization problem, wherein the corresponding expression is as follows,
wherein, Y (x) is an objective function, and when the yield of the total alcohol of the methanol and the glycol is maximized as a production target, Y (x) is YMeOH(x)+YEG(x) (ii) a When the production target is the maximum yield of ethylene glycol, Y (x) is YEG(x) (ii) a x is a decision variable vector comprising various design variables and operation variables; gk(x) Constraint functions for values of each design variable and operation variable;
s3, obtaining optimized decision variable values by adopting heuristic optimization algorithms such as genetic algorithm and the like, comprising the following steps: randomly selecting a decision variable as an optimized initial seed in a constraint function range to perform population initialization;
(i) sequentially inputting seeds in the population into a reactor mathematical model to obtain a target function value;
(ii) selecting an optimal group of solutions from the population as a new population, and updating the population according to a certain rule;
(iii) and (5) iterating according to the step (ii) (iii) until an iteration termination condition is met.
In the process of coproducing methanol and ethylene glycol by using the optimally designed ethylene carbonate hydrogenation reactor, referring to fig. 1 to 4, the method specifically comprises the following steps: premixed high-temperature ethylene carbonate gas and hydrogen enter the reactor shell 1 from the main feeding pipe 4 and are dispersed in the space above the first reaction bed layer 10 through the main distributor 5; after passing through a first filler layer 6, the ethylene carbonate and hydrogen mixed gas is further fully and uniformly mixed, enters a first catalyst layer 7 filled with catalyst particles, and generates ethylene carbonate heterogeneous hydrogenation reaction on the surfaces of copper-based catalyst particles to generate a first-stage product mixed gas containing reaction products of ethylene glycol and methanol, unreacted ethylene carbonate and hydrogen; the first-stage product mixed gas enters a space between a first reaction bed layer 10 and a second reaction bed layer 11 in the reaction shell 1, is mixed with ethylene carbonate gas which is introduced through a first interlayer feeding pipe 12 and dispersed through a first interlayer distributor 13, and is dispersed in a space above the second reaction bed layer 11; after entering the second filler layer 6, the ethylene carbonate and hydrogen mixed gas is further fully and uniformly mixed, enters the second catalyst layer 7 filled with catalyst particles, and generates ethylene carbonate heterogeneous hydrogenation reaction on the surfaces of copper-based catalyst particles to generate a second-stage product mixed gas containing reaction products of ethylene glycol and methanol, unreacted ethylene carbonate and hydrogen; and so on; the product mixed gas containing glycol, methanol, hydrogen and a very small amount of ethylene carbonate flowing out of the last stage reaction bed layer leaves the ethylene carbonate hydrogenation reactor through a product gas guide pipe 17 and a discharge pipe 18; and each stage of refrigerant is introduced into the corresponding interlayer heat exchange tube from the corresponding refrigerant inlet, performs heat exchange with the corresponding reaction bed layer, and is discharged from the corresponding refrigerant outlet.
The structural parameters and the operating parameters of the ethylene carbonate hydrogenation reactor are determined according to the optimized design method provided by the invention.
The following are preferred ranges obtained by the preferred design method, and the corresponding parameters in the examples can be reasonably selected from the following ranges:
the number of reaction beds of the ethylene carbonate hydrogenation reactor is 1-4;
the metal or ceramic filler filled in the filler layer is one or more of Raschig rings, pall rings and ladder rings, and the size of the filler is 5-20 mm;
the supported copper-based catalyst filled in the catalyst layer is cylindrical or honeycomb-shaped particles, the particle size is 2-8 mm, and the copper loading is 25-50%;
the refrigerant is pressurized hot water of 0.5-1.5 MPa, pressurized steam of 0.5-1.5 MPa or heat conducting oil of 150-200 ℃, and the flow direction of the refrigerant is parallel flow or counter flow.
Example 1
The method for coproducing methanol and ethylene glycol is carried out according to the ethylene carbonate hydrogenation reactor, and the reaction bed layer is 2 layers. The first layer and the second layer of copper-containing catalyst are both 35 percent of active metal copper, wherein the carrier is silicon dioxide, and the specific surface area of the catalyst is 308m2(iv)/g, catalyst particle diameter 5mm by 5mm cylinder; the main feeding pipe is used for feeding ethylene carbonate and hydrogen in a mixed mode, the first interlayer feeding pipe is used for feeding pure ethylene carbonate, and the mass ratio of the main feeding pipe to the ethylene carbonate of the first interlayer feeding pipe is 1: 9.3; the first reaction bed layer is adiabatic, the reaction temperature is 190 ℃, and the mass space velocity of the ethylene carbonate is 0.53h-1The molar ratio of hydrogen to ethylene carbonate is 200:1, and the reaction pressure is 3.0 MPa; the second reaction bed layer is not adiabatic, the refrigerant is heat conducting oil with the temperature of 190 ℃, the reaction temperature is 200 ℃, and the mass space velocity of the ethylene carbonate is 0.56h-1Under the conditions that the molar ratio of hydrogen to ethylene carbonate is 22:1 and the reaction pressure is 3.0MPa, the conversion rate of ethylene carbonate is 100%, the selectivity of ethylene glycol is 94.9% and the selectivity of methanol is 61.5%.
Example 2
The method for coproducing methanol and ethylene glycol is carried out according to the ethylene carbonate hydrogenation reactor, and the reaction bed layer is 2 layers. The catalysts of the first and second layers were in accordance with example 1; the main feeding pipe is used for feeding ethylene carbonate and hydrogen in a mixed mode, the first interlayer feeding pipe is used for feeding pure ethylene carbonate, and the mass ratio of the main feeding pipe to the ethylene carbonate of the first interlayer feeding pipe is 1: 2.4; the first reaction bed layer is adiabatic, the reaction temperature is 190 ℃, and the mass space velocity of the ethylene carbonate is 0.55h-1The molar ratio of hydrogen to ethylene carbonate is 200:1, and the reaction pressure is 3.0 MPa; the second reaction bed layer is not adiabatic, the refrigerant is heat conducting oil with the temperature of 190 ℃, the reaction temperature is 201 ℃, and the mass space velocity of the ethylene carbonate is 0.57h-1Hydrogen and ethylene carbonate in molesThe ratio is 82:1, the conversion rate of the ethylene carbonate is 99.9%, the selectivity of the ethylene glycol is 94.4%, and the selectivity of the methanol is 71.7% under the condition that the reaction pressure is 3.0 MPa.
Example 3
The method for coproducing methanol and ethylene glycol is carried out according to the ethylene carbonate hydrogenation reactor, and the reaction bed layer is 2 layers. The catalysts of the first and second layers were in accordance with example 1; the main feeding pipe is used for feeding ethylene carbonate and hydrogen in a mixed mode, the first interlayer feeding pipe is used for feeding pure ethylene carbonate, and the mass ratio of the ethylene carbonate in the main feeding pipe to the ethylene carbonate in the first interlayer feeding pipe is 1: 1; the first reaction bed layer is adiabatic, the reaction temperature is 190 ℃, and the mass space velocity of the ethylene carbonate is 2.75h-1The molar ratio of hydrogen to ethylene carbonate is 200:1, and the reaction pressure is 3.0 MPa; the second reaction bed layer is not adiabatic, the refrigerant is heat conducting oil with the temperature of 190 ℃, the reaction temperature is 194 ℃, and the mass space velocity of the ethylene carbonate is 0.50h-1Under the conditions that the molar ratio of hydrogen to ethylene carbonate is 121:1 and the reaction pressure is 3.0MPa, the conversion rate of ethylene carbonate is 99.3%, the selectivity of ethylene glycol is 95.1% and the selectivity of methanol is 72.6%.
Example 4
The method for coproducing methanol and ethylene glycol is carried out according to the ethylene carbonate hydrogenation reactor, and the reaction bed layer is 2 layers. The catalysts of the first and second layers were in accordance with example 1; the main feeding pipe is used for feeding ethylene carbonate and hydrogen in a mixed mode, the first interlayer feeding pipe is used for feeding pure ethylene carbonate, and the mass ratio of the ethylene carbonate in the main feeding pipe to the ethylene carbonate in the first interlayer feeding pipe is 1: 1; the first reaction bed layer is adiabatic, the reaction temperature is 190 ℃, and the mass space velocity of the ethylene carbonate is 0.92h-1The molar ratio of hydrogen to ethylene carbonate is 200:1, and the reaction pressure is 3.0 MPa; the second reaction bed layer is not adiabatic, the refrigerant is heat conducting oil with the temperature of 190 ℃, the reaction temperature is 199 ℃, and the mass space velocity of the ethylene carbonate is 0.49h-1Under the conditions that the molar ratio of hydrogen to ethylene carbonate is 160:1 and the reaction pressure is 3.0MPa, the conversion rate of ethylene carbonate is 98.3%, the selectivity of ethylene glycol is 94.5% and the selectivity of methanol is 74.2%.
Comparative example 1
The ethylene carbonate hydrogenation reactor is a two-stage adiabatic method for co-producing methanol and ethylene glycol, and serves as a comparative example, and the reaction bed layer is 2 layers. The catalysts of the first and second layers were in accordance with example 1; the main feeding pipe is used for feeding ethylene carbonate and hydrogen in a mixed mode, the first interlayer feeding pipe is used for feeding pure ethylene carbonate, and the mass ratio of the ethylene carbonate in the main feeding pipe to the ethylene carbonate in the first interlayer feeding pipe is 1: 1; all reaction beds are adiabatic, the reaction temperature of the first reaction bed is 190 ℃, and the mass space velocity of the ethylene carbonate is 0.55h-1The molar ratio of hydrogen to ethylene carbonate is 200:1, and the reaction pressure is 3.0 MPa; the reaction temperature of the second reaction bed layer is 201 ℃, and the mass space velocity of the ethylene carbonate is 0.59h-1Under the conditions that the molar ratio of hydrogen to ethylene carbonate is 184:1 and the reaction pressure is 3.0MPa, the conversion rate of ethylene carbonate is 97.0 percent, the selectivity of ethylene glycol is 88.5 percent and the selectivity of methanol is 75.3 percent.
Comparative example 2
The ethylene carbonate hydrogenation reactor is a two-layer isothermal tubular reactor and is used as a comparative example for co-producing methanol and ethylene glycol, and the reaction bed layer is 2 layers. The catalysts of the first and second layers were in accordance with example 1; the main feeding pipe is used for feeding ethylene carbonate and hydrogen in a mixed mode, the first interlayer feeding pipe is used for feeding pure ethylene carbonate, and the mass ratio of the ethylene carbonate in the main feeding pipe to the ethylene carbonate in the first interlayer feeding pipe is 1: 1; all the refrigerants of the reaction beds are heat conducting oil at 190 ℃, the reaction temperature of the first reaction bed is 190 ℃, and the mass space velocity of the ethylene carbonate is 0.55h-1The molar ratio of hydrogen to ethylene carbonate is 200:1, and the reaction pressure is 3.0 MPa; the reaction temperature of the second reaction bed layer is 190 ℃, and the mass space velocity of the ethylene carbonate is 0.60h-1Under the conditions that the molar ratio of hydrogen to ethylene carbonate is 181:1 and the reaction pressure is 3.0MPa, the conversion rate of ethylene carbonate is 95.2%, the selectivity of ethylene glycol is 95.0% and the selectivity of methanol is 74.8%.
Comparative example 3:
the method for coproducing methanol and ethylene glycol by ethylene carbonate hydrogenation comprises the steps of using a catalyst, reacting conditions and reacting raw materials, wherein the method is the same as the method in the comparative example 2, except that the refrigerant is heat conduction oil with the temperature of 200 ℃, the conversion rate of ethylene carbonate is 96.3%, the selectivity of ethylene glycol is 90.7% and the selectivity of methanol is 75.3%.
The embodiments described above are described to facilitate one of ordinary skill in the art to understand and use the invention patent. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. The ethylene carbonate hydrogenation reactor is characterized by comprising a reactor upper end socket, a reactor lower end socket and a reactor shell arranged between the reactor upper end socket and the reactor lower end socket;
the reactor upper end socket is provided with a main feeding pipe and a charging port, and the reactor lower end socket is provided with a discharging pipe and a discharging port;
the outer wall of the reactor shell is provided with at least one stage of interlayer feeding pipe comprising a first interlayer feeding pipe, at least one stage of refrigerant inlet comprising a first refrigerant inlet, at least one stage of refrigerant outlet comprising a first refrigerant outlet and a manhole;
the reactor is characterized in that a main distributor, at least one-stage interlayer distributor comprising a first interlayer distributor, at least two-stage reaction beds comprising a first reaction bed and a second reaction bed, at least one-stage interlayer heat exchange tube comprising a first interlayer heat exchange tube and a product gas guide tube are arranged in the inner cavity of the reactor shell.
2. The ethylene carbonate hydrogenation reactor according to claim 1, wherein the main feeding pipe and the discharging pipe are arranged vertically downwards, and central axes of the main feeding pipe and the discharging pipe are collinear or parallel with a central axis of the reactor shell;
the direction of the interlayer feeding pipe, the refrigerant inlet and the refrigerant outlet is vertical to the outer wall of the reactor shell.
3. The ethylene carbonate hydrogenation reactor according to claim 1, wherein the inlet of the primary distributor is connected with the primary feed pipe, and the outlet of the primary distributor is arranged above the first reaction bed layer;
the inlet of the first interlayer distributor is connected with the first interlayer feeding pipe, the outlet of the first interlayer distributor is arranged above the second reaction bed layer, and the like is carried out if a subsequent layer exists;
and the inlet of the product gas guide pipe is arranged below the last stage of the reaction bed layer, and the outlet of the product gas guide pipe is connected with the discharge pipe.
4. The ethylene carbonate hydrogenation reactor according to claim 1, wherein each reaction bed layer comprises a filler layer, a catalytic layer and a support sieve plate from top to bottom, the filler layer is filled with metal or ceramic filler, and the catalytic layer is filled with supported copper-based catalyst particles.
5. The ethylene carbonate hydrogenation reactor according to claim 1, wherein interlayer heat exchange tubes are embedded in at least one reaction bed layer, inlets of the interlayer heat exchange tubes are connected with corresponding refrigerant inlets, and outlets of the interlayer heat exchange tubes are connected with corresponding refrigerant outlets;
the interlayer heat exchange tubes are straight tubes or spiral coils, the straight tubes are parallel to the direction inside the reaction bed layer and vertically downward to the central axis of the reactor shell, and the spiral coils are arranged around the direction inside the reaction bed layer and spirally downward to the central axis of the reactor shell.
6. The ethylene carbonate hydrogenation reactor according to claim 1, wherein the optimized values of the structural parameters and the operational parameters of the ethylene carbonate hydrogenation reactor are determined by an operation mode;
the operation mode comprises the maximization of the total yield of methanol and glycol and the maximization of the yield of glycol;
the reactor structure parameters comprise the specific bed number of the ethylene carbonate hydrogenation reactor and the height of each stage of reaction bed;
the operating parameters comprise the operating pressure of each stage of reaction bed layer, the mass airspeed of each section of ethylene carbonate, the molar ratio of each section of hydrogen to ethylene carbonate, the pressure of each section of refrigerant, the flow rate of each section of refrigerant and the flow direction of each section of refrigerant.
7. The ethylene carbonate hydrogenation reactor according to claim 6, wherein the optimized values of the structural parameters and the operational parameters of the ethylene carbonate hydrogenation reactor are determined by:
s1, establishing a reactor mathematical model, including:
reactor design equation:
wherein F is the molar flow, V is the volume of the reaction bed, r is the reaction rate, n is the number of reactor bed layers, i is the component participating in the reaction, and 0 represents the inlet position;
reactor energy balance equation:
wherein T is the bed temperature, TmIs the average temperature of the heat exchange medium, H is the enthalpy, U is the total heat transfer coefficient, cpIs molal constant pressure heatC, holding;
the reaction kinetics equation:
wherein A is a pre-exponential factor, Ea is activation energy, R is an ideal gas constant, T is temperature, P isiIs a dimensionless partial pressure of component i, alphaiThe reaction number of the component i is shown, and j represents the reaction number;
the hydrogenation of ethylene carbonate on a supported copper-based catalyst corresponds to the following three macroscopic reactions:
①EC+3H2→EG+MeOH
②EC+H2→EG+CO
③EG+H2→EtOH+H2O
wherein EC represents ethylene carbonate, MeOH represents methanol, EG represents ethylene glycol, EtOH represents ethanol, the reaction kinetics parameters assume the following values: a. the1＝1～20mol/h，Ea1＝20～40kJ/mol，α1，EC＝0.5～1，A2＝1～20mol/h，Ea2＝20～40kJ/mol，α2，EC＝0.8～1.5，A3＝103～109mol/h，Ea3＝30～120kJ/mol，α3，EG＝0；
S2, establishing an objective function for maximizing methanol and glycol total alcohol yield, glycol yield or other production targets, determining the limit of each design variable and operation variable as a constraint function, and establishing an expression corresponding to the optimization problem as follows:
wherein, Y (x) is an objective function, and when the yield of the total alcohol of the methanol and the glycol is maximized as a production target, Y (x) is YMeOH(x)+YEG(x) (ii) a When the production target is the maximum yield of ethylene glycol, Y (x) is YEG(x) (ii) a x is a decision variable vector comprising various design variables andan operating variable; gk(x) Constraint functions for values of each design variable and operation variable;
and S3, performing optimization calculation by adopting a heuristic algorithm to obtain an optimal value of the decision variable.
8. The ethylene carbonate hydrogenation reactor according to claim 7, wherein the heuristic algorithm in S3 comprises a genetic algorithm, a swarm intelligence algorithm, wherein the process of obtaining the preferred value of the decision variable comprises:
(i) randomly selecting a decision variable as an optimized initial seed in a constraint function range to perform population initialization;
(ii) sequentially inputting seeds in the population into a reactor mathematical model to obtain a target function value;
(iii) selecting an optimal group of solutions from the population as a new population, and updating the population according to a certain rule;
(iv) and (5) iterating according to the step (ii) (iii) until an iteration termination condition is met.
9. The ethylene carbonate hydrogenation reactor according to claim 7, wherein the number of the reaction bed layers is 1-4, the temperature of each reaction bed layer is 185-205 ℃, and the mass space velocity of each section of ethylene carbonate is 0.4-2.8 h-1The molar ratio of the hydrogen to the ethylene carbonate at each section is 220: 1-150: 1, and the pressure is 2.5-3.5 MPa;
and/or the supported copper-based catalyst filled in the catalyst layer is cylindrical or honeycomb-shaped particles, the particle size is 2-8 mm, and the copper loading is 25-50%;
and/or the refrigerant is pressurized hot water of 0.5-1.5 MPa, pressurized steam of 0.5-1.5 MPa or heat conducting oil of 150-200 ℃, and the flow direction of the refrigerant is parallel flow or countercurrent flow.
10. Use of a reactor for hydrogenating ethylene carbonate according to any one of claims 1 to 9, comprising one or more of the following steps:
premixed high-temperature ethylene carbonate gas and hydrogen enter a reactor shell (1) from a main feeding pipe (4), and are dispersed in a space above a first reaction bed layer (10) through a main distributor (5);
after passing through a first filler layer (6), the ethylene carbonate and hydrogen mixed gas is further fully and uniformly mixed, enters a first catalyst layer (7) filled with catalyst particles, and generates ethylene carbonate heterogeneous hydrogenation reaction on the surfaces of copper-based catalyst particles to generate a first-stage product mixed gas containing reaction products of ethylene glycol and methanol, unreacted ethylene carbonate and hydrogen;
the first-stage product mixed gas enters a space between a first reaction bed layer (10) and a second reaction bed layer (11) in the reaction shell (1), is mixed with ethylene carbonate gas which is introduced through a first interlayer feeding pipe (12) and then dispersed through a first interlayer distributor (13), and is dispersed in a space above the second reaction bed layer (11);
after entering a second packing layer (6), the ethylene carbonate and hydrogen mixed gas is further fully and uniformly mixed, enters a second catalyst layer (7) filled with catalyst particles, and generates ethylene carbonate heterogeneous hydrogenation reaction on the surface of copper-based catalyst particles to generate a second-stage product mixed gas containing reaction products of ethylene glycol and methanol, unreacted ethylene carbonate and hydrogen, and so on, wherein the product mixed gas containing ethylene glycol, methanol, hydrogen and a very small amount of ethylene carbonate flowing out of the last-stage reaction bed layer leaves a ethylene carbonate hydrogenation reactor through a product gas guide pipe (17) and a discharge pipe (18);
and each stage of refrigerant is introduced into the corresponding interlayer heat exchange tube from the corresponding refrigerant inlet, exchanges heat with the corresponding reaction bed layer, and is discharged from the corresponding refrigerant outlet.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111305330.8A CN113856567A (en) | 2021-11-05 | 2021-11-05 | Ethylene carbonate hydrogenation reactor and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111305330.8A CN113856567A (en) | 2021-11-05 | 2021-11-05 | Ethylene carbonate hydrogenation reactor and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113856567A true CN113856567A (en) | 2021-12-31 |
Family
ID=78987338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111305330.8A Pending CN113856567A (en) | 2021-11-05 | 2021-11-05 | Ethylene carbonate hydrogenation reactor and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113856567A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993347A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Method for producing ethanediol from oxalate by hydrogenation |
| CN102649698A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | High-efficiency production method for ethylene glycol |
| CN102649709A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol by gas-phase catalytically hydrogenating oxalate raw material |
| CA2951165A1 (en) * | 2014-06-05 | 2015-12-10 | Shanghai Wuzheng Engineering Technology Co., Ltd | Method and device system for producing dimethyl oxalate through medium and high-pressure carbonylation of industrial synthesis gas and producing ethylene glycol through dimethyl oxalate hydrogenation |
| CN109395668A (en) * | 2017-08-18 | 2019-03-01 | 上海浦景化工技术股份有限公司 | A kind of coupled reactor for oxalic acid Arrcostab hydrogenation synthesizing of ethylene glycol |
| CN209378963U (en) * | 2018-10-10 | 2019-09-13 | 德艾柯工程技术（上海）有限公司 | A kind of plate-type reactor for the catalysis reaction of enlarged ester through hydrogenation |
| CN210906088U (en) * | 2019-08-07 | 2020-07-03 | 华东理工大学 | Ethylene carbonate hydrogenation heat-insulation type fixed bed reactor |
| CN112387219A (en) * | 2020-11-13 | 2021-02-23 | 华东理工大学 | Gasification-reaction integrated multi-stage reactor for ethylene carbonate hydrogenation |
-
2021
- 2021-11-05 CN CN202111305330.8A patent/CN113856567A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101993347A (en) * | 2009-08-31 | 2011-03-30 | 中国石油化工股份有限公司 | Method for producing ethanediol from oxalate by hydrogenation |
| CN102649698A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | High-efficiency production method for ethylene glycol |
| CN102649709A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Method for preparing ethylene glycol by gas-phase catalytically hydrogenating oxalate raw material |
| CA2951165A1 (en) * | 2014-06-05 | 2015-12-10 | Shanghai Wuzheng Engineering Technology Co., Ltd | Method and device system for producing dimethyl oxalate through medium and high-pressure carbonylation of industrial synthesis gas and producing ethylene glycol through dimethyl oxalate hydrogenation |
| CN109395668A (en) * | 2017-08-18 | 2019-03-01 | 上海浦景化工技术股份有限公司 | A kind of coupled reactor for oxalic acid Arrcostab hydrogenation synthesizing of ethylene glycol |
| CN209378963U (en) * | 2018-10-10 | 2019-09-13 | 德艾柯工程技术（上海）有限公司 | A kind of plate-type reactor for the catalysis reaction of enlarged ester through hydrogenation |
| CN210906088U (en) * | 2019-08-07 | 2020-07-03 | 华东理工大学 | Ethylene carbonate hydrogenation heat-insulation type fixed bed reactor |
| CN112387219A (en) * | 2020-11-13 | 2021-02-23 | 华东理工大学 | Gasification-reaction integrated multi-stage reactor for ethylene carbonate hydrogenation |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2017304582B2 (en) | Oxidative dehydrogenation (ODH) of ethane | |
| AU2017304583B2 (en) | Oxidative dehydrogenation (ODH) of ethane | |
| CN2621805Y (en) | Shell external cooling-thermal insulating and combined fixed bed catalyst chember | |
| CN106732201A (en) | Catalyst for Oxidative Coupling of Methane reactor | |
| NO178063B (en) | Process for the preparation of methanol | |
| CN113856567A (en) | Ethylene carbonate hydrogenation reactor and application thereof | |
| JPS6124372B2 (en) | ||
| US11760704B2 (en) | Oxidative dehydrogenation coproduction | |
| CN100386138C (en) | Process and equipment for internal heat exchanging catalytic reaction | |
| CN102649735A (en) | Method for producing oxalate through carbon monoxide gas phase-coupled catalytic reaction | |
| CN109294627B (en) | Isothermal conversion device and synthesis gas complete conversion reaction system comprising same | |
| CN217568762U (en) | Tower-type gas-liquid-phase chloroethylene production device | |
| CN112169710A (en) | Methyl acetate hydrogenation reactor and heat exchange system of multistage cold hydrogen feeding | |
| CN102337145A (en) | Fixed bed Fischer-Tropsch method for preparing liquid hydrocarbon | |
| CN109718791A (en) | Integral catalyzer and its application for catalytic oxidation of hydrogen chloride for preparing chlorine gas | |
| CN213254347U (en) | Tube array reactor with flow guide | |
| NO762211L (en) | ||
| CN210875254U (en) | Fluidized reaction system | |
| CN219898078U (en) | Reactor for producing ethylene oxide by two-step oxidation of ethylene | |
| CN112387219A (en) | Gasification-reaction integrated multi-stage reactor for ethylene carbonate hydrogenation | |
| EP4038044A1 (en) | Catalytic conversion of carbon dioxide | |
| CN214051563U (en) | Methyl acetate hydrogenation reactor and heat exchange system of multistage cold hydrogen feeding | |
| JP2012218994A (en) | Non-co2 emitting production method for synthesis gas | |
| CN220214862U (en) | Ethylene method vinyl acetate fixed bed reactor | |
| CN213376525U (en) | Oxidation reactor for continuous liquid phase oxidation of o-chlorotoluene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |