CN111905657B - Reactor for preparing ethylene glycol from large-scale synthesis gas - Google Patents
Reactor for preparing ethylene glycol from large-scale synthesis gas Download PDFInfo
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- CN111905657B CN111905657B CN201910376327.1A CN201910376327A CN111905657B CN 111905657 B CN111905657 B CN 111905657B CN 201910376327 A CN201910376327 A CN 201910376327A CN 111905657 B CN111905657 B CN 111905657B
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
Abstract
The invention relates to a large-scale reactor for preparing ethylene glycol from synthesis gas, which comprises: the reactor body comprises an upper end enclosure, a cylinder and a lower end enclosure which are integrally formed; the inside center of barrel is located to gas collection unit (9) axial, for top confined cavity component, includes: a gas collecting cylinder, the cylinder wall of which is provided with a plurality of through holes, the through holes are dense at the top and sparse at the bottom, and are small at the top and big at the bottom, and a product outlet (5) which is integrally arranged at the bottom end of the gas collecting cylinder and is positioned on the lower end enclosure; the heat exchange tube bundle (8) is axially arranged between the gas collection unit (9) and the inner wall of the cylinder; a plurality of groups of raw material inlets (1) are arranged on the upper end enclosure and/or the cylinder in pairs; the heat exchange medium outlet (6) and the at least one heat exchange medium inlet (4) are respectively arranged on the upper end enclosure and the lower end enclosure and are communicated with the heat exchange tube bundle (8); the catalyst bed layer (2) is distributed among the heat exchange tube bundles (8). Compared with the prior art, the catalyst layer has small pressure drop and low operation cost.
Description
Technical Field
The invention relates to a reactor for preparing ethylene glycol, in particular to a reactor for preparing ethylene glycol from large-scale synthesis gas.
Background
The carbonylation reactor and the hydrogenation reactor are one of the core devices of the device for preparing ethylene glycol from synthesis gas, and the reactions for preparing oxalate from synthesis gas and preparing ethylene glycol from oxalate through hydrogenation are exothermic reactions. The carbonylation reaction is a second-grade fast reaction, the reaction is mainly concentrated on the upper part of the catalyst tube for reaction, the lower part of the catalyst tube plays a balance role, and the heat of a bed layer is removed by mainly depending on the heat exchange area on the upper part of the catalyst tube; in an emergency, reaction heat is accumulated, a catalyst bed layer is over-heated, and nitrous acid ester is subjected to thermal decomposition, so that an explosion accident is easily caused. Because the hydrogenation catalyst is easy to coke and pulverize, the resistance of each catalyst tube in the reactor is different, gas bias flow can occur, the local over-temperature of the catalyst bed layer is high, the side reactant is high, and the catalyst utilization rate is low; the pressure drop of the catalyst bed is large, and the power consumption of a compressor is high.
The carbonylation reactor and the hydrogenation reactor which are put into operation and designed at present are tubular reactors, under the same transportation condition, the catalyst filling amount of a single reactor is small, the operation resistance of a reaction system is reduced, 2 carbonylation reactors and 3-4 hydrogenation reactors are generally required to be arranged for a 20 ten thousand ton/year ethylene glycol device, the occupied area is large, the engineering cost is high, gas bias flow is easy to cause, and the operation difficulty is large. The specification of a single set of 20 ten thousand tons/year dimethyl oxalate production device reactor is selected to be 6m in diameter and 8m in height, which brings many problems in the aspects of transportation, installation, operation and the like, and the tubular reactor limits the large-scale development.
In order to save energy, reduce consumption and investment, the scale of new glycol devices is getting bigger and bigger, some devices reach million tons, and the tubular carbonylation reactor and the hydrogenation reactor which are implemented at present limit the development of large-scale glycol, so that the reactor suitable for large-scale or ultra-large-scale devices needs to be developed in a matching way.
Patent CN204911449U discloses a novel carbonylation reactor for a process of preparing ethylene glycol from synthesis gas, the reactor is a radial reactor, and comprises a reactor shell, a heat exchange assembly, a flow dividing pipe, a flow collecting pipe and a catalyst, wherein the flow dividing pipe is positioned in the center of the reactor, the heat exchange assembly is arranged between the flow dividing pipe and the flow collecting pipe, the heat exchange assembly is arranged in a catalyst bed layer, and the reactor shell comprises a cylinder, an upper end enclosure, a lower end enclosure, a reaction gas inlet, a reaction gas outlet, a cooling medium inlet, a cooling medium outlet, a catalyst discharge opening and the like; the reaction gas inlet and the reaction gas outlet are both arranged on the upper sealing head, the reaction gas flows down along the central flow dividing pipe after entering the reactor from the reaction gas inlet, and then radially reacts through the catalyst bed layer, and the reaction product gas enters the collecting pipe, flows upwards along the collecting pipe and flows out from the reaction gas outlet. Although the reactor is used for preparing ethylene glycol from synthesis gas, the problem of large pressure drop of the device cannot be solved, and the reactor can only be used for carbonylation reaction and cannot be used for hydrogenation reaction.
Disclosure of Invention
The invention aims to solve the problems and provide a large-scale reactor for preparing ethylene glycol from synthesis gas.
The purpose of the invention is realized by the following technical scheme:
a reactor for large scale synthesis gas to ethylene glycol, the reactor comprising:
a reactor body integrally formed from top to bottom
An upper end enclosure is arranged on the upper end enclosure,
a cylinder and
a lower end enclosure;
a gas collection unit, the axial is located the inside center of barrel, for top confined cavity component, includes:
a gas collecting cylinder body, wherein the cylinder wall of the gas collecting cylinder body is provided with a hole
A plurality of through holes with dense top and sparse bottom, small top and large bottom, an
The product outlet is integrally arranged at the bottom end of the gas collecting cylinder body and is positioned on the lower end enclosure;
the heat exchange tube bundle is axially arranged between the gas collection unit and the inner wall of the cylinder;
the raw material inlets are arranged on the outer wall of the upper end enclosure and/or the cylinder in pairs;
the heat exchange medium inlet is arranged on the lower end enclosure and communicated with the heat exchange tube bundle;
the heat exchange medium outlet is arranged on the upper sealing head and communicated with the heat exchange tube bundle; and
and the catalyst bed layer is distributed among the heat exchange tube bundles.
Furthermore, the through holes are round holes or vertical strip holes, and play a role in controlling pressure drop distribution.
Further, the heat exchange tube bundle is a straight tube, a serpentine coil or a tube with a serpentine coil in the middle and straight tubes at two ends.
Furthermore, the outer diameter of the heat exchange tube bundle is 15-55 mm, and the tube center distance is 25-100 mm.
Further, the reactor is further provided with a gas distributor between the cylinder and the heat exchange tube bundle, an annular gap for gas flowing is arranged between the gas distributor and the cylinder wall, and the gas distributor comprises a gas distribution pipe and through holes arranged on the gas distribution pipe. Further optimally, the gas distribution pipe is a 1/4 circular ring, which is beneficial to the uniform distribution of the raw material gas in the reactor cylinder.
Furthermore, a catalyst frame is arranged on one side, close to the catalyst bed layer, of the gas distributor and the gas collecting cylinder body, and a stainless steel wire mesh is arranged on the catalyst frame, so that the catalyst is convenient to fix.
Furthermore, the diameter of the cylinder is 3000-8000 mm, and the height is 4000-12000 mm.
A large-scale synthesis gas ethylene glycol reactor, adopt this reactor to react, raw materials enter the reactor from the raw materials entrance, flow and react radially through the catalyst bed, the product reaches the gas collection unit, flow out from the product outlet; boiler feed water enters the heat exchange tube bundle through the heat exchange medium inlet, exchanges heat with the raw materials and the products of the reaction to become high-temperature boiling water or steam, and then flows out from the heat exchange medium outlet.
The invention adopts the gas collection unit, the through holes on the cylinder wall of the gas collection cylinder body of the gas collection unit are dense at the top and sparse at the bottom, and are small at the top and big at the bottom, and the gas collection unit is designed aiming at the properties of reaction raw materials and products, such as oxalate prepared by synthesis gas and glycol prepared by hydrogenation of oxalate; the radial reactor is adopted, the catalyst loading is large, and the pressure drop of a catalytic bed layer is small; the radial reactor has small temperature difference in the radial direction, which is beneficial to the full and effective utilization of the catalyst, reduces the temperature of the catalytic bed layer and prolongs the service life of the catalyst; by feeding raw material gas in multiple stages, the distribution of the raw material gas is strengthened, and the pressure drop of a bed layer is improved.
Compared with the prior art, the invention has the following beneficial effects:
the invention has the advantages of a common radial reactor, such as saving the energy consumption of the device, reducing the operation cost and the like; the method overcomes the defect that a large fixed bed reactor is difficult to manufacture and transport, can reduce the operation cost, and can be fully suitable for a large device for preparing the ethylene glycol from the synthesis gas.
Drawings
FIG. 1 is a schematic diagram of a reactor for producing ethylene glycol from large-scale synthesis gas;
FIG. 2 is a sectional view of a large scale reactor for producing ethylene glycol from synthesis gas;
FIG. 3 is a schematic view showing the flow direction of materials in the case of carrying out the reaction using the present invention.
In the figure: i, sealing an upper end; II, a cylinder body; III, lower end enclosure; 1-a raw material inlet; 2-catalyst bed layer; 3-a gas distributor; 4-heat exchange medium inlet; 5-a product outlet; 6-heat exchange medium outlet; 7-catalyst frame; 8-a heat exchange tube bundle; 9-a gas collection unit; a-starting material; b-the product; c-boiler feed water; d-high temperature boiling water or steam.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
A reactor for large scale synthesis gas to ethylene glycol, the reactor comprising:
a reactor body which is integrally formed from top to bottom
An upper end enclosure I is arranged on the upper end enclosure,
a cylinder II and
a lower end enclosure III;
a gas collection unit 9, the inside center of barrel II is located to the axial, for the top confined cavity component, includes:
a gas collecting cylinder body, the cylinder wall of the gas collecting cylinder body is provided with
A plurality of through holes with dense top and sparse bottom, small top and large bottom, an
A product outlet 5 which is integrally arranged at the bottom end of the gas collecting cylinder body and is positioned on the lower seal head III;
the heat exchange tube bundle 8 is axially arranged between the gas collection unit 9 and the inner wall of the cylinder II;
a plurality of groups of raw material inlets 1 are arranged on the outer wall of the upper end enclosure I and/or the cylinder II in pairs;
at least one heat exchange medium inlet 4 arranged on the lower end enclosure III and communicated with the heat exchange tube bundle 8;
a heat exchange medium outlet 6 arranged on the upper end enclosure I and communicated with the heat exchange tube bundle 8; and
a catalyst bed layer 2 distributed among the heat exchange tube bundles 8.
The through holes are round holes or vertical strip holes.
The heat exchange tube bundle 8 is a straight tube, a serpentine coil or a pipeline with the serpentine coil in the middle and straight tubes at two ends.
The reactor still is equipped with gas distributor 3 between barrel II and heat exchanger tube bundle 8, gas distributor 3 includes the gas distribution pipe and locates the through-hole on the gas distribution pipe. The gas distribution pipe is a 1/4 circular ring.
A catalyst frame 7 is arranged on one side of the gas distributor 3 and the gas collecting cylinder body close to the catalyst bed layer, and a stainless steel wire mesh is arranged on the catalyst frame 7.
A large-scale synthesis gas ethylene glycol reactor, adopt this reactor to react, raw materials a enter the reactor from raw materials entrance 1, flow and react radially through the bed of catalyst 2, the product b reaches the gas collecting unit 9, flow out from the product outlet 5; boiler feed water c enters the heat exchange tube bundle 8 through the heat exchange medium inlet 4, exchanges heat with the raw material a and the product b of the reaction to become high-temperature boiling water or steam d, and then flows out from the heat exchange medium outlet 6.
The reactor is used for carbonylation reaction, the height of a cylinder II is DN 8000mm, the diameter of the cylinder II is DN 4600mm, the outer diameter of a heat exchange tube in a heat exchange tube bundle is 30mm, the heat exchange tubes are arranged in a regular triangle shape, the tube center distance is 48mm, and the packing volume of a catalyst is more than 120m 3 And the normal load operation is carried out, the productivity of the dimethyl oxalate is more than 400kt/a, and the pressure drop of a catalyst bed layer is less than 15kPa.
Example 2
The reactor for preparing the ethylene glycol from the large-scale synthesis gas is specifically as described in example 1, the reactor is used for carbonylation, the height of a cylinder II is DN 8000mm, the diameter of the cylinder II is DN 5800mm, the outer diameter of a heat exchange tube in a heat exchange tube bundle is 30mm, the heat exchange tubes are arranged in a regular triangle shape, the tube center distance is 48mm, and the catalyst filling volume is more than 200m 3 And the normal load operation is carried out, the productivity of the dimethyl oxalate is more than 600kt/a, and the pressure drop of a catalyst bed layer is less than 18kPa.
Example 3
A large-scale reactor for preparing ethylene glycol from synthetic gas, as described in example 1, was used for carbonylation reaction, and the height of the cylinder II was highThe degree is DN 12000mm, the diameter is DN 5800mm, the external diameter of the heat exchange tubes in the heat exchange tube bundle is 28mm, the heat exchange tubes are arranged in a regular triangle, the tube center distance is 44mm, and the catalyst filling volume is larger than 270m 3 And the normal load operation is carried out, the productivity of the dimethyl oxalate is more than 900kt/a, and the pressure drop of a catalyst bed layer is less than 18kPa.
Example 4
The reactor for preparing ethylene glycol from large-scale synthesis gas is specifically described in example 1, the reactor is used for carbonylation, the height of a cylinder II is DN 5000mm, the diameter of the cylinder II is DN4000mm, the outer diameter of heat exchange tubes in a heat exchange tube bundle is 30mm, the heat exchange tubes are arranged in a regular triangle shape, the tube center distance is 48mm, and the catalyst packing volume is more than 60m 3 The method has the advantages of normal load operation, dimethyl oxalate capacity of more than 200kt/a and catalyst bed pressure drop of less than 13kPa.
Example 5
The reactor for preparing ethylene glycol from large-scale synthesis gas is specifically as described in example 1, the reactor is used for hydrogenation reaction, the height of a cylinder II is DN4000mm, the diameter is DN4000mm, the outer diameter of heat exchange tubes in a heat exchange tube bundle is 25mm, the heat exchange tubes are arranged in a regular triangle shape, the tube center distance is 44mm, and the packing volume of a catalyst is more than 55m 3 And the normal load operation is carried out, the ethylene glycol productivity is more than 100kt/a, and the pressure drop of a catalyst bed layer is less than 25kPa.
Example 6
The reactor for preparing the ethylene glycol from the large-scale synthesis gas is specifically described in example 1, the reactor is used for hydrogenation, the height of a cylinder II is DN6000mm, the diameter is DN 4600mm, the outer diameter of a heat exchange tube in a heat exchange tube bundle is 30mm, the heat exchange tube is a serpentine coil, the tube center distance is 50mm, and the packing volume of the catalyst is more than 110m 3 And the normal load operation is carried out, the ethylene glycol productivity is more than 200kt/a, and the pressure drop of a catalyst bed layer is less than 30kPa.
Example 7
The reactor for preparing ethylene glycol from large-scale synthesis gas is specifically described in example 1, the reactor is used for hydrogenation reaction, the height of a cylinder II is DN 8000mm (the cylinder II consists of two sections of cylinders with the height of DN4000 mm), the diameter of the cylinder II is DN 4200mm, the outer diameter of a heat exchange tube in a heat exchange tube bundle is 28mm, the heat exchange tubes are arranged in a regular triangle shape, the tube center distance is 48mm, and the packing volume of a catalyst is 48mmGreater than 110m 3 And the catalyst is operated under normal load, the productivity of the ethylene glycol is more than 200kt/a, and the pressure drop of a catalyst bed layer is less than 28kPa.
Example 8
The reactor for preparing ethylene glycol from large-scale synthesis gas is specifically described in example 1, the reactor is used for hydrogenation, the height of a cylinder II is DN 9000mm, the diameter of the cylinder II is DN 4600mm, the outer diameter of heat exchange tubes in heat exchange tube bundles is 30mm, the heat exchange tubes are arranged in a regular triangle shape, the tube center distance is 52mm, and the packing volume of a catalyst is larger than 165m 3 And the normal load operation is carried out, the ethylene glycol productivity is more than 300kt/a, and the pressure drop of a catalyst bed layer is less than 30kPa.
Example 9
The reactor for preparing ethylene glycol from large-scale synthesis gas is specifically shown in example 1, the reactor is used for hydrogenation reaction, the height of a cylinder II is DN 12000mm, the diameter of the cylinder II is DN 5800mm, the outer diameter of heat exchange tubes in a heat exchange tube bundle is 16mm, the heat exchange tubes are arranged in a regular triangle shape, the tube center distance is 25mm, and the catalyst packing volume is more than 245m 3 And the normal load operation is carried out, the ethylene glycol productivity is more than 450kt/a, and the pressure drop of a catalyst bed layer is less than 35kPa.
The embodiments described above are intended to facilitate a person of ordinary skill in the art in understanding and using the invention. 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 modifications and alterations without departing from the scope of the present invention.
Claims (9)
1. The large-scale synthesis gas ethylene glycol preparation reactor is characterized by comprising:
a reactor body integrally formed from top to bottom
An upper end enclosure (I) is arranged on the upper end enclosure,
a cylinder (II) and
a lower end enclosure (III);
a gas collection unit (9), the axial is located barrel (II) inside center, for the closed cavity component in top, includes:
a gas collecting cylinder body, the cylinder wall of which is provided with a gas collecting cylinder
A plurality of through holes with dense top and sparse bottom, small top and large bottom, an
A product outlet (5) which is integrally arranged at the bottom end of the gas collecting cylinder body and is positioned on the lower seal head (III);
the heat exchange tube bundle (8) is axially arranged between the gas collection unit (9) and the inner wall of the cylinder body (II);
the raw material inlets (1) are arranged on the top of the upper end enclosure (I) and the outer wall of the middle lower part of the cylinder body (II) in pairs;
the at least one heat exchange medium inlet (4) is arranged on the lower end socket (III) and communicated with the heat exchange tube bundle (8);
the heat exchange medium outlet (6) is arranged on the upper end enclosure (I) and communicated with the heat exchange tube bundle (8); and
and the catalyst bed layer (2) is distributed among the heat exchange tube bundles (8).
2. The reactor for preparing ethylene glycol from large-scale synthesis gas as claimed in claim 1, wherein the through holes are round holes or vertical strip holes.
3. The large-scale reactor for preparing glycol from synthesis gas according to claim 1, wherein the heat exchange tube bundle (8) is a straight tube, a serpentine coil or a tube with a serpentine coil in the middle and straight tubes at two ends.
4. The reactor for preparing ethylene glycol from large-scale synthesis gas according to claim 3, wherein the heat exchange tube bundle (8) has an outer tube diameter of 15-55 mm and a tube center distance of 25-100 mm.
5. The large-scale synthesis gas ethylene glycol reactor according to claim 1, wherein a gas distributor (3) is further disposed between the cylinder (II) and the heat exchange tube bundle (8), and the gas distributor (3) comprises a gas distribution pipe and through holes disposed on the gas distribution pipe.
6. The large-scale reactor for producing ethylene glycol from synthesis gas as claimed in claim 5, wherein the gas distribution pipe is 1/4 circular ring.
7. The large-scale reactor for preparing glycol from synthesis gas according to claim 5, wherein a catalyst frame (7) is arranged on one side of the gas distributor (3) and the gas collecting cylinder body close to the catalyst bed layer, and a stainless steel wire mesh is arranged on the catalyst frame (7).
8. The reactor for preparing ethylene glycol from large-scale synthesis gas according to claim 1, wherein the diameter of the cylinder (II) is 3000-8000 mm, and the height is 4000-12000 mm.
9. The large-scale synthesis gas ethylene glycol reactor according to any one of claims 1-8, wherein when the reactor is used for reaction, raw materials (a) enter the reactor from a raw material inlet (1), flow radially through the catalyst bed (2) and react, and products (b) reach a gas collecting unit (9) and flow out from a product outlet (5); boiler feed water (c) enters a heat exchange tube bundle (8) through a heat exchange medium inlet (4), exchanges heat with the raw material (a) and the product (b) of the reaction to become high-temperature boiling water or steam (d), and then flows out from a heat exchange medium outlet (6).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| AU2012220219B2 (en) * | 2011-02-25 | 2016-06-30 | China Petroleum & Chemical Corporation | Ethylene glycol preparation method |
| CN202876772U (en) * | 2012-10-23 | 2013-04-17 | 上海戊正工程技术有限公司 | Industrialized plate type reactor for synthesizing ester by carbonylation coupling |
| CN204638160U (en) * | 2015-05-25 | 2015-09-16 | 王顺明 | A kind of overall diameter containing multistage insulation layer is to water shifting heat shift-converter |
| CN105797650A (en) * | 2016-05-24 | 2016-07-27 | 华烁科技股份有限公司 | Fixed-bed catalytic temperature-control reactor with headers |
| CN105833804B (en) * | 2016-06-08 | 2018-12-28 | 成都赛普瑞兴科技有限公司 | Steam ascending manner radial flow reactors |
| CN207085853U (en) * | 2017-08-02 | 2018-03-13 | 中国成达工程有限公司 | A kind of radial direction steam ascending manner synthesis gas preparing ethylene glycol hydrogenation reactor |
| CN109395667B (en) * | 2017-08-18 | 2021-08-03 | 上海浦景化工技术股份有限公司 | Axial-radial reactor for synthesizing dimethyl oxalate through CO carbonylation coupling |
| CN109395669A (en) * | 2017-08-18 | 2019-03-01 | 上海浦景化工技术股份有限公司 | A kind of axial-radial flow reactor for oxalic acid Arrcostab hydrogenation synthesizing of ethylene glycol |
| CN108636298B (en) * | 2018-06-15 | 2023-06-23 | 南京聚拓化工科技有限公司 | Carbonylation reactor of device for preparing glycol from synthetic gas |
| CN108905906B (en) * | 2018-09-21 | 2023-09-19 | 东华工程科技股份有限公司 | Axial-radial reactor |
| CN109261082A (en) * | 2018-09-30 | 2019-01-25 | 中石化宁波工程有限公司 | Isothermal shift-converter |
| CN109173936B (en) * | 2018-09-30 | 2021-10-08 | 中石化宁波工程有限公司 | Methanol synthesis water-cooling reactor |
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