CN102649715A - Method for preparing aldehyde through olefin hydrogen formylation - Google Patents
Method for preparing aldehyde through olefin hydrogen formylation Download PDFInfo
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Abstract
The invention relates to a method for preparing aldehyde through olefin hydrogen formylation and mainly solves the technical problems of low raw material conversion rate and low objective product selectivity in the reaction process of the olefin hydrogen formylation existing in the prior art. With the adoption of the technical scheme that the method for preparing the aldehyde through the olefin hydrogen formylation comprises the following steps that: C2-C8 olefin, CO and hydrogen are taken as raw materials, rhodium-contained liquid solution is taken as a catalyst, and under the conditions that the reaction temperature is 40-160 DEG C, the reaction pressure is 0.5-5.0 MPa, the molar ratio of olefin to rhodium is (0.5-30):1, the raw materials are in contact with the rhodium-contained liquid solution catalyst in a highly-efficient reactor for reaction to generate a liquid effluent containing the aldehyde, wherein the high-performance reactor selects a rotating packed bed reactor, so the problems are better solved. The method can be used in the industrial production for preparing the aldehyde through the olefin hydrogen formylation.
Description
Technical field
The present invention relates to a kind of method of preparing aldehyde by hydro formylating defin, particularly under catalyst action, react the method that generates corresponding aldehyde through high efficiency reactor about alkene and synthetic gas (carbon monoxide and hydrogen).
Background technology
Hydroformylation reaction takes place in alkene and carbon monoxide and hydrogen under catalyst action
The aldehyde that generates can be made into corresponding alcohol through hydrogenation.Millions of ton of meter/year of throughput of synthol in this way in the world.Hydroformylation reaction takes place and generates propionic aldehyde or butyraldehyde in ethene or propylene and carbon monoxide and hydrogen under the effect of rhodium carbonyl catalyst, and further hydrogenation generates propyl alcohol or butanols is exactly one of them important chemical process.
No matter used hydroformylation reaction device on the industrial production is the reactor drum that still formula band stirs at present, or tower reactor; All belong to back-mix reactor; For the hydroformylation reaction of ethene (or propylene) with carbon monoxide and hydrogen, under reaction conditions, ethene (or propylene), carbon monoxide and hydrogen all are gas phases; Catalyst dissolution is a liquid phase in water.And ethene (or propylene), carbon monoxide and hydrogen solubleness in water are very little, in back-mix reactor, can only just can make mixing of materials by means of the bubbling of gas.In industrial reactor, this reaction is controlled by the rate of mass transfer of gas-liquid two-phase interface in fact.So for the hydroformylation reaction device of alkene, reinforcing mass transfer is to improve the key of reactor efficiency.
The main path of reactor drum reinforcing mass transfer is to increase the mass transfer interface, for the bubbling style reactor that does not add stirring, has only through suitable gas distributor and tightens and improves mass transfer.In this bubbling style back-mixing equipment (like the tower kind equipment), owing to there is not the input of mixing energy, it is enough thin that bubble can not reach; For enough mass transfer areas are arranged, just enough big space must be arranged, this just makes that equipment is huger; The utilising efficiency of equipment is just lower, and investment is also big.To the tank reactor of stirring is arranged, though the input of mixing energy can make bubble attenuate, thereby increase the mass transfer interface, the efficient of its increase is very limited.
Document CN200410081353.5 discloses a kind of loaded complex compound catalyst that is used for the iso-butylene hydroformylation reaction; Its reaction kettle that adopts the high pressure zone stirring is as reactor drum; Adopting iso-butylene under certain condition is raw material, and the selectivity of isovaleric aldehyde is merely about 89%.
The EP0023745 A3 patent that Britain Imperial Chemical Industries (ICI) propose is mentioned rotating bed and can be used for processes such as absorption, parsing, distillation, but does not disclose the utilisation technology of industrially scalable.CN1064338A discloses the method for utilizing rotating bed to carry out the oil-field flooding deoxidation; CN1116146A discloses a kind of method that under super gravity field, prepares ultrafine particle.
The super gravity field technology is the new technology that early eighties just occurs; Its internal mechanism is also continuing exploration; Research for application and development is still constantly being carried out; New Application Areas is also in continuous developing, and it also is not applied to the production report of hydroformylation of olefin for now as efficient mass transfer and conversion unit about efficient rotary packed bed reactor drum.
Summary of the invention
Technical problem to be solved by this invention be in the past in the technology in the hydroformylation of olefin process, feed stock conversion is low, the technical problem that the purpose selectivity of product is low.A kind of method of new preparing aldehyde by hydro formylating defin is provided.This method has the feed stock conversion height, the advantage that the purpose selectivity of product is high.
In order to solve the problems of the technologies described above; The technical scheme that the present invention adopts is following: a kind of method of preparing aldehyde by hydro formylating defin is a raw material with alkene, CO and the hydrogen of C2～C8, is catalyzer with rhodium-containing liquor; 40～160 ℃ of temperature of reaction; Reaction pressure 0.5～5.0MPa, the mol ratio of alkene and rhodium is under 0.5～30: 1 the condition, raw material and rhodium-containing liquor catalyzer get into contact reacts in the high efficiency reactor; Generation contains the liquid efflunent of aldehyde, it is characterized in that high efficiency reactor is selected from rotary packed bed reactor drum.
The reactor drum preferred reaction conditions is in the technique scheme: CO and H
2Mol ratio be 0.8～1.5: 1, the mol ratio of CO and alkene is 0.8～5: 1, the mol ratio of alkene and rhodium is 1～20: 1; Temperature of reaction is 60～140 ℃, and reaction pressure is 1～4.0MPa.The catalyzer of rhodium-containing liquor in the total catalyst weight umber, preferably includes 1～50 part of rhodium complex, 10～1000 parts of phosphine parts and 200～6000 parts of solvents.The phosphine part is preferably water miscible trisulfonated triphenylphosphine trisodium salt, at least a in two sulfonated triphenylphosphine disodium salts and a sulfonated triphenylphosphine one sodium salt.Rhodium complex is preferably a chlorine cyclooctadiene rhodium; Diacetyl acetone rhodium; One chlorine, one carbonyl diurethane (trisulfonated triphenylphosphine trisodium salt) rhodium; One chlorine, one carbonyl diurethane (two sulfonated triphenylphosphine disodium salts) rhodium, at least a in a chlorine one carbonyl diurethane (sulfonated triphenylphosphine one sodium salt) rhodium and a hydrogen one carbonyl three (trisulfonated triphenylphosphine trisodium salt) rhodium.
The rotating speed of the high efficiency reactor in the technique scheme is preferably 300～5000rpm, more preferably 300～3000rpm.Alkene is preferably selected from the terminal olefin of C2～C6.
As everyone knows, alkene hydroformylation reaction process is the reaction process of gas-liquid mass transfer control, if gas-liquid mass transfer efficient is high; Reaction efficiency is just high, and rotary packed bed hypergravity high efficiency reactor can improve mass-transfer efficiency by how much orders of magnitude as efficient mass transfer equipment; And then improve speed of reaction greatly, simultaneously, owing to shortened the residence time greatly; Also avoid the generation of secondary reaction, effectively improved selectivity.
Adopted high efficiency reactor in the method for preparing aldehyde by hydro formylating defin of the present invention, relatively simple for structure owing to having adopted, the rotary filler layer that volume is little replaces huge tower in the traditional technology.Make total system compact to design, easy and simple to handle, the operation and maintenance cost is low, and floor space is little, and turndown ratio is big.Can reduce processing cost significantly.Simultaneously in the olefin hydroformylation high efficiency reactor two gas inletes the effective distribution that can optimize gas-liquid mass transfer and gas to greatest extent is set, and then significantly improve reaction efficiency, improve the purpose product yield.
The present invention is a raw material with alkene, CO and the hydrogen of C2～C8, is catalyzer with rhodium-containing liquor; 40～160 ℃ of temperature of reaction, reaction pressure 0.5～5.0MPa, the mol ratio of alkene and rhodium is under 0.5～30: 1 the condition; Raw material and rhodium-containing liquor catalyzer get into contact reacts in the rotary packed bed reactor drum, generate the liquid efflunent that contains aldehyde, and its result is: the conversion of olefines rate can be greater than 98%; The selectivity of aldehyde can reach 100%, has obtained effect preferably.
Description of drawings
Fig. 1 is the reactor drum synoptic diagram that method adopted that alkene passes through hydroformylation.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1]
Adopt the device shown in the accompanying drawing 1, adopting the rhodium catalyst among the document CN200910058201.6 embodiment 1 is catalyzer, and alkene is selected from ethene, and in total mole number, at hydrogen: CO: the mol ratio of ethene: Rh is 1: 1: 0.8: 0.2; The total amount of gas is 100m
3/ h; The mol ratio of the mixed gas of hydrogen, CO and the ethene of the mixed gas of first strand of hydrogen, CO and ethene and second strand is under 2: 1 the condition; Two strands of mixed gass are got in the hydroformylation of olefin device from first gas inlet 2 and second gas inlet 16 respectively; Under differential pressure action, diffuse into lower floor's filler 15, rotation filler rotating speed transfers to 2000rpm.The solution of rhodium-containing catalyst gets into the liquid distributor 8 of hydroformylation of olefin device and sprays to the filler inboard through liquid-inlet 3; Gas and liquid counter current contact in the packing layer 6 on the hydroformylation of olefin device obtains unreacted gaseous effluent I and the liquid efflunent II that contains catalyzer and reaction product aldehyde.Unreacted gaseous effluent I sends into follow-up system through pneumatic outlet 4 after through the mist eliminator of rotary packed bed reactor drum 1; Liquid efflunent II gets into 1 time packing layer 15 of rotary packed bed reactor drum; After the further hybrid reaction of gas from first gas feed 2 and second gas feed 16, liquid is discharged through liquid exit 11.Temperature of reaction is 80 ℃, and pressure is 1.0MPa, and its result does, the transformation efficiency of ethene is 96%, and the selectivity of propionic aldehyde is 100%.
[embodiment 2]
Adopt the device shown in the accompanying drawing 1; Adopting the rhodium catalyst among the document CN200510085899.2 embodiment 1 is catalyzer, and alkene is selected from propylene, in total mole number; At hydrogen: CO: the mol ratio of propylene: Rh is 1: 1: 0.8: 0.2, and the total amount of gas is 100m
3/ h; The mol ratio of the mixed gas of hydrogen, CO and the propylene of the mixed gas of first strand of hydrogen, CO and propylene and second strand is under 30: 1 the condition; First strand of mixed gas, second strand of mixed gas and the component that contains liquid catalyst are introduced in the high efficiency reactor rotary filler layer 2 from first gas inlet 1, second gas inlet 10 and fluid inlet 4 respectively; The rotary filler layer rotating speed transfers to 500rpm, and wherein the introducing of first strand of gas is to be realized by the pressure reduction that system forms.Converge the fluid inlet 4 of back introducing high efficiency reactor and get into liquid distributor 9 and rotary filler layer 2 through fluid inlet pipeline 5 component of introducing that contains liquid catalyst and second strand of gas introducing through second gas inlet 10; Gas, liquid carry out abundant contact reacts in rotary filler layer, adverse current is adopted in the way of contact.After the mixed gas of the hydrogen in the gas, CO and propylene reacted with the component process that contains liquid catalyst, the gas of surplus was discharged by venting port 3, and reacted liquid passes through the liquid outlet 7 of high efficiency reactor through 6 discharges of fluid pipeline.Wherein, temperature of reaction is 100 ℃, and pressure is 2.5MPa, and be 3 seconds duration of contact, and its result does, propylene conversion is 94%, and the selectivity of butyraldehyde is 100%.
[embodiment 3]
Adopt the device shown in the accompanying drawing 1, adopting the rhodium catalyst among document CN 200910058201.6 embodiment 2 is catalyzer, and alkene is selected from butylene, and in total mole number, at hydrogen: CO: the mol ratio of butylene: Rh is 1: 1: 0.7: 0.2; The mol ratio of the mixed gas of hydrogen, CO and the butylene of the mixed gas of first strand of hydrogen, CO and butylene and second strand is under 30: 1 the condition; First strand of mixed gas, second strand of mixed gas and the component that contains liquid catalyst are introduced in the high efficiency reactor rotary filler layer 2 from first gas inlet 1, second gas inlet 10 and fluid inlet 4 respectively; The rotary filler layer rotating speed transfers to 500rpm, and wherein the introducing of first strand of gas is to be realized by the pressure reduction that system forms.Converge the fluid inlet 4 of back introducing high efficiency reactor and get into liquid distributor 9 and rotary filler layer 2 through fluid inlet pipeline 5 component of introducing that contains liquid catalyst and second strand of gas introducing through second gas inlet 10; Gas, liquid carry out abundant contact reacts in rotary filler layer, adverse current is adopted in the way of contact.After the mixed gas of the hydrogen in the gas, CO and butylene reacted with the component process that contains liquid catalyst, the gas of surplus was discharged by venting port 3, and reacted liquid passes through the liquid outlet 7 of high efficiency reactor through 6 discharges of fluid pipeline.Wherein, temperature of reaction is 100 ℃, and pressure is 2.5MPa, and be 3 seconds duration of contact, and its result does, the transformation efficiency of butylene is 94%, and the selectivity of valeral is 100%.
[embodiment 4]
Adopt the device shown in the accompanying drawing 1, adopting the rhodium catalyst among document CN 200910058201.6 embodiment 3 is catalyzer, and alkene is selected from butylene, and in total mole number, at hydrogen: CO: the mol ratio of butylene: Rh is 1: 1: 0.85: 0.1; The mol ratio of the mixed gas of hydrogen, CO and the butylene of the mixed gas of first strand of hydrogen, CO and butylene and second strand is under 30: 1 the condition; First strand of mixed gas, second strand of mixed gas and the component that contains liquid catalyst are introduced in the high efficiency reactor rotary filler layer 2 from first gas inlet 1, second gas inlet 10 and fluid inlet 4 respectively; The rotary filler layer rotating speed transfers to 2000rpm, and wherein the introducing of first strand of gas is to be realized by the pressure reduction that system forms.Converge the fluid inlet 4 of back introducing high efficiency reactor and get into liquid distributor 9 and rotary filler layer 2 through fluid inlet pipeline 5 component of introducing that contains liquid catalyst and second strand of gas introducing through second gas inlet 10; Gas, liquid carry out abundant contact reacts in rotary filler layer, adverse current is adopted in the way of contact.After the mixed gas of the hydrogen in the gas, CO and butylene reacted with the component process that contains liquid catalyst, the gas of surplus was discharged by venting port 3, and reacted liquid passes through the liquid outlet 7 of high efficiency reactor through 6 discharges of fluid pipeline.Wherein, temperature of reaction is 110 ℃, and pressure is 1.5MPa, and be 3 seconds duration of contact, and its result does, the transformation efficiency of butylene is 93%, and the selectivity of valeral is 100%.
[embodiment 5]
Adopt the device shown in the accompanying drawing 1, adopting the rhodium catalyst among the document CN200510085899.2 embodiment 9 is catalyzer, and alkene is selected from the 1-octene, and in total mole number, at hydrogen: CO: the mol ratio of 1-octene: Rh is 1: 1: 0.85: 0.1; The mol ratio of the mixed gas of the mixed gas of first strand of hydrogen, CO and 1-octene and second strand hydrogen, CO and 1-octene is under 30: 1 the condition; First strand of mixed gas, second strand of mixed gas and the component that contains liquid catalyst are introduced in the high efficiency reactor rotary filler layer 2 from first gas inlet 1, second gas inlet 10 and fluid inlet 4 respectively; The rotary filler layer rotating speed transfers to 2000rpm, and wherein the introducing of first strand of gas is to be realized by the pressure reduction that system forms.Converge the fluid inlet 4 of back introducing high efficiency reactor and get into liquid distributor 9 and rotary filler layer 2 through fluid inlet pipeline 5 component of introducing that contains liquid catalyst and second strand of gas introducing through second gas inlet 10; Gas, liquid carry out abundant contact reacts in rotary filler layer, adverse current is adopted in the way of contact.After the mixed gas of the hydrogen in the gas, CO and 1-octene reacted with the component process that contains liquid catalyst, the gas of surplus was discharged by venting port 3, and reacted liquid passes through the liquid outlet 7 of high efficiency reactor through 6 discharges of fluid pipeline.Wherein, temperature of reaction is 110 ℃, and pressure is 1.5MPa, and be 3 seconds duration of contact, and its result does, the transformation efficiency of 1-octene is 90%, and the selectivity of aldehyde C-9 is 99.8%.
[Comparative Examples 1]
According to the reaction conditions of embodiment 1, the gas-liquid total feed, just reactor drum adopts the reaction kettle in the conventional gravity field, and gas, liquid carry out abundant contact reacts with catalyzer in reaction.Its result does, the transformation efficiency of ethene is 80%, and the selectivity of propionic aldehyde is 98.5%.
Claims (8)
1. the method for a preparing aldehyde by hydro formylating defin is a raw material with alkene, CO and the hydrogen of C2～C8, is catalyzer with rhodium-containing liquor; 40～160 ℃ of temperature of reaction; Reaction pressure 0.5～5.0MPa, the mol ratio of alkene and rhodium is under 0.5～30: 1 the condition, raw material and rhodium-containing liquor catalyzer get into contact reacts in the high efficiency reactor; Generation contains the liquid efflunent of aldehyde, it is characterized in that high efficiency reactor is selected from rotary packed bed reactor drum.
2. according to the said olefin hydroformylation method of claim 1, it is characterized in that CO and H
2Mol ratio be 0.8～1.5: 1, the mol ratio of CO and alkene is 0.8～5: 1, the mol ratio of alkene and rhodium is 1～20: 1; Temperature of reaction is 60～140 ℃, and reaction pressure is 1～4.0MPa.
3. according to the said olefin hydroformylation method of claim 1, it is characterized in that the catalyzer of rhodium-containing liquor,, comprise 1～50 part of rhodium complex, 10～1000 parts of phosphine parts and 200～6000 parts of solvents in the total catalyst weight umber.
4. according to the said olefin hydroformylation method of claim 3, it is characterized in that the phosphine part is water miscible trisulfonated triphenylphosphine trisodium salt, at least a in two sulfonated triphenylphosphine disodium salts and a sulfonated triphenylphosphine one sodium salt.
5. according to the said olefin hydroformylation method of claim 3; It is characterized in that rhodium complex is a chlorine cyclooctadiene rhodium; Diacetyl acetone rhodium; One chlorine, one carbonyl diurethane (trisulfonated triphenylphosphine trisodium salt) rhodium, a chlorine one carbonyl diurethane (two sulfonated triphenylphosphine disodium salts) rhodium, at least a in a chlorine one carbonyl diurethane (sulfonated triphenylphosphine one sodium salt) rhodium and a hydrogen one carbonyl three (trisulfonated triphenylphosphine trisodium salt) rhodium.
6. according to the said olefin hydroformylation method of claim 1, the rotating speed that it is characterized in that high efficiency reactor is 300～5000rpm.
7. according to the said olefin hydroformylation method of claim 6, the rotating speed that it is characterized in that high efficiency reactor is 300～3000rpm.
8. according to the said olefin hydroformylation method of claim 1, it is characterized in that alkene is selected from the alhpa olefin of C2～C6.
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| CN102649716A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Olefin hydroformylation method |
| CN102911021A (en) * | 2012-11-12 | 2013-02-06 | 青岛三力本诺化学工业有限公司 | Method for preparing aldehyde through linear chain olefin hydroformylation |
| CN103990495A (en) * | 2014-04-24 | 2014-08-20 | 上海华谊（集团）公司 | Olefin hydroformylation catalyst |
| CN104058944A (en) * | 2014-04-24 | 2014-09-24 | 上海华谊（集团）公司 | Method for preparing aldehyde through alkene hydroformylation reaction |
| CN104667976A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院大连化学物理研究所 | Multi-phase catalyst for preparing propionaldehyde by ethene hydroformylation and method for using multi-phase catalyst |
| US9611203B2 (en) | 2013-12-11 | 2017-04-04 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for olefin hydroformylation reaction using solid heterogeneous catalyst |
| CN106607093A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst composition and use thereof |
| CN106607092A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst composition and use thereof |
| CN106608816A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for preparing C4-C8 aldehydes |
| CN111302917A (en) * | 2020-03-27 | 2020-06-19 | 中国海洋石油集团有限公司 | Olefin hydroformylation device and method |
| CN113480415A (en) * | 2021-06-30 | 2021-10-08 | 中国成达工程有限公司 | Process for synthesizing butanedialdehyde by acrolein hydroformylation |
| CN113698281A (en) * | 2020-05-21 | 2021-11-26 | 中国石油化工股份有限公司 | Hydroformylation process |
| CN113698280A (en) * | 2020-05-21 | 2021-11-26 | 中国石油化工股份有限公司 | Olefin hydroformylation method |
| CN114072429A (en) * | 2019-05-24 | 2022-02-18 | 伊士曼化工公司 | Recovery of constituent cellulose ester |
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| CN102649716A (en) * | 2011-02-25 | 2012-08-29 | 中国石油化工股份有限公司 | Olefin hydroformylation method |
| CN102911021A (en) * | 2012-11-12 | 2013-02-06 | 青岛三力本诺化学工业有限公司 | Method for preparing aldehyde through linear chain olefin hydroformylation |
| CN104667976A (en) * | 2013-11-29 | 2015-06-03 | 中国科学院大连化学物理研究所 | Multi-phase catalyst for preparing propionaldehyde by ethene hydroformylation and method for using multi-phase catalyst |
| US9611203B2 (en) | 2013-12-11 | 2017-04-04 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Method for olefin hydroformylation reaction using solid heterogeneous catalyst |
| CN103990495B (en) * | 2014-04-24 | 2017-12-26 | 上海华谊（集团）公司 | Olefin hydroformylation catalyst |
| CN103990495A (en) * | 2014-04-24 | 2014-08-20 | 上海华谊（集团）公司 | Olefin hydroformylation catalyst |
| CN104058944A (en) * | 2014-04-24 | 2014-09-24 | 上海华谊（集团）公司 | Method for preparing aldehyde through alkene hydroformylation reaction |
| CN106607093B (en) * | 2015-10-22 | 2019-07-09 | 中国石油化工股份有限公司 | Carbon monoxide-olefin polymeric and application thereof |
| CN106607092A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst composition and use thereof |
| CN106607093A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Catalyst composition and use thereof |
| CN106607092B (en) * | 2015-10-22 | 2019-10-08 | 中国石油化工股份有限公司 | Carbon monoxide-olefin polymeric and its application |
| CN106608816A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Method for preparing C4-C8 aldehydes |
| CN114072429A (en) * | 2019-05-24 | 2022-02-18 | 伊士曼化工公司 | Recovery of constituent cellulose ester |
| CN114072429B (en) * | 2019-05-24 | 2023-12-26 | 伊士曼化工公司 | Recovery of component cellulose esters |
| CN111302917B (en) * | 2020-03-27 | 2022-10-14 | 中国海洋石油集团有限公司 | Olefin hydroformylation device and method |
| CN111302917A (en) * | 2020-03-27 | 2020-06-19 | 中国海洋石油集团有限公司 | Olefin hydroformylation device and method |
| CN113698280A (en) * | 2020-05-21 | 2021-11-26 | 中国石油化工股份有限公司 | Olefin hydroformylation method |
| CN113698281A (en) * | 2020-05-21 | 2021-11-26 | 中国石油化工股份有限公司 | Hydroformylation process |
| CN113698281B (en) * | 2020-05-21 | 2023-10-10 | 中国石油化工股份有限公司 | Method for hydroformylation |
| CN113698280B (en) * | 2020-05-21 | 2023-10-13 | 中国石油化工股份有限公司 | Olefin hydroformylation method |
| CN113480415A (en) * | 2021-06-30 | 2021-10-08 | 中国成达工程有限公司 | Process for synthesizing butanedialdehyde by acrolein hydroformylation |
| CN113480415B (en) * | 2021-06-30 | 2023-10-24 | 中国成达工程有限公司 | Process for synthesizing glyoxal by hydroformylation of acrolein |
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