CN102826972B - Method for preparing aldehydes though hydroformylation of olefins - Google Patents
Method for preparing aldehydes though hydroformylation of olefins Download PDFInfo
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Abstract
The invention relates to a method for preparing aldehydes though hydroformylation of olefins. According to the method, (1) C2-C4 olefins and synthesis gases are contacted with a catalyst-containing solution in a first reaction kettle to prepare aldehydes at 80-100 DEG C and at the pressure of 1.0-3.0MPa; (2) the unseparated product steam from the first reaction kettle and the supplemented synthesis gases enter into a second reaction kettle for a continuous reaction at 80-100 DEG C and at the pressure of 1.0-3.0MPa; (3) a little inert gases are discharged from the second reaction kettle, the unseparated liquid-phase products enter a gas stripping column and are contacted with the synthesis gases at 30-60 DEG C and at the pressure of 1.0-3.0MPa, the unreacted raw materials are taken out and returned into the reaction kettles, and the products are transferred into a post-treatment unit after the gas stripping process. Due to the adoption of a manner of connecting two kettles in series, the single pass conversion rate of the olefins is increased to 94.2% and the total utilization rate of the olefins can be as high as 99%. Compared with the latter gas stripping manner in flash evaporation-absorption-gas stripping in the prior art, the method provided by the invention simplifies the process and obviously increases the comprehensive efficiency.
Description
Technical field
The present invention relates to a kind of method of hydroformylation of olefin aldehyde, be specifically related to C
2-C
4hydroformylation of olefin prepares the method for aldehyde.Belong to the preparation field of aldehyde.
Background technology
The production technology relating to hydroformylation of olefin is updated because it is commercially significant.This improvement can be divided into the improvement around catalyzer and the improvement around technological process.
The mainstream technology that current industrial adopts uses what is called " homogeneous catalysis " technology that rhodium-phosphine complex is catalyzer.The problem that corresponding technological process needs solve is:
(1) at least one reaction zone is provided to make raw material olefin and synthetic gas (CO/H
2) effectively carried out being obtained by reacting product by under the catalyst action that dissolves.Comprising the selection of reactor types, number of reactors, and reaction conditions etc.;
(2) provide separation method that reaction product, unconverted raw material and catalyst solution are effectively separated;
(3) array mode providing said units to operate.
Due to the complicacy of hydroformylation reaction, the selection that can make is various.Prior art has proposed multiple solution for the problem of above-mentioned three aspects.
Such as: with a large amount of unstripped gas with circulation, reaction product taken out of with gaseous form and make catalyst solution retain in what is called " gas phase circulation " technique in reactor.For another example: reactant flow is all discharged by reactor, catalyst solution recirculation is made to return what is called " liquid phase circulation " technique etc. of reaction zone through being separated.
In " Chemical carbon monoxide " edited by J. Fa Erbei, " application of organometallics in homogeneous catalysis " of jointly being edited by B. Kao Niersi and W.A. Elman, and in the book such as " hydroformylation reaction of rhodium catalysis " not jointly edited by C. carat gentle in P.W.N.M.Van, the various techniques of hydroformylation are documented and are commented on.
In the prior art, for the setting of reaction zone, adopting continuous flow to stir autoclave gas-liquid reaction device is a kind of common practice.In order to improve the per pass conversion of raw material olefin, multiple reactors in series can be adopted to operate.Such as, disclose a kind of hydroformylation process of improvement in Chinese patent CN86101063A, the method allows at the first unconverted raw material in reaction zone and the CO/H supplemented
2gas jointly enters second reaction zone and continues reaction, thus the per pass conversion of alkene is improved.Similar way also has disclosure in GB1387657, US5105018 and US5367106.
Alkene, especially low-carbon alkene, when carrying out hydroformylation reaction due to by the restriction of some kinetic factor, namely one way reaches very high conversion by reaction zone and is difficulty and uneconomic.Again because unconverted olefin is mainly present among liquid phase under typical reaction conditions.Therefore need one to isolate unconverted alkene from product liquid phase stream, make it the method that reaction zone is gone back in recirculation.
Available simple method is an air-extraction, namely allows CO/H as reaction raw materials
2gas first carries out two with the product liquid phase stream containing unconverted olefin and contacts, and makes alkene by air lift to gas phase, with CO/H
2return to reaction zone together.
The technical scheme comprising air lift method can be found from prior art.Such as: propose in Chinese patent CN95121416.0, single reaction still with the gas phase recycle system can be connected with a gas stripping column, reaction liquid product after outflow reactor first raised temperature at least higher than 5 DEG C, reaction zone, enter gas stripping column and CO/H afterwards
2feed gas, makes unconverted alkene take out of and return.
The obvious problem that this scheme exists is that stripping temperature is too high.Owing to not separating catalyst solution, and temperature is higher than temperature of reactor, can infer can continue to react in gas stripping column, and its condition departs from the reasonable terms of this reaction greatly; In addition according to existing document, such as record in US Patent No. 4277627, rhodium catalyst can accelerate inactivation process under high temperature and high CO dividing potential drop.Although claim the considerable change not observing catalyst activity in CN95121416, the existence of risk is conceivable.Further analysis, why adopt high-temperature operation in air stripping unit, because reaction zone have employed single still working method, this way conversion of olefines rate is lower, in reaction zone, concentration of olefin is higher, though the efficiency that can improve reactor causes raising stripping temperature of having to just can make the whole air lift of unconverted alkene out.
The hydroformylation process that another kind comprises air lift method is disclosed in Chinese patent CN91110549.2.The method allows the liquid product stream containing unconverted olefin first make alkene be transferred to gas phase through vacuum flashing, then carries out absorption with the isolated product aldehyde of subsequent cell to flash gas and make alkene enter liquid phase, finally uses aforementioned CO/H again
2the method of air lift by alkene air lift out and take back reactor.Adopt the combined method of this " flash distillation-absorption-air lift " can accomplish first to be separated by catalyst solution before air lift, avoid because air lift may cause the risk of disadvantageous effect to catalyzer.But this way obviously increases equipment, technological process is made to become complicated.
Summary of the invention
The technical problem to be solved in the present invention:
Ensure that conversion of olefines needs to make the problem of unconverted olefin recycle simultaneously for needing in continuous hydroformylation process; and for improving the shortcoming existed in prior art, the object of this invention is to provide the method for alkene utilising efficiency in a kind of effective solution hydroformylation reaction.More particularly, a kind of " reaction-be separated " array mode is newly provided, thus when not affecting catalyst performance, technological process is simplified, ensure effective utilization of raw material olefin.
Technical solution of the present invention is:
The technical scheme that the present invention proposes adopts the mode of two still series connection to arrange hydroformylation reaction district, adopts the mode of directly carrying out low temperature air lift to the liquid product stream of reaction to arrange disengaging zone for unconverted olefin.Relative to the scheme of " flash distillation-absorption-air lift " in prior art, the present invention is called " before two still air lift " scheme.
Main points of the present invention are as follows:
Hydroformylation of olefin prepares a method for aldehyde, comprises following processing step:
(1) C
2-C
4alkene and synthetic gas contact with the solution containing catalyzer and generate aldehyde in the first reactor under temperature 80-100 DEG C with the condition of pressure 1.0-3.0MPa;
(2) first reactor product streams enter the second reactor without separation together with the synthetic gas supplemented to be continued to react under temperature 80-100 DEG C and pressure 1.0-3.0MPa condition;
A small amount of rare gas element discharged by (3) second reactors and liquid product stream enters gas stripping column without separation, contact with synthetic gas under 30-60 DEG C with pressure 1.0-3.0MPa condition, unreacted raw material taken out of and returns the first reactor and the second reactor, and sending into subsequent processing units through the product stream of air lift.
Two reactors of described series connection belong to liquid phase circulation technique.
In step (2), the first described reactor product stream comprises one gaseous stream and one liquid phase stream, and gaseous stream comprises unconverted reaction raw materials, as H
2, CO, alkene and inert component CH
4, CO
2, N
2, alkane, also comprise a small amount of vaporized product aldehyde; Liquid phase stream comprises by the reaction raw materials dissolved, as H
2, the aldehyde that generates of CO, alkene and inert component, reaction product aldehyde and side reaction two, three, polymer, by the catalyzer dissolved.
In step (3), described liquid product stream comprises by the H dissolved
2, the aldehyde that generates of CO, inert component, alkene, reaction product aldehyde and side reaction two, three, polymer, by the catalyzer dissolved.
In step (3), the described product stream through air lift comprise aldehyde, aldehyde two, three, tetramer and by the catalyzer dissolved.
In step (3), described unreacted raw material to be taken out of and any one or two that return in the first reactor and the second reactor.
Catalyzer of the present invention is rhodium-phosphine complex catalyst, the rhodium compound wherein added in system can be selected from rhodium dicarbonyl acetylacetonate, acetylacetonatodicarrhodium rhodium, three (triphenylphosphine) carbonyl hydrogen rhodium, two (triphenylphosphine) rhodium chloride, dichloro four carbonyl diurethane rhodium, rhodium sesquioxide, ten dicarbapentaborane four rhodiums, 16 carbonyl six rhodiums, rhodium nitrate, rhodium acetate etc.
The Phosphine ligands added in system can be selected from trialkyl phosphine, triaryl phosphine, alkyl diaryl phosphine, dialkyl aryl phosphine, bicyclic alkyl aryl phosphine, cycloalkyl diaryl phosphine, tris(aralkyl)phosphine, tricyclic alkyl phosphine, alkyl and/or aryl diphosphine, cycloalkyl and/or aryl diphosphine, single organo phosphinates, two organo phosphinates, the mixture of single compounds such as three organo phosphinates and Organophosphonate or many persons.
The catalyst solvent adopted in the present invention can be selected from the C of straight or branched
1-C
30contain or do not contain the alkane of other atoms except hydrocarbon atom, aromatic hydrocarbons, alcohol, ketone, ether, ester, sulfoxide, phenols, such as pentane, petroleum naphtha, kerosene, hexanaphthene, toluene, dimethylbenzene, methyl phenyl ketone, benzonitrile, poly-butyraldehyde etc.
Special restriction is not made to the condition of hydroformylation reaction in the present invention; these conditions can find in known technology, and wherein crucial reaction conditions such as temperature of reaction is selected from 80-120 DEG C, are preferably 85-110 DEG C; reaction pressure is selected from 0.5-5.0MPa, is preferably 1.0-3.0MPa.
The air lift equipment adopted in the present invention can be selected from any unit equipment realizing function of the present invention in known technology, preferably selects tower equipment, and as packing tower, tray column, bubble tower etc., stage number requires as target to meet air lift.
In order to further illustrate concrete technology step of the present invention, 1 be described in detail by reference to the accompanying drawings.Two stirring tanks (R1, R2) and a gas stripping column (T1) form flow process of the present invention, and wherein the gas phase of second reactor (R2) and liquid phase are discharged logistics and be connected with water cooler.Alkene, synthetic gas enter First reactor together with catalyst solution, carry out hydroformylation reaction wherein and generate butyraldehyde.Unreacted raw material, reaction product and catalyzer enter second reactor from the outflow of First reactor together with the synthetic gas supplemented to be continued to react.Second reactor has a small amount of tail gas to discharge after condensation, and liquid phase stream enters gas stripping column (T1) after cooling.The liquid phase stream reacted in tower contacts with synthetic gas is reverse, allows the unconverted raw material air lift of dissolving in liquid phase stream to gas phase and enters the first reactor and the second reactor respectively.Liquid phase stream through air lift enters subsequent processing units.
When implementing of the present invention, unrestriced ins and outs all can find in corresponding prior art, and these well known to a person skilled in the art.Therefore will not enumerate at this.
The invention has the beneficial effects as follows:
Owing to have employed two still series system, the per pass conversion of alkene is improved, decreases the load needing the material quantity of recycle simultaneously to reduce gas stripping column, make it can operate under lesser temps, thus avoid the risk affecting catalyst performance.Relative to " rear air lift " mode of prior art flash distillation-absorption-air lift, flow process of the present invention is simplified.Overall efficiency is improved significantly.
Accompanying drawing explanation
Fig. 1 is gas stripping process schematic flow sheet before two still
Embodiment
A specific embodiments of the present invention is further illustrated as follows with accompanying drawing 1:
Propylene stream (1) and by gas stripping column T1 come synthetic gas (10) and by catalyst separating unit (not shown in FIG.) come catalyst solution logistics (2) enter the first reactor R1 together, wherein propylene (1) inlet amount is 21Sg/h, and catalyst stream (2) inlet amount is 211g/h; Under the effect of rhodium-triphenylphosphine catalysis and 91 DEG C and 1.9MPa stagnation pressure condition, there is hydroformylation reaction at the first reactor Raw and generate butyraldehyde.One gaseous stream (3) and one liquid phase stream (4) shift out in the first reactor, gas phase discharging (3) is 33g/h, liquid phase discharging (4) is 585g/h, without be separated and with supplement synthesis gas stream (11) together with enter the second reactor with 91 DEG C with 1.8MPa stagnation pressure under continue to react.One vapor phase stream (5) is emptying (6) after condenser E1 condensation.And (not shown) enters water cooler E2 logistics is cooled to 40 DEG C after liquid phase stream (7) supercharging.Enter gas stripping column T1 afterwards.One synthesis gas stream (9) enters bottom gas stripping column, tower is built with the filler reaching 12 theoretical stages, working pressure is 2.1MPa, and temperature is 40 DEG C, and in tower, synthetic gas and reacting product stream fully contact and wherein unconverted raw band is returned reactor to gas phase.And be admitted to subsequent processing units through the product stream (12) of air lift.
Operate according under said process and condition, analyze from each logistics sampling in process, the per pass conversion that can be calculated propylene by analytical results is 94.2%, and the overall utilization of propylene is 99%, substantially not containing unconverted propylene in gas stripping column tower reactor liquid effluent.
Claims (8)
1. hydroformylation of olefin prepares a method for aldehyde, comprises following processing step:
(1) C
2-C
4alkene and synthetic gas contact with the solution containing catalyzer and generate aldehyde in the first reactor at temperature 80 ~ 100 DEG C with the condition of pressure 1.0-3.0MPa;
(2) first reactor product streams enter the second reactor without separation together with the synthetic gas supplemented to be continued to react under temperature 80-100 DEG C and pressure 1.0-3.0MPa condition;
A small amount of rare gas element discharged by (3) second reactors and liquid product stream enters gas stripping column without separation, contact with synthetic gas under 30-60 DEG C with pressure 1.0-3.0MPa condition, unreacted raw material taken out of and returns reactor, and sending into subsequent processing units through the product stream of air lift.
2. method according to claim 1, is characterized in that two reactors of connecting belong to liquid phase circulation technique.
3. method according to claim 1, is characterized in that in step (2), the first reactor product stream comprises one gaseous stream and one liquid phase stream.
4. method according to claim 3, is characterized in that gaseous stream comprises unconverted reaction raw materials gas, inert component gas, a small amount of vaporized product aldehyde.
5. method according to claim 3, it is characterized in that liquid phase stream comprise the aldehyde generated by reaction raw materials, inert component, reaction product aldehyde and the side reaction of dissolving two, three, polymer, by the catalyzer dissolved.
6. method according to claim 1, it is characterized in that liquid product stream in step (3) comprise the aldehyde generated by reaction raw materials, inert component, reaction product aldehyde and the side reaction of dissolving two, three, polymer, by the catalyzer dissolved.
7. method according to claim 1, it is characterized in that in step (3) through the product stream of air lift comprise aldehyde, aldehyde two, three, tetramer and by the catalyzer dissolved.
8. method according to claim 1, is characterized in that being taken out of by unreacted raw material in step (3) and to return in the first reactor, the second reactor any one or two.
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103130623A (en) * | 2011-12-05 | 2013-06-05 | 中国石油化工集团公司 | Reaction system and reaction method of gas-liquid double-circulation hydroformylation of preparing butyraldehyde with propylene |
| MY184826A (en) | 2014-12-04 | 2021-04-24 | Dow Technology Investments Llc | Hydroformylation process |
| CN108586219A (en) * | 2018-06-28 | 2018-09-28 | 南京荣欣化工有限公司 | A kind of method that hydroformylation of olefin prepares aldehyde |
| CN111646883A (en) * | 2019-03-04 | 2020-09-11 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for preparing aldehyde by hydroformylation of low-carbon olefin |
| CN111153782A (en) * | 2019-12-31 | 2020-05-15 | 南京中设石化工程有限公司 | Method for preparing high-carbon aldehyde by hydroformylation of high-carbon olefin |
| CN115028520B (en) * | 2021-03-05 | 2024-09-20 | 中国石油化工股份有限公司 | Hydroformylation reaction product separation method and hydroformylation reaction separation method |
| CN116102401A (en) * | 2022-12-30 | 2023-05-12 | 广东希必达新材料科技有限公司 | Continuous production method for synthesizing tricyclodecane dimethanol by dicyclopentadiene |
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