CN102826975B - A kind of propene hydroformylation reaction prepares the method for butyraldehyde - Google Patents
A kind of propene hydroformylation reaction prepares the method for butyraldehyde Download PDFInfo
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- CN102826975B CN102826975B CN201110163702.8A CN201110163702A CN102826975B CN 102826975 B CN102826975 B CN 102826975B CN 201110163702 A CN201110163702 A CN 201110163702A CN 102826975 B CN102826975 B CN 102826975B
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Abstract
Propene hydroformylation reaction prepares a method for butyraldehyde, belongs to the preparation field of aldehyde.Comprising propylene and synthetic gas prepares butyraldehyde through hydroformylation reaction under the effect of rhodium-phosphine complex catalyst, it is characterized in that when use polymerization-grade propylene carries out for allowing reaction during raw material under 80-120 DEG C and 0.5-5MPa pressure; When using chemical grade propylene for reaction controlling during raw material is with in the polymerization-grade propylene identical temperature range that is raw material reaction, the reaction pressure that reaction pressure is raw material than polymerization-grade propylene at least improves 0.4MPa.Use technical scheme provided by the invention, when using the propylene of different stage for raw material, the loss amount of alkene can be made unaffected as far as possible, and this will bring considerable economic benefit.
Description
Technical field
The present invention relates to a kind of method that hydroformylation of olefin prepares aldehyde, relate to a kind of method of hydroformylation of propene producing butyladehyde particularly, relate more specifically to a kind ofly adapt to the hydroformylation of propene producing butyladehyde reaction method that raw material made by different content propylene.Belong to the preparation field of aldehyde.
Background technology
The hydroformylation reaction of alkene has essential industry meaning.At present, there is tens of cover industrial installation in the whole world in operation, the annual various products producing millions of tons.Wherein accounted for the overwhelming majority of production capacity by production of propylene butyraldehyde, therefore its production technology is extremely paid attention to.
The commercial run of production of propylene butyraldehyde mostly adopts rhodium-phosphine complex catalysis system, and it belongs to so-called " homogeneous catalysis " field.Large-scale industrial production adopts the operating method of serialization, raw material H
2/ CO and propylene are passed in catalyst solution, control certain condition and hydroformylation reaction is carried out in liquid phase main body.After reaction, product is separated, unreacted raw material and catalyst solution is looped back reactor, and product is sent into subsequent cell.About the method for hydroformylation of propene producing butyladehyde can with reference to " hydroformylation reaction of the rhodium catalysis " book jointly edited by C. Clavel gentle in P.W.N.M.Van.
In the prior art of hydroformylation of propene producing butyladehyde; the source of general tree propylene feedstocks is particularly limited to; its source is mainly through 3 approach: the by product (accounting for 68%) of ethylene plant's steam cracking; catalytic cracking by product (accounting for 29%), remaining 3% is obtained by methods such as conversion of olefines, dehydrogenating propane and preparing olefin by conversion of methanols.
In the prior art, relate to that to make the document of restriction to the content of propylene also less.The polymerization-grade propylene of high-content can be adopted, propylene content >=99% of this raw material in actual production.Also can adopt the chemical grade propylene of general content, the propylene content of this raw material is generally 95%, and remaining part is propane mainly.
But in the hydroformylation reaction of propylene, different propylene contents will affect the utilising efficiency of raw material.This is because in the production process of a serialization, the inert fraction induced one with raw material, such as propane, must discharge equally from system.Only in this way could keep-process be in stable state under run.And when discharging this inert fraction, unreacted propylene also can discharge thereupon.That is, the propylene utilising efficiency that higher propylene content is corresponding higher, but it is evident that this is by simultaneously corresponding higher cost of material.
Chinese patent CN01811921 discloses a kind of continuous process method that then alkene first preparing 2-8 carbon atom carry out hydroformylation reaction.The source this method giving alkene is the dehydrogenation by hydrocarbon feed, thermo-cracking, and obtaining after catalytic pyrolysis is rich in the splitting gas of alkene, through fractionation, and the raw material olefin of preparation needed for hydroformylation.What provide in embodiment is the reaction result of the hydroformylation of chemical pure propylene (95%) by obtaining after steam cracking tower.
A kind of method preparing aldehyde is disclosed in Chinese patent CN200580009313.This patent gives the source of propylene stream, namely the propylene stream formed after oxygenatedchemicals and molecular sieve catalyst contact reacts, and the content of wherein propylene is limited, point out that the content of propylene stream used is at least greater than 50%, be preferably greater than 60%, be most preferably greater than 96%.Simultaneously to dme wherein, the content of the impurity such as ethene and sulphur has also made restriction.Embodiment compared for the reaction result of the propylene (95%) adopting chemical grade and the propylene (97.5%) adopting oxygenatedchemicals and molecular sieve catalyst reaction to transform, and the transformation efficiency of propylene is respectively 93.06% and 93.88%.
A kind of hydroformylation reaction method of propylene is disclosed in Chinese patent CN200580009317.Its adopts the propylene (about 97%) being different from the propylene (95%) of the industrial chemical grade generally adopted and recommendation more high-content, by regulate synthetic gas with the charge proportion of propylene, H in synthetic gas
2with the ratio of CO, the loss amount of propylene is reduced to minimum.Provide in an embodiment chemical grade propylene and polymerization-grade propylene by regulate synthetic gas with the ratio of propylene, the transformation efficiency of propylene reaches 93.06% and 94.54% respectively.
In the face of prior art, the producer needs to select between raw materials cost and raw material utilization efficiency.It is obviously, a kind of that to adapt to the method that different stage raw material simultaneously do not make raw material utilization efficiency decline be needs.
Summary of the invention
The technical problem to be solved in the present invention:
The invention provides a kind of reaction method of hydroformylation of propene aldehyde.Specifically, provide a kind of and adapt to the reaction method that raw material made by different content propylene.Object makes the utilising efficiency of propylene unaffected when the content of raw material propylene changes, with the economy of keep-process.
Technical solution of the present invention is:
A kind of propene hydroformylation reaction prepares the method for butyraldehyde, comprise propylene and synthetic gas prepares butyraldehyde through hydroformylation reaction under the effect of rhodium-phosphine complex catalyst, when use polymerization-grade propylene carries out under 80-120 DEG C and 0.5-5MPa pressure for allowing reaction during raw material; When using chemical grade propylene for reaction controlling during raw material is with in the polymerization-grade propylene identical temperature range that is raw material reaction, the reaction pressure that reaction pressure is raw material than polymerization-grade propylene at least improves 0.4MPa.
Described polymerization-grade propylene refers to the propylene of content >=99%.
Described chemical grade propylene refers to the propylene of 90% < propylene content≤95%.
Described rhodium-phosphine complex catalyst refers to the catalyzer that rhodium compound and organophosphorus ligand generate, rhodium compound used 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, any one in rhodium acetate.
Phosphine ligands used can be selected from trialkyl phosphine, triaryl phosphine, alkyl diaryl phosphine, dialkyl aryl phosphine, bicyclic alkyl aryl phosphine, cycloalkyl diaryl phosphine, tris(aralkyl)phosphine, the own phosphine of three cycloalkanes and alkyl and/or aryl diphosphine, single organophosphite, two organophosphites, any one in phosphoric acid ester.
The catalyst solvent adopted in the present invention can be selected from the C that solvent comprises straight or branched
1-C
30containing or not containing the alkane of other atoms except hydrocarbon atom, aromatic hydrocarbons, alcohol, ketone, ether, ester, sulfoxide, in phenols any one or multiple.
In order to further illustrate the present invention, two sections of hydroformylation process that two stills of 1 are connected by reference to the accompanying drawings are illustrated, but the present invention is not limited to the two-stage process of two still series connection.Propylene (1) and synthetic gas (2) enter the first reactor (R1) together with the circulation gas (9) comprising unreacting material and the catalyst solution (10) that circulates, the pressure and temperature certain according to the different choice of propylene content in propylene feedstocks used, the hydroformylation of carrying out propylene obtains butyraldehyde, reacted containing unconverted olefin, the gas phase (3) of the materials such as the butyraldehyde of synthetic gas and gasification and comprise product and catalyst solution, the liquid phase (4) of the materials such as the aldehyde do not gasified and condensation by-product enters the second reactor R2, second reactor continues reaction under certain temperature and pressure after supplementing a certain amount of synthetic gas (5).Second reactor vapor phase stream (6) by after condensation as exhaust emissions (7).The liquid phase stream (8) that second reactor shifts out enters separating unit (S1) and is isolated into the vapor phase stream (9) comprising unreacting material, comprises the liquid phase stream (10) of catalyzer and comprises the liquid phase stream (11) of product aldehyde.Wherein vapor phase stream (9) and liquid phase stream (10) are returned to the first reaction zone, and liquid phase stream (11) is admitted to subsequent processing units.
The invention has the beneficial effects as follows:
Adopting technical scheme provided by the invention, when using the propylene of different stage for raw material, the loss amount of alkene can be made unaffected as far as possible.This will bring considerable economic benefit.
Accompanying drawing explanation
Fig. 1 is two sections of hydroformylation of propene process flow sheets of two still series connection
Embodiment
In order to further illustrate the present invention, two sections of hydroformylation process that two stills of 1 are connected by reference to the accompanying drawings are illustrated, but the present invention is not limited to the two-stage process of two still series connection.
Embodiment 1
Test according to Fig. 1 technical process, adopt polymerization-grade propylene (mole content 99.6%) to be raw material, the volume of reactor used is 2L, and the pressure of the first reactor is set to 1.9MPa, the pressure of the second reactor is set to 1.8MPa, and the temperature of reaction of two stills is 90 DEG C.The inlet amount of propylene is 200.1g/hr, and after two-stage reaction, the propylene flow of discharging from the condensed exhaust port of the second reactor is 1.44g/hr.
Comparative example 1
Test according to above-mentioned flow process, conversion unit used and temperature of reaction are with embodiment 1, and adopt chemical grade propylene (propylene content is 95%), the pressure of the first reactor is set to 1.9MPa, the pressure of the second reactor is set to 1.8MPa, and the temperature of reaction of two stills is 90 DEG C.The inlet amount of propylene is 200.2g/hr, and after two-stage reaction, the propylene flow of discharging from the condensed exhaust port of the second reactor is 2.07g/hr.Its loss amount adds 43.75% than use polymerization-grade propylene.
Embodiment 2
Test according to above-mentioned flow process, conversion unit used and temperature of reaction are with embodiment 1, and adopt chemical grade propylene (propylene content is 95%), the pressure of the first reactor is set to 23MPa, the pressure of the second reactor is set to 2.2MPa, and the temperature of reaction of two stills is 90 DEG C.The inlet amount of propylene is 200.3g/hr, and after two-stage reaction, the propylene flow of discharging from the condensed exhaust port of the second reactor is 1.44g/hr.
Claims (5)
1. a propene hydroformylation reaction prepares the method for butyraldehyde, comprising propylene and synthetic gas prepares butyraldehyde through hydroformylation reaction under the effect of rhodium-phosphine complex catalyst, it is characterized in that when use polymerization-grade propylene carries out for allowing reaction during raw material under 80-120 DEG C and 0.5-5MPa pressure; When using chemical grade propylene for reaction controlling during raw material is with in the polymerization-grade propylene identical temperature range that is raw material reaction, the reaction pressure that reaction pressure is raw material than polymerization-grade propylene at least improves 0.4MPa;
Polymerization-grade propylene refers to the propylene of content >=99%;
Chemical grade propylene refers to the propylene of 90% < propylene content≤95%;
Propene hydroformylation reaction is prepared in butyraldehyde process and is selected rhodium-phosphine complex catalyst to be the catalyzer that rhodium compound and organophosphorus ligand generate.
2. method according to claim 1, it is characterized in that rhodium compound used 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, any one in rhodium acetate.
3. method according to claim 1, it is characterized in that Phosphine ligands used can be selected from trialkyl phosphine, triaryl phosphine, alkyl diaryl phosphine, dialkyl aryl phosphine, bicyclic alkyl aryl phosphine, cycloalkyl diaryl phosphine, tris(aralkyl)phosphine, the own phosphine of three cycloalkanes and alkyl and/or aryl diphosphine, single organophosphite, two organophosphites, any one in phosphoric acid ester.
4. method according to claim 1, is characterized in that the catalyst solvent adopted can be selected from the C that solvent comprises straight or branched
1-C
30containing or not containing the alkane of other atoms except hydrocarbon atom, aromatic hydrocarbons, alcohol, ketone, ether, ester, sulfoxide, in phenols any one or multiple.
5. method according to claim 1, it is characterized in that propylene (1) and synthetic gas (2) enter the first reactor (R1) together with the circulation gas (9) comprising unreacting material and the catalyst solution (10) that circulates, the pressure and temperature certain according to the different choice of propylene content in propylene feedstocks used, the hydroformylation of carrying out propylene obtains butyraldehyde, reacted containing unconverted olefin, the gas phase (3) of the butyraldehyde of synthetic gas and gasification and comprise product and catalyst solution, the liquid phase (4) of the aldehyde do not gasified and condensation by-product enters the second reactor R2, second reactor continues reaction under certain temperature and pressure after supplementing a certain amount of synthetic gas (5), second reactor vapor phase stream (6) by after condensation as exhaust emissions (7), the liquid phase stream (8) that second reactor shifts out enters separating unit (S1) and is isolated into the vapor phase stream (9) comprising unreacting material, comprises the liquid phase stream (10) of catalyzer and comprises the liquid phase stream (11) of product aldehyde, wherein vapor phase stream (9) and liquid phase stream (10) are returned to the first reaction zone, and liquid phase stream (11) is admitted to subsequent processing units.
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| CN114082210B (en) * | 2021-11-29 | 2022-11-04 | 万华化学集团股份有限公司 | Recovery method and recovery system for waste gas and waste liquid in hydroformylation device |
| CN115716781A (en) * | 2022-10-27 | 2023-02-28 | 万华化学集团股份有限公司 | Process for preparing butyraldehyde by propane dehydrogenation coupled oxo synthesis |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1272485A (en) * | 1999-04-29 | 2000-11-08 | 中国石油化工集团公司 | Preparation method of aldehyde |
| US6642420B1 (en) * | 1998-08-14 | 2003-11-04 | Basf Aktiengesellschaft | Method for producing aldehydes and/or alcohols or amines |
| CN101293818A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Two-stage reaction method for mixed butylene hydroformylation |
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| JP2001213835A (en) * | 2000-02-01 | 2001-08-07 | Mitsubishi Chemicals Corp | Method for producing aldehyde |
| DE10031519A1 (en) * | 2000-06-28 | 2002-01-10 | Basf Ag | Process for the hydroformylation of olefins having 2 to 8 carbon atoms, I |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6642420B1 (en) * | 1998-08-14 | 2003-11-04 | Basf Aktiengesellschaft | Method for producing aldehydes and/or alcohols or amines |
| CN1272485A (en) * | 1999-04-29 | 2000-11-08 | 中国石油化工集团公司 | Preparation method of aldehyde |
| CN101293818A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Two-stage reaction method for mixed butylene hydroformylation |
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