CN104667977B - The catalyst system of hydroformylation of propene producing butyladehyde a kind of and use its method - Google Patents
The catalyst system of hydroformylation of propene producing butyladehyde a kind of and use its method Download PDFInfo
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Abstract
The present invention provides a kind of catalyst system of hydroformylation of propene producing butyladehyde; it is characterized in that; the catalyst system is made up of the heterogeneous catalyst of the conceited carried transition metal of organic ligand polymer and the co-catalyst of bidentate phosphite ester; wherein described organic ligand polymer is to polymerize the organic ligand polymer with hierarchical porous structure that the organic ligand monomer containing phosphorus and vinyl is obtained by solvent thermal polymerization method, and the transition metal is the one or more in Rh, Ir and Co.The present invention, which is additionally provided in, to be filled with the paste state bed reactor of such catalyst system, makes the raw material containing propylene and CO and H2Gaseous mixture react in the method for producing butyladehyde.The preparation method of the novel catalyst system, reaction process and device are simple; and the performance for hydroformylation of propene is stable, activity is high and selectivity is good, and especially hutanal selectivity is high; multiphase hydroformylation reaction is realized, with wide prospects for commercial application.
Description
Technical field
Come the present invention relates to a kind of novel catalyst system of hydroformylation of propene producing butyladehyde and using the catalyst system
The method for carrying out hydroformylation of propene producing butyladehyde.
Technical background
Butyraldehyde (Chemical Reviews, 2012,112,5675-5732) is that the important organic chemical industries such as production octyl alconyl are former
The intermediate of material, is also the important source material for producing various fine chemical products.Butyraldehyde has hutanal and isobutylaldehyde both isomeries
Body, hutanal is additionally operable to production trimethylolpropane, polyvinyl butyral resin mainly for the production of n-butanol and 2-Ethylhexyl Alcohol
Deng fine chemical product；Isobutylaldehyde is mainly for the production of isobutanol, neopentyl glycol, condensation and esterification products 2,2,4- trimethyls penta
Glycol, isobutyric acid, isobutyronitrile etc..The production method of butyraldehyde mainly has three kinds：Acetaldehyde condensation method, oxo synthesis (i.e. hydrogen formyl
Change method) and n-butanol dehydriding.At present, the technology path overwhelming majority of industrial production butyraldehyde uses hydroformylation method.
Octyl alconyl (the European Journal of Organic Chemistry, 2012,6309- produced with butyraldehyde
6320) it is important basic organic chemical industry raw material.Latex can be used separately as by the various ethers and aminated compounds of production of butanol
Paint, fabric processing adhesive, agricultural chemicals and rubber processing and leather treatment etc..Butanol is production butyraldehyde, butyric acid, butylamine and acetic acid
The raw material of the organic compounds such as fourth vinegar.Octanol is mainly for the manufacture of the pungent vinegar (DOP) of phthalic acid two.DOP products have trump
The title of plasticizer, is a kind of quality-high and inexpensive preferable plasticizer, is widely used in the processing of polyvinyl chloride, synthetic rubber and resin
Deng.Due to the important use and huge demand of chemicals butyraldehyde, therefore hydroformylation of propene produces butyraldehyde, further production
Octyl alconyl turns into the field of researchers' extensive concern and research.
It is the most widely used hydroformylation of propene production technology in the world today using low pressure Rh method homogeneous catalysis systems.State
This technical study is improved outside, development forms the proprietary technology having their own characteristics each.
The Rh method low pressure carbonylic synthesis technologies of Mitsubishi's chemical conversion exploitation.The technology makees the solvent of Rh catalyst, tool using toluene
Have that viscosity is low, conduct heat, catalyst activity is high, product quality is high, rhodium entrainment loss is small, catalyst activity reduction slow and reactor
The features such as production efficiency is high.Catalyst recovery system is carried inside device, is returned using crystallization and centrifugal filtration from dead catalyst
Receive organophosphorus ligand and Rh complex compounds.Catalyst manufactory is periodically sent to reclaim Rh, system after not recoverable useless Rh catalyst concentrations
Standby raw catelyst returns to factory and reused,, can not due to being homogeneous reaction although such a technology is with higher reactivity
Metal loss problem occurs with avoiding.
Rh catalyst is expensive, to reduce its loss, Rule eighties chemical (chemical science and technology market, 2005,28,1-
8) a kind of two-phase technique is developed, make ligand with a triphenylphosphine three-sulfonate is modified to Rh catalyst.This catalysis
There is catalyst and product can be easily separated for agent, product just with isomer ratios it is high the characteristics of, and use water as solvent, both cheaply, peace
Entirely, environmental protection is conducive to again.The technology is also applied for the production of long-chain olefin.Catalyst preparation is provided with process unit and useless
Rh catalyst recovery process, therefore useless Rh catalyst is not required to send out outside battery limit (BL), can reclaim and use in the present apparatus.But this technique
Have weak point, mainly due to olefin feedstock in aqueous medium than in organic phase solubility it is low, so rate of catalysis reaction
Decrease.Simultaneously as this reaction is heterogeneous, so catalyst activity is at a fairly low, the behaviour of water-soluble catalyst technique
Make pressure and temperature higher, and Rh contents are higher.
The industrialization technology of current hydroformylation of propene still mainly uses homogeneous catalysis system, how to develop a kind of new
Heterogeneous catalyst and Industrialized processing technique, make its both have homogeneous reaction high activity and selectivity, how opposite have concurrently again
The advantage that can be reused should be easily isolated, the main target studied as this area.
The content of the invention
For the deficiencies in the prior art, industrially can easily it be realized it is an object of the invention to provide one kind
High activity and high selectivity hydroformylation of propene producing butyladehyde new catalyst system and its slurry reactor technique.
Therefore, on the one hand, the present invention provides a kind of catalyst system of hydroformylation of propene producing butyladehyde, its feature exists
In the catalyst system is by the conceited heterogeneous catalyst of carried transition metal of organic ligand polymer and helping for bidentate phosphite ester
Catalyst is constituted, wherein the organic ligand polymer is to be matched somebody with somebody by the polymerization of solvent thermal polymerization method containing phosphorus P and the organic of alkenyl
The organic ligand polymer with hierarchical porous structure that body monomer is obtained, the transition metal be one kind in Rh, Ir and Co or
It is several.
In a preferred embodiment, the gross weight based on the heterogeneous catalyst, the content of the transition metal is
0.01~20.0%.
In a preferred embodiment, the organic ligand polymer is to contain phosphorus P by the polymerization of solvent thermal polymerization method
The organic ligand polymer with hierarchical porous structure obtained with the organic ligand monomer of vinyl.
In a preferred embodiment, the bidentate phosphite ester has following structural formula：
Wherein, X is substituted or unsubstituted C6-C28Arylene or sub- heteroaryl perfume base；Y1、Y2、Z1And Z2Independently of one another
It is hydrogen, the tert-butyl group or methoxyl group；Each Q represents to be not present or direct bond independently of one another.
In a preferred embodiment, the bidentate phosphite ester is：
In a preferred embodiment, the P in the bidentate phosphite ester and the transition gold in the heterogeneous catalyst
The mol ratio of category is 1：1~30：1.
On the other hand, the present invention provides a kind of method of hydroformylation of propene producing butyladehyde, it is characterised in that be filled with
In the paste state bed reactor of above-mentioned catalyst system, make the raw material containing propylene and CO and H2Gaseous mixture react.
In a preferred embodiment, the mixture of the pure propylene of the raw material containing propylene or propylene and alkane,
The CO and H2Gaseous mixture in CO/H2Volume ratio is 1：1.
In a preferred embodiment, the raw material containing propylene and the CO and H2The mol ratio of gaseous mixture be
0.1：1~1：0.1.
In a preferred embodiment, the raw material containing propylene with high-pressure pump liquid enter mixing preheater and
Liquid weight air speed is 0.01~10h-1, and the CO and H2Gaseous mixture be passed directly into the mixing and preheater and contain with described
After the raw material for having propylene is sufficiently mixed, substantial amounts of small gas is dispersed into from the bottom of the paste state bed reactor through gas distributor
Enter back into paste state bed reactor and react after bubble.
In a preferred embodiment, the temperature of the reaction is 343~453K, and pressure is 1.0~20.0MPa.
In a preferred embodiment, the step of methods described also includes separation butyraldehyde product, wherein being flowed out with tail gas
The fraction butyraldehyde product of the paste state bed reactor through gas-liquid separator separates, and most of butyraldehyde product by interior filtering with
After the heterogeneous catalyst separation, the paste state bed reactor is removed.Preferably, the butyraldehyde production of the paste state bed reactor is removed
Thing obtains butyraldehyde in point tower at the beginning of butyraldehyde-bidentate phosphite ester by flash separation, and remaining bidentate phosphite ester butyraldehyde is molten
Liquid carries out circular response through paste state bed reactor described in high-pressure pump blowback；And through the unreacted after the gas-liquid separator separates
Raw material tail gas mixed with the fresh raw material after through being circulated in paste state bed reactor described in recycle compressor compression and back
Reaction.Preferably, the butyraldehyde that is obtained through the gas-liquid separator separates and through at the beginning of the butyraldehyde-bidentate phosphite ester points of tower flash distillation
Enter after obtained butyraldehyde mixing and take off light rectifying knockout tower, divide again from the bottom stream for taking off light rectifying knockout tower into de-
Pure butyraldehyde product is obtained from tower, and from the tower top of the de- heavy knockout tower.
The beneficial effect that the present invention is produced includes but is not limited to following：Compared with existing hydroformylation reaction technology, this
Invention constitutes catalyst system as a result of novel heterogeneous catalytic agent and bidentate phosphite ester co-catalyst, so slurry bed system is anti-
Answer technique and device simple；Catalyst separation uses such as built-in filter, and separation is simple.Bidentate phosphite ester co-catalyst is returned
House easy；Method for preparing catalyst is simple, and the hydroformylation performance of catalyst is stable, and high income is solved and deposited in the prior art
Either metal component be lost in or part is lost in, or catalyst is the problems such as be difficult to recycle and reuse, with wide
Prospects for commercial application.
Brief description of the drawings
Fig. 1 is a kind of slurry bed system propene hydroformylation reaction flow of the novel catalyst system used according to the invention
Figure.
Fig. 2 is the structural representation of three (4- vinyl benzenes) base Phosphine ligands monomers.
Embodiment
The present invention is using a kind of heterogeneous catalyst and bidentate phosphorous acid of carried transition metal of being thought highly of oneself by organic ligand polymer
The novel catalyst system of the co-catalyst composition of ester part, and matched slurry reactor new technology, it is possible to achieve
The slurry reactor technique of high activity and with high selectivity hydroformylation of propene producing butyladehyde, the heterogeneous catalyst is by transition metal group
Divide and constituted with hierarchical porous structure organic ligand polymer.Hierarchical porous structure organic ligand polymer support has carrier and matched somebody with somebody
The double effects of body, it is ensured that catalyst can stably be present in carrier duct to form heterogeneous catalyst.Use this
The problem of catalyst is separated and recycled with product can be solved by planting catalyst, meanwhile, using bidentate phosphite ester as co-catalysis
Agent can effectively improve the just different ratio in butyraldehyde product.The catalyst system can carry out the first of propylene in paste state bed reactor
Acylation reaction.
Specifically, the present invention provides a kind of new catalyst system and its slurry reactor of hydroformylation of propene producing butyladehyde
Technique, the catalyst system is thought highly of oneself the heterogeneous catalyst and bidentate phosphite ester of carried transition metal by organic ligand polymer
Co-catalyst is constituted, and wherein metal component is the one or more in metal Rh, Ir or Co, and organic ligand polymer is from phosphorous
(P) and alkenyl organic ligand monomer through hierarchical porous structure polymer formed by the polymerization of solvent thermal polymerization method, this is porous poly-
The heterogeneous catalyst of the self-supported such as Rh metals of compound, and using bidentate phosphite ester as co-catalyst, constitute new catalyst
System, the catalyst system is more suitable for slurry reactor technique, wherein it is preferred that slurry liquid uses propene hydroformylation reaction
Product butyraldehyde (mixture of hutanal and isobutylaldehyde and its dimer etc.).Gas-liquid-solid three-phase hydroformylation of propene and slurry bed system work
Skill effectively can be removed from reactor substantial amounts of reaction heat by the vaporization of butyraldehyde liquid.
Described metal component is the one or more in metal Rh, Ir or Co, described organic with hierarchical porous structure
Ligand polymer part polymerize the polymer to be formed from the organic ligand monomer containing P through solvent thermal polymerization method.With multi-stage porous
Organic ligand monomer of the structure organic ligand Polymeric ligands preferably containing P and containing alkenyl polymerize to be formed through solvent thermal polymerization method
Polymer, wherein particularly preferably the organophosphorus ligand monomer containing vinyl polymerize the polymer to be formed through solvent thermal polymerization method.
Metal component accounts for 0.02~5.0% in heterogeneous catalyst gross weight.Preferably, the organic ligand polymerization with hierarchical porous structure
The specific surface area of thing is 200~2000m2/ g, pore volume is 0.5~5.0cm3/ g, pore-size distribution is in 0.5~100.0nm.
Described hydroformylation reaction is carried out preferably in paste state bed reactor.Reaction may be carried out batchwise or continuously enter
OK.The representative condition of the hydroformylation reaction is：343~453K of reaction temperature；1.0~20.0MPa of reaction pressure.It is preferred that
The mol ratio of P in ground, the bidentate phosphite ester and the transition metal in the heterogeneous catalyst of carrying transition metal is 1：1~
30：1.The raw material of the propene hydroformylation reaction can be the mixture of pure propylene or propylene and alkane, it is preferable that with CO/
H2(preferred volume ratio is 1：1) mol ratio of gaseous mixture is 0.1：1~1：0.1.Preferably, pure propylene or propylene and alkane is mixed
Compound delivers into mixing preheater using high-pressure pump liquid, and liquid weight air speed is 0.01~10h-1, and CO/H2Mixed gas
Mixing preheater is passed directly into, after being sufficiently mixed with propylene, is dispersed into greatly through gas distributor from the bottom of paste state bed reactor
Enter paste state bed reactor after the micro-bubble of amount.When being reacted in paste state bed reactor, hydroformylation reaction is in solid catalyst
Upper to carry out, a part of butyraldehyde persistently flows out paste state bed reactor with tail gas, and butyraldehyde and gas production are isolated in gas-liquid separator
Thing, it is preferable that the temperature control of gas-liquid separator is at -18~40 DEG C.
The product butyraldehyde and slurry liquid (including bidentate phosphite ester co-catalyst) of another part generation pass through built-in filtering
Device outflow reactor by heterogeneous catalyst it is separated after, paste state bed reactor is persistently removed, at the beginning of butyraldehyde-bidentate phosphite ester
Divide tower, a part of butyraldehyde of flash separation, the bidentate phosphite ester butyraldehyde solution of part concentration is anti-through high-pressure pump blowback slurry bed system
Device is answered, a small circulation is achieved in that.Unreacted propylene tail gas after gas-liquid separator separates with fresh propylene feedstocks
Through recycle compressor compression and back paste state bed reactor after mixing, a big circulation is realized.Use the propylene hydrogen formyl of the present invention
The schematic flow sheet for changing the slurry reactor technique of the new catalyst system of producing butyladehyde is as shown in Figure 1.
Preferably, the phosphite ester auxiliary agent has following general structure：
Wherein, X is substituted or unsubstituted C6-C28Arylene or sub- heteroaryl perfume base；Y1、Y2、Z1And Z2Independently of one another
It is hydrogen, the tert-butyl group or methoxyl group；Each Q represents to be not present or direct bond independently of one another.
It is preferred that bidentate phosphite ester be：
Preferably, prepare above-mentioned L1 and use following compound A and B：
Prepare above-mentioned L2 and use following compound C and D：
In a kind of specific embodiment, the present invention in heterogeneous catalyst system prepare it is as follows：
Under 293-473K and inert gas such as nitrogen or argon gas protection atmosphere, to containing (the 4- vinyl benzenes of 10~1000g tri-
Base) Phosphine ligands monomer (its molecular structure is shown in Fig. 2) organic solvent in, add 1.0~100g radical initiator, stirring
0.5~100 hour.Wherein preferably, the organic solvent uses benzene, toluene, tetrahydrofuran, methanol, ethanol or chloroform,
Radical initiator uses cyclohexanone peroxide, dibenzoyl peroxide, TBHP, azodiisobutyronitrile or azo
Two different heptonitriles.
Then, under 293~473K and inert gas shielding atmosphere, by above-mentioned solution left standstill 10~100 hours.In room temperature
Under the conditions of vacuum extract solvent, that is, obtain the organic ligand Polymeric ligands with hierarchical porous structure.
Then, the above-mentioned organic ligand Polymeric ligands with hierarchical porous structure are put into having containing transition metal component
In machine solvent, stirred 0.5~100 hour under 293~473K and inert gas shielding atmosphere.Room temperature is down to after stirring,
Vacuum extracts solvent at ambient temperature, that is, obtains the heterogeneous catalyst of hydroformylation reaction.
Finally, above-mentioned bidentate phosphite ester co-catalyst such as L1 and L2 are mixed with novel heterogeneous catalytic agent obtained above
And constitute the catalyst system.
In order to better illustrate the preparation of novel catalyst system and its answering in propene hydroformylation reaction producing butyladehyde
With enumerating the preparation embodiment and its slurry reactor of some heterogeneous catalysts and bidentate phosphite ester co-catalyst sample below
The Application Example of technique, but the invention is not restricted to cited example.Unless otherwise expressly specified, it is use herein
" percentage " is based on weight.
In the following embodiments, used raw material is as follows：
H2/ CO gaseous mixtures (the H containing 50 volume %2, 50 volume % CO)：Middle Wu's Guangming Chemical Research And Design Institute is limited
Company
Propylene：Zhong Wu Guangming Chemical Research And Design Institutes Co., Ltd, the volume % of purity >=99.999.
Embodiment 1
In the case where 298K and nitrogen protective atmosphere enclose, 100.0 gram of three (4- vinyl benzenes) base Phosphine ligands monomer is dissolved in
1000.0ml tetrahydrofuran solvents, 10.0 grams of radical initiator azodiisobutyronitriles are added into above-mentioned solution, and stirring 2 is small
When.The solution being stirred is enclosed into lower standing 24h in 373K and nitrogen protective atmosphere.Solution after above-mentioned standing is cooled to room temperature,
Vacuum takes solvent away at ambient temperature, that is, obtains having as formed by three (4- vinyl benzenes) base phosphines polymerize through solvent-thermal method
The carrier of ligand polymer containing P of hierarchical porous structure.Three (4- vinyl benzenes) base Phosphine ligands polymer supports in the present embodiment gather
Close technology path as follows：
Here polymerization degree n each independent scope in 450-550.
The specific surface area and pore-size distribution of the sample are determined in Quantachrome Instruments companies
Carried out on Autosorb-1 Sorption Analyzers.Before test, sample is pre-processed 20 hours in 373K, and N is carried out in 77K liquid nitrogen temperatures2
Adsorption-desorption is tested.Measured specific surface area is 981m2/ g, pore volume is 1.45cm3/g。
Under 298K and nitrogen gas protection atmosphere, 2.505 grams of rhodium dicarbonyl acetylacetonate (I) is taken to be dissolved in 1000.0ml
In tetrahydrofuran solvent, being polymerize by three (4- vinyl benzenes) base phosphines through solvent-thermal method and forming tool for 50.0 grams of above-mentioned preparations is added
There is the carrier of ligand polymer containing P of hierarchical porous structure, stirring 24 is small in the case where 298K and nitrogen gas protect atmosphere by this mixture
When, then vacuum takes solvent away at ambient temperature, that is, obtains through solvent-thermal method polymerizeing and being formed and contain P with hierarchical porous structure
The self-supported metal Rh of ligand polymer heterogeneous catalyst.
The synthetic route of L1 bidentate phosphite esters is as follows：
2,2 '-xenol is added to excessive PCl3In, it is heated to reflux after 5 hours, vacuum distillation removes excessive
PCl3, obtain the compound A of white solid.Under the conditions of -20 DEG C, by compound B (6.9 grams, 20mmol) and triethylamine
The tetrahydrofuran solution of (28ml, 200mmol) is added drop-wise in the tetrahydrofuran solution of compound A (9.6 grams, 40mmol), is added dropwise
After the completion of be slowly ramped to room temperature, stir 24 hours, add acetonitrile and recrystallized, obtain bidentate phosphite ester co-catalyst
L1。
By mole of the transition metal ions in the P in bidentate phosphite ester and carrying transition metal ion heterogeneous catalyst
Than for 10：1 prepares the catalyst system being made up of above-mentioned heterogeneous catalyst and bidentate phosphite ester co-catalyst L1.
The self-supported heterogeneous catalyst of the carrier of the ligand polymer containing P with hierarchical porous structure of above-mentioned preparation is added to
In φ 25 (internal diameter) × 12000 paste state bed reactor, in 373K, 3.0MPa and H2(volume ratio is 1 to/CO：1) reaction mixture gas body
Product air speed 1000h-1It is 2.0h with propylene liguid weight space velocity-1Under conditions of start reaction.Reaction product butyraldehyde is collected in cold-trap
In collecting tank.Product liquid uses the HP-7890N gas chromatographic analysis equipped with HP-5 capillary columns and fid detector, using second
Alcohol makees internal standard.Reaction end gas uses the HP-7890N gas-chromatographies equipped with Porapak-QS posts and TCD detectors to be divided online
Analysis.Reaction result is shown in Table 1.
Embodiment 2
In addition to synthesizing bidentate phosphite ester co-catalyst L2 by following step, other processes are same as Example 1.
The synthetic route of L2 bidentate phosphite esters is as follows：
The tetrahydrofuran solution of compound B (71.6g, 20mmol) and triethylamine (280ml, 2mol) is added dropwise in ice-water bath
To PCl3In the tetrahydrofuran solution of (17ml, 200mmol), after being added dropwise to complete, backflow is slowly ramped to, stirring subtracts after 2 hours
Repoussage removes solvent, obtains compound C.Add and be added drop-wise at the toluene solution (500ml) of triethylamine (60ml, 400mmol), 0 DEG C
In the compound D (21.6g, 80mmol) of ice-water bath cooling and the toluene solution (1000ml) of triethylamine (6ml, 40mmol), shape
Into white precipitate.It is heated to 80 DEG C and is stirred overnight, crosses silicagel column and obtain bidentate phosphite ester co-catalyst L2 after purification.Reaction
It the results are shown in Table 1.
Embodiment 3
Except substituting rhodium dicarbonyl acetylacetonate (I) using 47.5 grams of acetylacetone,2,4-pentanedione iridium (III) in catalyst preparation, its
His process is same as Example 1.Reaction result is shown in Table 1.
Embodiment 4
Except used in catalyst preparation 125.0 grams of acetylacetone cobalts (II) substitute rhodium dicarbonyl acetylacetonates (I) with
And reaction pressure substitutes 3.0Mpa by 10.0Mpa, and reaction temperature is brought up to outside 453K, and other processes are same as Example 1.
Reaction result is shown in Table 1.
Embodiment 5
Except in hydroformylation reaction raw material by 85% propylene and low-carbon alkanes (propane 7.5% and butane 7.5%)
The pure propylene of mixture replacing simultaneously brings up to hydroformylation reaction pressure outside 5.0Mpa, and other processes are same as Example 1.Reaction
It the results are shown in Table 1.
Embodiment 6
Except feed gas volume air speed is by 10000h-1Substitute 1000h-1Outside, other processes are same as Example 1.Reaction knot
Fruit is shown in Table 1.
Embodiment 7
Except the batch autoclave using 10 liters substitutes the fixation bubbling bed reactor of successive reaction, unstripped gas is filled with
Keep in reactor that reaction pressure is constant after body, reaction pressure is 20.0MPa, and the reaction time is 10 hours outer, other processes with
Embodiment 4 is identical.Reaction result is shown in Table 1.
Comparative example 1
In addition to without any bidentate phosphite ester co-catalyst, other processes are same as Example 1.Reaction result is shown in
Table 1.
Table 1
As shown in Table 1, what what the present invention was provided be made up of heterogeneous catalyst and bidentate phosphite ester co-catalyst
The novel catalyst system and its slurry reactor of catalyst composition, it is adaptable to which propene hydroformylation reaction prepares butyraldehyde, are obtained
Higher butyraldehyde it is just different than (up to 42).Propene hydroformylation reaction performance is stable, and positive structure propionic aldehyde high income is solved existing
Either metal component is lost in present in technology or part is lost in, or catalyst is the problems such as be difficult to recycle and reuse, together
When, the slurry reactor can easily by the reaction heat of strongly exothermic hydroformylation of propene by the vaporization of butyraldehyde liquid from reaction
Removed in device.Therefore, with wide prospects for commercial application.
Above to the present invention have been described in detail, but the invention is not limited in specific embodiment party described herein
Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes can be made and deformed.This hair
Bright scope is defined by the following claims.
Claims (13)
1. a kind of catalyst system of hydroformylation of propene producing butyladehyde, it is characterised in that the catalyst system is by organic ligand
The heterogeneous catalyst of the conceited carried transition metal of polymer and the co-catalyst composition of bidentate phosphite ester, wherein the organic ligand
Polymer is that have hierarchical porous structure by what organic ligand monomer of the solvent thermal polymerization method polymerization containing phosphorus and vinyl was obtained
Organic ligand polymer, the transition metal is the one or more in Rh, Ir and Co, and wherein described organic ligand list
Phosphorus in body is connected directly to the aryl containing the vinyl in the organic ligand monomer by P-C keys, described organic
Ligand monomer is three (4- vinyl benzenes) base Phosphine ligands.
2. the catalyst system of hydroformylation of propene producing butyladehyde according to claim 1, it is characterised in that based on described many
The gross weight of phase catalyst, the content of the transition metal is 0.01~20.0%.
3. the catalyst system of hydroformylation of propene producing butyladehyde according to claim 1, it is characterised in that the bidentate is sub-
Phosphate has following structural formula：
Wherein, X is substituted or unsubstituted C6-C28Arylene or sub- heteroaryl perfume base；Y1、Y2、Z1And Z2Be independently of one another hydrogen,
The tert-butyl group or methoxyl group；Each Q represents to be not present or direct bond independently of one another.
4. the catalyst system of the hydroformylation of propene producing butyladehyde according to claim 1 or 3, it is characterised in that described double
Tooth phosphite ester is：
5. the catalyst system of the hydroformylation of propene producing butyladehyde according to claim 1 or 3, it is characterised in that described double
The mol ratio of P in tooth phosphite ester and the transition metal in the heterogeneous catalyst is 1:1~30:1.
6. a kind of method of hydroformylation of propene producing butyladehyde, it is characterised in that be filled with according to any one of claim 1-5 institutes
In the paste state bed reactor for the catalyst system stated, make the raw material containing propylene and CO and H2Gaseous mixture react.
7. the method for hydroformylation of propene producing butyladehyde according to claim 6, it is characterised in that the original containing propylene
Material is the mixture of pure propylene or propylene and alkane, the CO and H2Gaseous mixture in CO/H2Volume ratio is 1:1.
8. the method for hydroformylation of propene producing butyladehyde according to claim 7, it is characterised in that the original containing propylene
Material and the CO and H2Gaseous mixture mol ratio be 0.1:1~1:0.1.
9. the method for hydroformylation of propene producing butyladehyde according to claim 6, it is characterised in that the original containing propylene
Material high-pressure pump liquid enters mixing preheater and liquid weight air speed is 0.01~10h-1, and the CO and H2Gaseous mixture
After being passed directly into the mixing preheater and being sufficiently mixed with the raw material containing propylene, from the bottom of the paste state bed reactor
Portion enters back into paste state bed reactor after being dispersed into substantial amounts of micro-bubble through gas distributor and reacted.
10. the method for hydroformylation of propene producing butyladehyde according to claim 6, it is characterised in that the temperature of the reaction
For 343~453K, pressure is 1.0~20.0MPa.
11. the method for hydroformylation of propene producing butyladehyde according to claim 6, it is characterised in that methods described also includes
The step of separating butyraldehyde product, wherein flowing out the fraction butyraldehyde product of the paste state bed reactor through gas-liquid separator with tail gas
Separation, and after most of butyraldehyde product is separated by interior filtering with the heterogeneous catalyst, remove the paste state bed reactor.
12. the method for hydroformylation of propene producing butyladehyde according to claim 11, it is characterised in that remove the slurry bed system
Butyraldehyde is obtained by flash separation in the butyraldehyde product of reactor point tower at the beginning of butyraldehyde-bidentate phosphite ester, and remaining bidentate
Phosphite ester butyraldehyde solution carries out circular response through paste state bed reactor described in high-pressure pump blowback；And through the gas-liquid separator
Unreacted raw material tail gas after separation is anti-through slurry bed system described in recycle compressor compression and back after being mixed with the fresh raw material
Answer and circular response is carried out in device.
13. the method for hydroformylation of propene producing butyladehyde according to claim 12, it is characterised in that through the gas-liquid separation
Enter de- light essence after the isolated butyraldehyde of device and the butyraldehyde mixing obtained through at the beginning of the butyraldehyde-bidentate phosphite ester points of tower flash distillation
Knockout tower is evaporated, enters de- weight knockout tower from the bottom stream for taking off light rectifying knockout tower, and from the de- heavy knockout tower
Tower top obtain pure butyraldehyde product.
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| CN106140301B (en) * | 2015-04-03 | 2018-11-27 | 中国科学院大连化学物理研究所 | Containing organic mixed polymers-metal heterogeneous catalyst of phosphine and its preparation method and application |
| CN112898139B (en) * | 2019-12-03 | 2022-10-04 | 中国科学院大连化学物理研究所 | Method for preparing n-valeraldehyde from Raffinate II |
| CN112898138B (en) * | 2019-12-03 | 2022-09-27 | 中国科学院大连化学物理研究所 | High-value utilization method of Fischer-Tropsch product |
| 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 |
| CN115722267B (en) * | 2021-08-25 | 2024-02-02 | 万华化学集团股份有限公司 | Hydroformylation catalyst and method for preparing aldehyde by catalyzing propylene hydroformylation reaction by using same |
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| JP2000159720A (en) * | 1998-12-02 | 2000-06-13 | Mitsubishi Chemicals Corp | Production of aldehyde |
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