CN104667977A - Catalyst system for preparing butyraldehyde by propylene hydroformylation and use method of catalyst system - Google Patents
Catalyst system for preparing butyraldehyde by propylene hydroformylation and use method of catalyst system Download PDFInfo
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Abstract
The invention provides a catalyst system for preparing butyraldehyde by propylene hydroformylation and a use method of the catalyst system. The catalyst system is characterized by consisting of a multi-phase catalyst of an organic-ligand polymer self-loading transition metal and a cocatalyst of bidentate phosphate, wherein the organic-ligand polymer is of a hierarchical pore structure and is obtained by polymerizing an organic ligand monomer containing phosphorus and vinyl by virtue of a solvent thermal polymerization method, and the transition metal is one or more than one of Rh, Ir and Co. The invention also provides a method for preparing butyraldehyde by the reaction of a raw material containing propylene and a gas mixture of CO and H2 in a slurry bed reactor filled with the catalyst system. The novel catalyst system is simple in preparation method, reaction technology and device, is stable in performance when being applied to propylene hydroformylation, is high in activity, good in selectivity, is especially high in n-butanal selectivity, achieves multiphase hydroformylation reaction, and has wide industrial application prospect.
Description
Technical field
The present invention relates to a kind of novel catalyst system of hydroformylation of propene producing butyladehyde and use this catalyst system to carry out the method for hydroformylation of propene producing butyladehyde.
Technical background
Butyraldehyde (Chemical Reviews, 2012,112,5675-5732) is the intermediate producing the important Organic Chemicals such as octyl alconyl, is also the important source material of producing various fine chemical product.Butyraldehyde has hutanal and these two kinds of isomers of isobutylaldehyde, hutanal mainly for the production of n-butanol and 2-Ethylhexyl Alcohol, also for the production of the fine chemical product such as trimethylolpropane, polyvinyl butyral resin; Isobutylaldehyde is mainly for the production of isobutanol, neopentyl glycol, condensation and esterification products 2,2,4-TMPD, isobutyric acid, isobutyronitrile etc.The production method of butyraldehyde mainly contains three kinds: acetaldehyde condensation method, oxo synthesis (i.e. hydroformylation method) and n-butanol dehydriding.At present, the technology path overwhelming majority of industrial production butyraldehyde adopts hydroformylation method.
With butyraldehyde produce octyl alconyl (European Journal of Organic Chemistry, 2012,6309-6320) be important basic organic chemical industry raw material.Emulsion paint can be used separately as by the various ethers of production of butanol and aminated compounds, fabric processes adhesive, agricultural chemicals and rubber processing and leather treatment etc.Butanols is the raw material producing the organic compounds such as butyraldehyde, butyric acid, butylamine and acetic acid fourth vinegar.Octanol is mainly for the manufacture of the pungent vinegar of phthalic acid two (DOP).DOP product have the title of trump plasticizer, is a kind of inexpensive desirable plasticizer, is widely used in the processing etc. of polyvinyl chloride, synthetic rubber and resin.Due to important use and the huge demand of chemicals butyraldehyde, therefore hydroformylation of propene produces butyraldehyde, produces the field that octyl alconyl becomes researchers' extensive concern and research further.
Low pressure Rh method homogeneous catalysis system is adopted to be the most widely used hydroformylation of propene production technology in the world today.Abroad improved this technical study, development forms the proprietary technology had their own characteristics each.
Mitsubishi changes into the Rh method low pressure carbonylic synthesis technology of exploitation.This technology adopts toluene to make the solvent of Rh catalyst, have viscosity low, conduct heat, catalyst activity is high, product quality is high, rhodium entrainment loss is little, catalyst activity reduction slowly and reactor production efficiency high.Device is inner with catalyst recovery system, adopts crystallization and centrifugal filtration from dead catalyst, reclaim organophosphorus ligand and Rh complex compound.Regularly send catalyst manufactory to reclaim Rh after not recoverable useless Rh catalyst concentration, prepare raw catelyst and return factory and re-use, although this kind of technology has higher reactivity, owing to being homogeneous reaction, inevitably metal loss problem.
Rh catalyst is expensive, and for reducing its loss, Rule chemistry eighties (chemical science and technology market, 2005,28,1-8) develops a kind of two-phase technique, makes ligand carry out modification to Rh catalyst with a triphenylphosphine three-sulfonate.This catalyst has the advantages that catalyst is easily separated with product, product is just high with isomer ratios, and uses water as solvent, both cheaply, safety, be conducive to environmental protection again.This technology is also applicable to the production of long-chain olefin.Be provided with catalyst preparing and useless Rh catalyst recovery operation in process unit, therefore useless Rh catalyst does not need to send outside battery limit (BL), can reclaim use in this device.But this technique also has weak point, mainly because olefin feedstock solubility in aqueous medium than in organic phase is low, so rate of catalysis reaction decreases.Meanwhile, because this reaction is heterogeneous, so catalyst activity is quite low, operating pressure and the temperature of water-soluble catalyst technique are higher, and Rh content is higher.
The industrialization technology of current hydroformylation of propene still mainly uses homogeneous catalysis system; how to develop a kind of novel heterogeneous catalyst and Industrialized processing technique; make its high activity both with homogeneous reaction and selective; have again heterogeneous reaction concurrently to be easy to be separated the advantage that can reuse, become the main target of this area research.
Summary of the invention
For the deficiencies in the prior art, the object of the present invention is to provide new catalyst system and the slurry reactor technique thereof of the hydroformylation of propene producing butyladehyde of a kind of high activity that can industrially easily realize and high selectivity.
For this reason; on the one hand; the invention provides a kind of catalyst system of hydroformylation of propene producing butyladehyde; it is characterized in that; described catalyst system is made up of from the heterogeneous catalyst of carrying transition metal and the co-catalyst of bidentate phosphite ester organic ligand polymer; wherein said organic ligand polymer is the organic ligand polymer with hierarchical porous structure that the organic ligand monomer containing phosphorus P and thiazolinyl by the polymerization of solvent thermal polymerization method obtains, and described transition metal is one or more in Rh, Ir and Co.
In a preferred embodiment, based on the gross weight of described heterogeneous catalyst, the content of described transition metal is 0.01 ~ 20.0%.
In a preferred embodiment, described organic ligand polymer is the organic ligand polymer with hierarchical porous structure that the organic ligand monomer containing phosphorus P and vinyl by the polymerization of solvent thermal polymerization method obtains.
In a preferred embodiment, described bidentate phosphite ester has following structural formula:
Wherein, X is substituted or unsubstituted C
6-C
28arylene or sub-assorted aromatic radical; Y
1, Y
2, Z
1and Z
2hydrogen, the tert-butyl group or methoxyl group independently of one another; Each Q represents not exist or direct bond independently of one another.
In a preferred embodiment, described bidentate phosphite ester is:
In a preferred embodiment, the mol ratio of the P in described bidentate phosphite ester and the transition metal in described heterogeneous catalyst is 1:1 ~ 30:1.
On the other hand, the invention provides a kind of method of hydroformylation of propene producing butyladehyde, it is characterized in that, in the paste state bed reactor being filled with above-mentioned catalyst system, make the raw material containing propylene and CO and H
2gaseous mixture react.
In a preferred embodiment, the described pure propylene of raw material or the mixture of propylene and alkane containing propylene, described CO and H
2gaseous mixture in CO/H
2volume ratio is 1:1.
In a preferred embodiment, described raw material containing propylene and described CO and H
2the mol ratio of gaseous mixture be 0.1:1 ~ 1:0.1.
In a preferred embodiment, the described raw material high-pressure pump liquid state containing propylene enters mixing preheater and liquid weight air speed is 0.01 ~ 10h
-1, and described CO and H
2gaseous mixture directly pass into described mixing preheater and after fully mixing with the described raw material containing propylene, be dispersed into enter paste state bed reactor again after a large amount of micro-bubbles through gas distributor from the bottom of described paste state bed reactor and react.
In a preferred embodiment, the temperature of described reaction is 343 ~ 453K, and pressure is 1.0 ~ 20.0MPa.
In a preferred embodiment, described method also comprises the step being separated butyraldehyde product, wherein flow out the fraction butyraldehyde product of described paste state bed reactor through gas-liquid separator separates with tail gas, and after most of butyraldehyde product is separated with described heterogeneous catalyst by inner filtration, shift out described paste state bed reactor.Preferably, the butyraldehyde product shifting out described paste state bed reactor just divides in tower at butyraldehyde-bidentate phosphite ester and obtains butyraldehyde by flash separation, and remaining bidentate phosphite ester butyraldehyde solution carries out circular response through paste state bed reactor described in high-pressure pump blowback; And in paste state bed reactor described in recycle compressor compression and back, carry out circular response after the unreacted raw material tail gas after described gas-liquid separator separates mixes with fresh described raw material.Preferably, de-light rectifying knockout tower is entered after the butyraldehyde obtained through described gas-liquid separator separates and the butyraldehyde mixing just dividing tower flash distillation to obtain through described butyraldehyde-bidentate phosphite ester, enter de-heavy knockout tower from the bottom stream of described de-light rectifying knockout tower, and obtain pure butyraldehyde product from the tower top of described de-heavy knockout tower.
The beneficial effect that the present invention produces includes but not limited to following: compared with existing hydroformylation reaction technology, the present invention due to have employed novel heterogeneous catalytic agent and bidentate phosphite ester co-catalyst composition catalyst system, so slurry reactor technique and device simple; Catalyst separation adopts such as built-in filter, is separated simple.Bidentate phosphite ester co-catalyst reclaims easily; Method for preparing catalyst is simple, the hydroformylation stable performance of catalyst, and yield is high; solve exist in prior art or metal component run off; or part runs off, or catalyst is difficult to the problems such as recycle and reuse, has wide prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is a kind of slurry bed system propene hydroformylation reaction flow chart of described novel catalyst system used according to the invention.
Fig. 2 is the structural representation of three (4-vinyl benzene) base Phosphine ligands monomer.
Detailed description of the invention
The present invention adopts a kind of novel catalyst system be made up of from the heterogeneous catalyst of carrying transition metal and the co-catalyst of bidentate phosphite ester ligand organic ligand polymer; and supporting slurry reactor new technology with it; can realize the slurry reactor technique of high activity and highly selective hydroformylation of propene producing butyladehyde, this heterogeneous catalyst is by transition metal component and have hierarchical porous structure organic ligand polymer and form.Hierarchical porous structure organic ligand polymer support has the double effects of carrier and part, guarantees that catalyst stably can be present in carrier duct thus to define heterogeneous catalyst.Using the problem that this catalyst can solve catalyst and product separation and recycle, meanwhile, take bidentate phosphite ester as the just different ratio that co-catalyst effectively can improve in butyraldehyde product.This catalyst system can carry out the formylation reaction of propylene in paste state bed reactor.
Specifically, the invention provides a kind of new catalyst system and slurry reactor technique thereof of hydroformylation of propene producing butyladehyde, described catalyst system is made up of from the heterogeneous catalyst of carrying transition metal and the co-catalyst of bidentate phosphite ester organic ligand polymer, wherein metal component is metal Rh, one or more in Ir or Co, the hierarchical porous structure polymer that organic ligand polymer selects the organic ligand monomer of phosphorous (P) and thiazolinyl to be formed through the polymerization of solvent thermal polymerization method, this porous polymer is from the heterogeneous catalyst of load as Rh metal, and be co-catalyst with bidentate phosphite ester, constitute novel catalyst system, this catalyst system is comparatively suitable for slurry reactor technique, wherein preferably slurry liquid adopts propene hydroformylation reaction product butyraldehyde (mixture of hutanal and isobutylaldehyde and dimer etc. thereof).The vaporization of a large amount of reaction heat by butyraldehyde liquid can be shifted out by gas-liquid-solid three-phase hydroformylation of propene and slurry bed system technique effectively from reactor.
Described metal component is one or more in metal Rh, Ir or Co, described in there is hierarchical porous structure the organic ligand Polymeric ligands polymer of selecting the organic ligand monomer containing P to be formed through the polymerization of solvent thermal polymerization method.There is the polymer that the organic ligand monomer of hierarchical porous structure organic ligand Polymeric ligands preferably containing P and containing thiazolinyl is formed through the polymerization of solvent thermal polymerization method, wherein particularly preferably containing the polymer that the organophosphorus ligand monomer of vinyl is formed through the polymerization of solvent thermal polymerization method.Metal component accounts for 0.02 ~ 5.0% in heterogeneous catalyst gross weight.Preferably, the specific area with the organic ligand polymer of hierarchical porous structure is 200 ~ 2000m
2/ g, pore volume is 0.5 ~ 5.0cm
3/ g, pore-size distribution is at 0.5 ~ 100.0nm.
Described hydroformylation reaction preferably carries out in paste state bed reactor.Reaction may be carried out batchwise or carry out continuously.The representative condition of described hydroformylation reaction is: reaction temperature 343 ~ 453K; Reaction pressure 1.0 ~ 20.0MPa.Preferably, the mol ratio of the transition metal in the P in described bidentate phosphite ester and the heterogeneous catalyst of carrying transition metal is 1:1 ~ 30:1.The raw material of described propene hydroformylation reaction can be the mixture of pure propylene or propylene and alkane, preferably, with CO/H
2the mol ratio of (preferred volume ratio is 1:1) gaseous mixture is 0.1:1 ~ 1:0.1.Preferably, pure propylene or propylene adopt high-pressure pump liquid state to deliver into the mixture of alkane to mix preheater, and liquid weight air speed is 0.01 ~ 10h
-1, and CO/H
2mist directly passes into mixing preheater, after fully mixing, is dispersed into after a large amount of micro-bubbles enters paste state bed reactor from the bottom of paste state bed reactor through gas distributor with propylene.When reacting in paste state bed reactor; hydroformylation reaction carries out on solid catalyst, and a part of butyraldehyde continues to flow out paste state bed reactor with tail gas, isolates butyraldehyde and gaseous product in gas-liquid separator; preferably, the temperature of gas-liquid separator controls at-18 ~ 40 DEG C.
After heterogeneous catalyst is separated with it by built-in filter outflow reactor with slurry liquid (comprising bidentate phosphite ester co-catalyst) by the product butyraldehyde that another part generates, continue to shift out paste state bed reactor, just tower is divided at butyraldehyde-bidentate phosphite ester, flash separation part butyraldehyde, the concentrated bidentate phosphite ester butyraldehyde solution of a part, through high-pressure pump blowback paste state bed reactor, realizes a little circulation like this.Through recycle compressor compression and back paste state bed reactor after unreacted propylene tail gas mixes with fresh propylene feedstocks after gas-liquid separator separates, realize a large circulation.Use the schematic flow sheet of the slurry reactor technique of the new catalyst system of hydroformylation of propene producing butyladehyde of the present invention as shown in Figure 1.
Preferably, described phosphite ester auxiliary agent has following general structure:
Wherein, X is substituted or unsubstituted C
6-C
28arylene or sub-assorted aromatic radical; Y
1, Y
2, Z
1and Z
2hydrogen, the tert-butyl group or methoxyl group independently of one another; Each Q represents not exist or direct bond independently of one another.
Preferred bidentate phosphite ester is:
Preferably, prepare above-mentioned L1 and use following compd A and B:
Prepare above-mentioned L2 and use following Compound C and D:
In a kind of specific embodiments, being prepared as follows of the heterogeneous catalyst system in the present invention:
At 293-473K and inert gas as under nitrogen or argon shield atmosphere; to in the organic solvent containing 10 ~ 1000g tri-(4-ethenylphenyl) Phosphine ligands monomer (its molecular structure is shown in Fig. 2); add the radical initiator of 1.0 ~ 100g, stir 0.5 ~ 100 hour.Wherein preferably, described organic solvent adopts benzene, toluene, oxolane, methyl alcohol, ethanol or chloroform, and radical initiator adopts cyclohexanone peroxide, dibenzoyl peroxide, TBHP, azodiisobutyronitrile or ABVN.
Then, under 293 ~ 473K and inert gas shielding atmosphere, by above-mentioned solution left standstill 10 ~ 100 hours.Vacuum extracts solvent at ambient temperature, namely obtains the organic ligand Polymeric ligands with hierarchical porous structure.
Then, the above-mentioned organic ligand Polymeric ligands with hierarchical porous structure is dropped in the organic solvent containing transition metal component, stirs 0.5 ~ 100 hour under 293 ~ 473K and inert gas shielding atmosphere.Be down to room temperature after stirring, vacuum extracts solvent at ambient temperature, namely obtains the heterogeneous catalyst of hydroformylation reaction.
Finally, above-mentioned bidentate phosphite ester co-catalyst is mixed with above-mentioned obtained novel heterogeneous catalytic agent as L1 and L2 and catalyst system as described in forming.
In order to the preparation of novel catalyst system and the application in propene hydroformylation reaction producing butyladehyde thereof are better described; enumerate the preparation embodiment of some heterogeneous catalysts and bidentate phosphite ester co-catalyst sample and the Application Example of slurry reactor technique thereof below, but the invention is not restricted to cited example.Unless otherwise expressly specified, " percentage " used in the application is based on weight.
In the following embodiments, the raw material used is as follows:
H
2/ CO gaseous mixture (the H containing 50 volume %
2, 50 volume % CO): Zhong Wu Guangming Chemical Research And Design Institute Co., Ltd
Propylene: Zhong Wu Guangming Chemical Research And Design Institute Co., Ltd, purity >=99.999 volume %.
Embodiment 1
Under 298K and nitrogen protection atmosphere, 100.0 gram of three (4-vinyl benzene) base Phosphine ligands monomer is dissolved in 1000.0ml tetrahydrofuran solvent, in above-mentioned solution, adds 10.0 grams of radical initiator azodiisobutyronitriles, stir 2 hours.The solution be stirred is left standstill 24h under 373K and nitrogen protection atmosphere.By above-mentioned leave standstill after solution be cooled to room temperature, vacuum takes solvent away at ambient temperature, namely obtain by three (4-vinyl benzene) base phosphine through solvent-thermal method be polymerized and is formed have hierarchical porous structure contain P ligand polymer carrier.In the present embodiment three (4-vinyl benzene) base Phosphine ligands polymer support polymerization technique route is as follows:
Here polymerization degree n separately independently scope at 450-550.
The Autosorb-1 Sorption Analyzer that the specific area of this sample and pore-size distribution are determined at Quantachrome Instruments company carries out.Before test, sample, 373K pretreatment 20 hours, carries out N in 77K liquid nitrogen temperature
2adsorption-desorption is tested.Measured specific area is 981m
2/ g, pore volume is 1.45cm
3/ g.
Under 298K and nitrogen gas protection atmosphere, the rhodium dicarbonyl acetylacetonate (I) getting 2.505 grams is dissolved in 1000.0ml tetrahydrofuran solvent, add 50.0 grams of above-mentioned preparations by three (4-vinyl benzene) base phosphine through solvent-thermal method be polymerized and is formed have hierarchical porous structure contain P ligand polymer carrier, this mixture is stirred 24 hours under 298K and nitrogen gas protection atmosphere, then vacuum takes solvent away at ambient temperature, namely obtain being formed through solvent-thermal method polymerization have hierarchical porous structure containing P ligand polymer from the heterogeneous catalyst of the metal Rh of load.
The synthetic route of L1 bidentate phosphite ester is as follows:
2,2 '-xenol is joined excessive PCl
3in, add hot reflux after 5 hours, decompression distillation removes excessive PCl
3, obtain the compd A of white solid.Under-20 DEG C of conditions, by compd B (6.9 grams, 20mmol) with triethylamine (28ml, tetrahydrofuran solution 200mmol) is added drop-wise to compd A (9.6 grams, in tetrahydrofuran solution 40mmol), after being added dropwise to complete, be slowly warming up to room temperature, stir 24 hours, add acetonitrile to be recrystallized, obtain bidentate phosphite ester co-catalyst L1.
Be that 10:1 prepares the catalyst system be made up of above-mentioned heterogeneous catalyst and bidentate phosphite ester co-catalyst L1 by the mol ratio of the transition metal ions in the P in bidentate phosphite ester and carrying transition metal ion heterogeneous catalyst.
The P ligand polymer carrier that contains with hierarchical porous structure of above-mentioned preparation is joined in the paste state bed reactor of φ 25 (internal diameter) × 12000, at 373K, 3.0MPa and H from the heterogeneous catalyst of load
2/ CO (volume ratio is 1:1) reaction mixture gas volume space velocity 1000h
-1be 2.0h with propylene liguid weight space velocity
-1condition under start reaction.Product butyraldehyde is collected in cold-trap collecting tank.Product liquid uses the HP-7890N gas chromatographic analysis of being furnished with HP-5 capillary column and fid detector, adopts ethanol to make interior mark.Reaction end gas uses the HP-7890N gas-chromatography of being furnished with Porapak-QS post and TCD detector to carry out on-line analysis.Reaction result is in table 1.
Embodiment 2
Except synthesizing except bidentate phosphite ester co-catalyst L2 by step below, other process is identical with embodiment 1.
The synthetic route of L2 bidentate phosphite ester is as follows:
In ice-water bath, the tetrahydrofuran solution of compd B (71.6g, 20mmol) and triethylamine (280ml, 2mol) is added drop-wise to PCl
3in the tetrahydrofuran solution of (17ml, 200mmol), after being added dropwise to complete, be slowly warming up to backflow, stir decompression after 2 hours and divide exactly solvent, obtain Compound C.Add triethylamine (60ml, toluene solution (500ml) 400mmol), Compound D (the 21.6g of ice-water bath cooling is added drop-wise at 0 DEG C, 80mmol) with triethylamine (6ml, in toluene solution (1000ml) 40mmol), form white precipitate.Be heated to 80 DEG C and stir and spend the night, after crossing silica column purification, obtain bidentate phosphite ester co-catalyst L2.Reaction result is in table 1.
Embodiment 3
Except adopting 47.5 grams of acetylacetone,2,4-pentanedione iridium (III) to substitute rhodium dicarbonyl acetylacetonate (I) in catalyst preparing, other processes are identical with embodiment 1.Reaction result is in table 1.
Embodiment 4
3.0Mpa is substituted by 10.0Mpa except adopting the alternative rhodium dicarbonyl acetylacetonate (I) of 125.0 grams of acetylacetone cobalts (II) and reaction pressure in catalyst preparing, and reaction temperature is brought up to outside 453K, other processes are identical with embodiment 1.Reaction result is in table 1.
Embodiment 5
Except bringing up to 5.0Mpa except by hydroformylation reaction pressure at hydroformylation reaction Raw by the pure propylene of mixture replacing of 85% propylene and low-carbon alkanes (propane 7.5% and butane 7.5%), other processes are identical with embodiment 1.Reaction result is in table 1.
Embodiment 6
Except feed gas volume air speed is by 10000h
-1substitute 1000h
-1outward, other processes are identical with embodiment 1.Reaction result is in table 1.
Embodiment 7
Except the fixing bubbling bed reactor adopting the batch autoclave of 10 liters to substitute successive reaction, keep reaction pressure in reactor constant after being filled with unstrpped gas, reaction pressure is 20.0MPa, and the reaction time is outside 10 hours, and other processes are identical with embodiment 4.Reaction result is in table 1.
Comparative example 1
Except not adding any bidentate phosphite ester co-catalyst, other processes are identical with embodiment 1.Reaction result is in table 1.
Table 1
As shown in Table 1; the novel catalyst system that the catalyst be made up of heterogeneous catalyst and bidentate phosphite ester co-catalyst provided by the invention forms and slurry reactor thereof; be applicable to propene hydroformylation reaction and prepare butyraldehyde, what obtain higher butyraldehyde is just different from (can up to 42).Propene hydroformylation reaction stable performance; positive structure propionic aldehyde yield is high; solve exist in prior art or metal component run off; or part runs off; or catalyst is difficult to the problems such as recycle and reuse; meanwhile, the vaporization of the reaction heat of the hydroformylation of propene of strong heat release by butyraldehyde liquid can easily be shifted out by this slurry reactor from reactor.Therefore, there is wide prospects for commercial application.
Below to invention has been detailed description, but the present invention is not limited to detailed description of the invention described herein.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 and distortion can be made.Scope of the present invention is defined by the following claims.
Claims (14)
1. the catalyst system of a hydroformylation of propene producing butyladehyde; it is characterized in that; described catalyst system is made up of from the heterogeneous catalyst of carrying transition metal and the co-catalyst of bidentate phosphite ester organic ligand polymer; wherein said organic ligand polymer is the organic ligand polymer with hierarchical porous structure that the organic ligand monomer containing phosphorus and vinyl by the polymerization of solvent thermal polymerization method obtains, and described transition metal is one or more in Rh, Ir and Co.
2. the catalyst system of hydroformylation of propene producing butyladehyde according to claim 1, is characterized in that, based on the gross weight of described heterogeneous catalyst, the content of described transition metal is 0.01 ~ 20.0%.
3. the catalyst system of hydroformylation of propene producing butyladehyde according to claim 1; it is characterized in that, described organic ligand polymer is the organic ligand polymer with hierarchical porous structure that the organic ligand monomer containing phosphorus P and vinyl by the polymerization of solvent thermal polymerization method obtains.
4. the catalyst system of hydroformylation of propene producing butyladehyde according to claim 1, is characterized in that, described bidentate phosphite ester has following structural formula:
Wherein, X is substituted or unsubstituted C
6-C
28arylene or sub-assorted aromatic radical; Y
1, Y
2, Z
1and Z
2hydrogen, the tert-butyl group or methoxyl group independently of one another; Each Q represents not exist or direct bond independently of one another.
5. the catalyst system of the hydroformylation of propene producing butyladehyde according to claim 1 or 4, is characterized in that, described bidentate phosphite ester is:
6. the catalyst system of the hydroformylation of propene producing butyladehyde according to claim 1,4 or 5, is characterized in that, the mol ratio of the transition metal in the P in described bidentate phosphite ester and described heterogeneous catalyst is 1:1 ~ 30:1.
7. a method for hydroformylation of propene producing butyladehyde, is characterized in that, is being filled with in the paste state bed reactor according to the catalyst system described in claim 1-6, is making the raw material containing propylene and CO and H
2gaseous mixture react.
8. the method for hydroformylation of propene producing butyladehyde according to claim 7, is characterized in that, the described pure propylene of raw material or the mixture of propylene and alkane containing propylene, described CO and H
2gaseous mixture in CO/H
2volume ratio is 1:1.
9. the method for hydroformylation of propene producing butyladehyde according to claim 8, is characterized in that, described raw material containing propylene and described CO and H
2the mol ratio of gaseous mixture be 0.1:1 ~ 1:0.1.
10. the method for hydroformylation of propene producing butyladehyde according to claim 7, is characterized in that, the described raw material high-pressure pump liquid state containing propylene enters mixing preheater and liquid weight air speed is 0.01 ~ 10h
-1, and described CO and H
2gaseous mixture directly pass into described mixing preheater and after fully mixing with the described raw material containing propylene, be dispersed into enter paste state bed reactor again after a large amount of micro-bubbles through gas distributor from the bottom of described paste state bed reactor and react.
The method of 11. hydroformylation of propene producing butyladehydes according to claim 7, is characterized in that, the temperature of described reaction is 343 ~ 453K, and pressure is 1.0 ~ 20.0MPa.
The method of 12. hydroformylation of propene producing butyladehydes according to claim 7; it is characterized in that; described method also comprises the step being separated butyraldehyde product; wherein flow out the fraction butyraldehyde product of described paste state bed reactor through gas-liquid separator separates with tail gas; and after most of butyraldehyde product is separated with described heterogeneous catalyst by inner filtration, shift out described paste state bed reactor.
The method of 13. hydroformylation of propene producing butyladehydes according to claim 12, it is characterized in that, the butyraldehyde product shifting out described paste state bed reactor just divides in tower at butyraldehyde-bidentate phosphite ester and obtains butyraldehyde by flash separation, and remaining bidentate phosphite ester butyraldehyde solution carries out circular response through paste state bed reactor described in high-pressure pump blowback; And in paste state bed reactor described in recycle compressor compression and back, carry out circular response after the unreacted raw material tail gas after described gas-liquid separator separates mixes with fresh described raw material.
The method of 14. hydroformylation of propene producing butyladehydes according to claim 12; it is characterized in that; de-light rectifying knockout tower is entered after the butyraldehyde obtained through described gas-liquid separator separates and the butyraldehyde mixing just dividing tower flash distillation to obtain through described butyraldehyde-bidentate phosphite ester; enter de-heavy knockout tower from the bottom stream of described de-light rectifying knockout tower, and obtain pure butyraldehyde product from the tower top of described de-heavy knockout tower.
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| WO2016155338A1 (en) * | 2015-04-03 | 2016-10-06 | 中国科学院大连化学物理研究所 | Method for preparing butyraldehyde by means of propylene hydroformylation |
| 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 |
| CN112898139A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing n-valeraldehyde from Raffinate II |
| CN112898138A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | High-value utilization method of Fischer-Tropsch product |
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| CN112898139A (en) * | 2019-12-03 | 2021-06-04 | 中国科学院大连化学物理研究所 | Method for preparing n-valeraldehyde from Raffinate II |
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