CN100526279C - Process of continuously preparing n-pentanal - Google Patents
Process of continuously preparing n-pentanal Download PDFInfo
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- CN100526279C CN100526279C CNB2006100426550A CN200610042655A CN100526279C CN 100526279 C CN100526279 C CN 100526279C CN B2006100426550 A CNB2006100426550 A CN B2006100426550A CN 200610042655 A CN200610042655 A CN 200610042655A CN 100526279 C CN100526279 C CN 100526279C
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Abstract
The invention discloses a process for continually preparing valeraldehyde, which reacts 1-butene raw material continually containing a little of trans/cis-2-butene, isobutene, butane with synthesis gas in the presence of the organic phosphinerhodium catalyst and triphenylphosphine. The process of the invention includes a reaction region, separation region and an activation region. Butene hydroformylation reaction liquid is evaporated, condensed and separated to two streams of raw product and circulating catalyst solution by film evaporation equipment, under shielding gas atmosphere of synthesis gas, and activated circulating catalyst solution enters reactor again. The present invention activates rhodium catalyst by catalyst activator, and controls or reduces acetal high boiling point byproducts which are generated by aldehyde polycondensation, enhance catalyst activity and regioselectivity of aldehyde. The film evaporation equipment used in the present invention is more effective than flash evaporator to separate catalyst solution and valeraldehyde producers in reaction liquor. Appropriate operational condition of film evaporation equipment can reduce or not generate aldehyde condensation, protive rhodium catalyst, enhance catalyst activity and prolong usage time of catalyst.
Description
Technical field
The present invention relates to a kind of process of hydroformylation of olefin system valeraldehyde.Or rather, the present invention relates to a kind of butene hydroformylation reaction technological process of preparation valeraldehyde continuously.
Background technology
Butene hydroformylation prepared in reaction valeraldehyde has important economic implications.Valeraldehyde is important organic synthesis intermediate, is widely used in industries such as spices, medicine, agricultural chemicals, coating, ore dressing.The 2-propyl enanthol that valeral condensation, hydrogenation reaction are produced is the current good PVC softening agent raw material of manufacturing of developing both at home and abroad.
For a long time, the reaction process to butene hydroformylation system valeral has many researchs in the global range.The industrial production of early stage butene hydroformylation prepared in reaction valeraldehyde adopts cobalt catalyst.The product valeraldehyde is about 3: 1 to 4: 1 with the ratio of isovaleric aldehyde.Reaction needs to carry out the product separation difficulty under High Temperature High Pressure.And under cobalt carbonyl catalyst catalyzing butene hydroformylation reaction condition, when containing iso-butylene in the C 4 olefin raw material, iso-butylene can generate resin makes reaction complicated.
Last century the seventies, modification rhodium catalyst catalyzing propone hydroformylation reaction production aldehyde and alcohol realization industrialization.The atom coefficient ratio cobalt height of rhodium, atomic volume is big, easily forms the compound of high ligancy, so catalyst activity is than cobalt carbonyl catalyst height.Patent US 3,527, and 809 reports are compared with cobalt carbonyl catalyst, and hydroformylation of olefin is when the triphenylphosphine rhodium carbonyl catalyst, and temperature of reaction needs only 50～100 ℃, and reaction pressure is lower than 3.2MPa.
The homogeneous reaction catalyzer is dissolved in the reaction solvent equably, causes and the product separation difficulty.German patent DE 2,627,354 propose profit phase catalyst system, and catalyzer is soluble in the aqueous phase, and reaction product is in organic phase, objectionable intermingling.Being reflected at water oil two-phase interface carries out.Reaction back water oil two-phase standing demix, product and catalyzer are easily separated.Avoid fractionation by distillation to cause the condensation of hydroformylation of olefin product aldehyde to generate high boiling by product, also avoided the rhodium catalyst of thermo-sensitivity to decompose and inactivation.
Yet, along with olefin carbon number increases, water-soluble variation, the water-soluble rhodium hydroformylation reaction needs harsh more processing condition, increases production cost.For example, U.S. Pat 5,463,147 and 5,410,072 has reported the process of the synthetic valeral of butene hydroformylation reaction in the presence of the water-soluble rhodium catalyzer.The butene hydroformylation reaction needed divides two sections to carry out; first section with water-soluble rhodium catalyst catalyzing butene hydroformylation reaction under 70～150 ℃, 0.4～5.0MPa reaction conditions, second section in the presence of cobalt carbonyl catalyst under 130～180 ℃, 8～30MPa reaction conditions the catalyzing butene hydroformylation reaction.In addition, the PEP report (Process Economics Program 21D) that U.S. SRI consulting firm delivers is analyzed, and propene hydroformylation reaction prepares butyraldehyde-n, adopts the water-soluble rhodium catalyzer than oil soluble triphenylphosphine rhodium carbonyl production cost height.
U.S. Pat 4,748,261 have reported with methyl ethyl diketone rhodium carbonyl and biphosphine ligand catalyzer 1-butylene hydroformylation reaction and have prepared valeraldehyde.Such rhodium catalyst has the high positive isomery ratio of advantages of high catalytic activity and product aldehyde.UCC company with phosphite ligands substitute the further improved catalyzer of triphenylphosphine ligand be called as the 4th generation the olefin hydroformylation catalyzer.The activity of this rhodium catalyst can make propene hydroformylation reaction propylene in " one way " react completely, and does not need recirculation; And obtain 98/2 the positive isomery ratio of product aldehyde, the regioselectivity of product aldehyde is very high.Nineteen ninety-five, this technology was carried out industrial production.
UCC company has also developed this technology to the process of butene hydroformylation prepared in reaction valeraldehyde.Technology comprises condensation/hydrogenation two big steps of n-butene hydroformylation reaction and valeral.Linear chain aldehyde is up to 94% in the valeral.But the used phosphite ligands of this technology is the preparation cost height not only, and decomposes easily in using.The alkyl hydroxy phosphonic acids meeting gelation that the phosphite ligands degraded generates, thus liquid recycle unit (contemporary petroleum and petrochemical industry, 10 (10): 15) stopped up.Therefore this technology is at present in industrial not widespread use as yet.
In the continuous hydroformylation reaction process of alkene, catalyzer and product are in liquid phase together, and product aldehyde is separated from reaction solution, and catalyst solution is recycled in the reactor.How to guarantee that in sepn process the thermo-sensitivity rhodium catalyst do not suffer a loss, be one of improved emphasis of olefin hydroformylation technological process always.
In order to solve the separation problem of continuous flowing type reaction process process product aldehyde and catalyst solution, Chinese patent ZL 01804852 once proposed the C with the triphenylphosphine rhodium carbonyl catalyst
2～C
20The separation method of the continuous hydroformylation reaction device of alkene effluent.This invention comprises two sections voltage drop method separating aldehydes and catalyst solution.First section step-down separates unreacting material and the reaction solution that comprises product aldehyde and catalyst solution and aldehyde polycondensate.Second section is that the reaction solution step-down that first section separation obtains is separated into product aldehyde and catalyst solution.In above-mentioned sepn process, reactor effluent and reaction solution must be heated above 5～50 ℃ of hydroformylation reaction temperature.Because the used organic phosphine rhodium carbonyl catalyst of olefin hydroformylation is temperature and atmosphere susceptibility organometallics, degrades easily at high temperature or when not having the synthetic gas protection, thereby reduced activity of such catalysts.Therefore adopt this method separated product aldehyde and catalyzer, may cause catalyst activity to descend fast.
On the other hand, U.S. Pat 4,287,370 are reported in the mobile hydroformylation reaction flow process, and product n-alkanal and isomery aldehyde can condensation generate polycondensate under reaction conditions, generate high boiling dimerization, trimerization and tetramer.Possible superpolymer formation mechanism is as shown below:
And ZL 01804852 makes temperature be higher than 5～50 ℃ of temperature of reactor the two sections step-down product separation aldehyde of fluid removal thing employing and the catalyst solution of continuous hydroformylation.Its weak point is to make reaction solution be in comparatively high temps for a long time, will increase the polycondensation of olefin hydroformylation aldehyde product, increases high boiling superpolymer, reduces catalyst activity.
Summary of the invention
The purpose of this invention is to provide the technological process that a kind of hydroformylation of olefin with industrial application value prepares aldehyde.
Synthetic gas after the present invention also purifies with suitable hydrogen and carbon monoxide proportioning with the 1-butylene raw material that contains a small amount of butane, suitable/anti-2-butylene and iso-butylene, in the presence of the organic phosphine rhodium carbonyl catalyst, continuous hydroformylation reaction; Adopt step-down gas-liquid separation and malleation thin film evaporation combination separation method subsequently, isolate valeral, butane and unreacted butylene that reaction generates, residue contains the catalyst solution of active organic phosphine rhodium carbonyl catalyst, solvent and a small amount of high boiling material, and being circulated to reactor after activated again continues catalyzed reaction.
The present invention proposes a kind of continuity technological process for preparing valeraldehyde, and this process comprises:
A, a reaction zone, in single-stage or multistage stirred autoclave, with organic phosphine rhodium carbonyl complex compound and triphenylphosphine as catalyzer, form under the existence of recycling catalyst solution after being dissolved in the valeral solvent, 1-butylene raw material and control synthetic gas carry out hydroformylation reaction continuously under 70～130 ℃, 1.0～3.0MPa; From the continuous effusive reactor stream fluid of reaction zone, except that the valeraldehyde that contains generation, a spot of isovaleric aldehyde, with the polycondensate of the corresponding butane of alkene and very a spot of amylalcohol and valeral, also contain above-mentioned unreacting material and catalyzer;
B, a disengaging zone comprise single-stage or multi-stage gas-liquid separator, header tank and film-type evaporation equipment, are composed in series; From the effusive reactor stream fluid of above-mentioned reaction zone, cooling, step-down are also carried out sending into header tank after the gas-liquid separation through gas-liquid separator, continuously flow into film-type evaporation equipment again, evaporation, condensation under the synthetic gas protective atmosphere are separated into two stream thighs of thick product and recycling catalyst; Thick product mainly contains valeral and C4 hydrocarbon, and recycling catalyst solution contains above-mentioned rhodium complex, triphenylphosphine, valeral and a spot of amylalcohol, aldehyde polycondensate;
C, a region of activation, recycling catalyst solution is sent into activator, after fully contacting, activate with synthetic gas, returns reaction zone again and carries out hydroformylation reaction; Its operational condition is 50～100 ℃, 1.1～3.5MPa.
At reaction zone, the H of synthetic gas
2/ CO mol ratio is 0.5～5.0, adopts various sorbent materials to remove wherein micro-O
2, S, Cl.The mol ratio of synthetic gas and alkene is 2.05～5.0, mixes with recycling catalyst by activator, enters reactor and participates in hydroformylation of olefin.
At reaction zone; that the 1-butylene raw material contains is suitable on a small quantity/anti--2-butylene, iso-butylene and butane; 1-butylene content is not less than the butene feedstock that 50wt%, iso-butylene content are not higher than 5wt%; the back volume ratio with alkene and recycling catalyst of purification is 0.1～1.5 flow velocity adding reactor, participates in hydroformylation of olefin.
At reaction zone, the organic phosphine rhodium carbonyl catalyst derives from various rhodium complexs, such as being selected from RhH (CO) (C
18H
15P)
3, Rh (CO) (C
5H
7O
2) (C
18H
15P) or Rh (CO)
2(C
5H
7O
2).
The catalyst solution that organic phosphine rhodium carbonyl, triphenylphosphine and solvent valeral are formed, rhodium concentration is 0.5～5mmol/L, the P/Rh mol ratio is 10～1000.
Preparation of Catalyst is such: organic phosphine rhodium carbonyl, triphenylphosphine and solvent valeral material dissolution, mix after, at H
2/ CO volume ratio is that 1.0 synthetic gas exists down, prepares acquisition in 0.2～2 hour in the stirring tank under 50～100 ℃, 0.3～1.5MPa.
In the disengaging zone, film-type evaporation equipment is selected from lift-film evaporator, scraper-type or does not have scrapper thin film evaporator, and its operational condition is 20～100 ℃ of vaporization temperatures, pressure 0.08～0.6MPa, is preferably 30～80 ℃, 0.09～0.3MPa.
In the region of activation, its volume of recycling catalyst activator is 1/5～1/500 of a reactor, is preferably 1/10～1/100; The member that is selected from various high certain pore fillers or all kinds static mixer is equipped with in inside, to strengthen the gas-to-liquid contact effect; Its operational condition is 50～100 ℃, 1.1～3.5MPa, is preferably 60～90 ℃, 1.3～3.0MPa.
Following main contents of the present invention are illustrated:
1. the film-type evaporation equipment of positive pressure operation
In the flowing-type technical process of butene hydroformylation reaction; reaction solution not only contains rhodium complex, triphenylphosphine, reaction product valeraldehyde, isovaleric aldehyde, also contains the intact 1-butylene of part butane, unreacted, suitable/anti--2-butylene and a spot of valeral polycondensate.Have many methods all or part of valeral product and C4 hydrocarbon can be separated from reaction solution, the solution that residue contains catalyzer is recycled to reaction zone, continues the catalyzed alkene hydroformylation reaction.These methods comprise film-type evaporation, simple distillation, underpressure distillation, flash distillation and the pressure distillation under the synthetic gas protection etc.
Hydroformylation of propene prepares in the process of butyraldehyde; most of propylene and propane are overflowed in the gas-liquid separation stage with synthetic gas in the reaction solution, the method that adopts flash distillation just effectively separating reaction liquid be to contain thick product and the catalyst solution that boiling point is 75 ℃ butyraldehyde-n and the boiling point isobutyric aldehyde that is 63 ℃.But in the butene hydroformylation reaction process; because valeraldehyde and 2 methyl butyraldehyde normal boiling point are 103 ℃ and 92 ℃; contain more C4 hydrocarbon in the reaction solution; need higher temperature and severe condition with flash distillation or distillating method; ability is product separation aldehyde and catalyst solution effectively, and it is more to cause metal rhodium complex compound and organophosphorus ligand to lose in sepn process.In addition, because temperature is higher, the residence time is longer, the polycondensation of product valeral becomes dipolymer, trimer and polymer to increase in sepn process.
On the other hand, conventional film-type evaporation equipment all is to use under decompression or high vacuum condition, though reserves are few, the residence time is short,, cause the decomposition of the active rhodium metal complex compound of part unavoidably for the organic phosphine rhodium carbonyl catalyst material that contains temperature and atmosphere susceptibility.
In order to realize effective separation of thick product of valeral and active triphenylphosphine rhodium carbonyl catalyst solution; can guarantee that again vaporization temperature is low, the residence time short; and the carbon monoxide protective atmosphere is arranged; we find in the sepn process of butene hydroformylation reaction solution; use the film-type evaporation equipment of positive pressure operation, comprise conventional lift-film evaporator and scraper-type or the thin-film evaporator of belt scraping plate not.Owing to contain the catalyst solution of organic phosphine rhodium metal complex compound; all can add the low pressure synthetic gas in header tank and receiving tank is protected; not only vaporization temperature is low for the film-type evaporation equipment of positive pressure operation, the residence time short; and isolated catalyst solution is still under the atmosphere of synthetic gas; therefore in thick product of whole valeral and the catalyst solution sepn process, active triphenylphosphine rhodium carbonyl complex compound is adequately protected.Adopt continuous butene hydroformylation process of the present invention, the film-type evaporation device separates valeral product and the catalyst solution of positive pressure operation, more superior than the flash distillation and the reduction vaporization method of routine, its implementation result fully shows in embodiment 4.
2. activator
Hydroformylation of olefin prepares in the technological process of aldehyde in the presence of the organic phosphine rhodium carbonyl catalyst, and not only the active of rhodium catalyst slowly descends under reaction conditions, and the polycondensate of product aldehyde also weakens the hydroformylation activity of rhodium catalyst.
U.S. Pat 4,148,830 propose hydroformylation of propene prepares that butyraldehyde is condensed into dimerization, trimerization, four poly-and polymers in the butyraldehyde process.US 4,287, and valeral self polycondensation and mutual polycondensation generate high boiling dipolymer, trimer, tetramer in the 370 report butene hydroformylation reaction successive processess.
When we study butene hydroformylation and prepare valeraldehyde, condenses increase with temperature of reaction in hydroformylation reaction of also finding valeral increases, for example reacted 2 hours down for 100 ℃ in temperature, the valeral polycondensate is respectively dimer 0.51wt% in the reaction solution, tripolymer 5.48wt%, tetramer 1.31wt%; And reacted 2 hours valeral dimer 0.92wt% in the reaction solution, tripolymer 8.51wt%, tetramer 5.91wt% for 110 ℃ down in temperature.
In addition, some textbooks are (as Rhodium Catalyzed Hydroformylation, Kluwer AcademicPublishers:2000) points out under some process environments, to interact between the rhodium organic phosphine complex compound, form the multinuclear rhodium cluster compound such as the Rh that do not have catalytic activity
4(CO)
12-n(TPP)
n(n=1-4).The formation of multinuclear rhodium cluster compound is influenced by many processing condition, and for example the temperature of reaction process process, organophosphorus ligand and rhodium concentration and ratio thereof, carbon monoxide and hydrogen dividing potential drop etc. all can generate inactive rhodium cluster compound.The influence of high temperature and carbon monoxide pressure of tension factor is particularly important.
A lot of reports point out guaranteeing do not have under the situation of catalyzer poison that the catalytic activity of triphenylphosphine rhodium carbonyl catalyst still descends with the speed of every day 1～3%.U.S. Pat 4,277,527 report activity of such catalysts reduce with the speed of every day 3%.To the active influence of rhodium catalyst, the present invention proposes to add activator equipment in the technological process of the continuous hydroformylation reaction of butylene at above-mentioned each factor.
The activator volume has only 1/5～1/500 of reactor volume, keeps optimum temperature and pressure.Inner members such as high certain pore fillers and/or static mixer such as SV type static mixer are housed in the activator.These inner members make recycling catalyst solution that enters in the activator and the suitable H that together enters
2The fresh synthesis gas of/CO ratio fully contacts, and gas-liquid mixture is turbulent flow, shearing, mixing in runner, and rhodium catalyst is able to abundant activation.Aggregate in the catalyst solution is sheared in activator, disperses, and multinuclear rhodium cluster compound decomposes, is reassembled as active monokaryon organic phosphine-rhodium carbonylcomplex, further deactivated catalyst.The effect of activator fully shows (embodiment 5) in flow reactor test in continuous 1000 hours.
Description of drawings
Content of the present invention is further set forth by means of accompanying drawing.Accompanying drawing is only used for illustrating block diagram of the present invention, the necessaries of the interpretation process of only drawing, and the facility of other significant need, the omissions such as equipment, pump, valve, tundish of confluxing as instrument, gas.The process described in the figure that the present invention is not limited thereto.
It is as follows that the present invention prepares valeraldehyde process step:
(1) catalyst preparation: drive or when adding catalyst, acetylacetonatodicarrhodium rhodium and triphenylphosphine solve homogeneously in the solvent, add catalyst circulation tank V6 by pipeline 26, with the N after purifying2Or synthetic Gas finds time to replace, and after pump P2 is delivered to the reactor preparation, is circulated to whole system again.
(2) butene hydroformylation reaction: whole system N2And/or synthesis gas replaces respectively, from emission The detection system oxygen content is lower than 0.1ppm. Hydrogen through pipeline 2, passes through respectively gas through pipeline 1, carbon monoxide Mass velocity meter (attached not shown in FIG.) metering, the preparation synthesis gas that confluxes enters the C1 clean unit, after the purification Synthesis gas in oxygen, sulphur and chlorinity be lower than 0.1ppm. Fresh synthesis gas and pipeline 17 contain unreacted With the recycling catalyst of pipeline 22, be mixed into the catalyst activation through pipeline 3 after the voltage stabilizing of C4 hydrocarbon recycled offgas Device V1 continuously flows into hydroformylation reaction device R1. Olefin feedstock purifies by clean unit C2, and metering is sent Enter reactor R1, hydroformylation reaction takes place. Reactor is equipped with the adjustable speed magnetic stirrer, adds the cover heating. Reaction end gas, enters gas-liquid separator V2 through pipeline 9 and separates gas by cooler E1 cooling through pipeline 8 Body advances fuel manifold (attached not shown in FIG.) through pipeline 10 metering emptying, and liquid is through pipeline 11 Returning reactors.
(3) gas-liquid separation: the reactor stream fluid is transported to gas-liquid separator V3 by reactor R1 through pipeline 12. Isolated gas phase is butane, unreacted butylene and synthesis gas, passes through cooler E2 through pipeline 13, again through pipe Line 14 enters gas-liquid separator V4 to be separated, and recycled offgas is through pipeline 16 and supercharger P3, again through pipeline 17 Returning reacting system; Liquid returns gas-liquid separator V3 through pipeline 15. Liquid phase comprises catalyst solution, product Aldehyde, a small amount of product aldehyde polycondensate and C4 hydrocarbon are delivered to kestner long-tube evaporator equipment through pipeline 18 by pump P1 V5.
(4) the thick product of valeral separates with catalyst solution: from the isolated reactant liquor of gas-liquid separator V3, and bag The rhodium catalyst, triphenylphosphine, solvent, product valeraldehyde, the isopentyl aldehyde, a small amount of that contain uniform dissolution Raw material and the aldehyde polycondensate of reaction by pipeline 18 and pump P1, are sent into film-type evaporation equipment V5 through pipeline 19. Along the catalyst solution that film-type evaporation equipment tube wall flows through, compile by pipeline 20 inflow catalyst circulating tank V6, Be circulated to activator V1 through pump P2 again. The thick product of the valeral that is evaporated compiles after condenser E3 condensation, Enter thick products pot V7 through pipeline 24. Thick product distills or rectifying as required, can obtain purity greater than 99wt% Valeraldehyde. Thick product removes direct polycondensation behind the C4 hydrocarbon, the standby plasticizer alcohol 2-propyl enanthol of Hydrogenation.
(5) raw material of synthetic gas and tail gas: prepare on demand accurate H with the gas mass velocity meter2Synthesizing of/CO ratio Gas. Synthesis gas strictly purifies at clean unit C1, and its oxygen, sulphur, chlorinity all are lower than 0.1ppm. The gas phase look The H of spectrometer timing on-line analysis raw material of synthetic gas and tail gas2/ CO ratio is by regulating the H of raw material of synthetic gas2/ CO ratio and exhaust flow, H in the control tail gas2/ CO volume ratio is 0.8～5.0, is preferably 0.9～3.0, And then the just different of adjusting hydroformylation of olefin product is 6～30 than (L/B).
In above-mentioned continuous process, in step (2), the reaction temperature of hydroformylation reaction device R1 is 70～130 ℃, pressure 1.0～2.5MPa.
In above-mentioned continuous process, the pressure 0.4～1.0MPa of gas-liquid separator in step (3), temperature Spend 50～90 ℃.
In above-mentioned continuous process, in step (4) film-type evaporation equipment be selected from lift-film evaporator, Scraper-type or do not have scrapper thin film evaporator, its operating condition be 20～100 ℃ of evaporating temperatures, pressure 0.08～0.6MPa, be preferably 30～80 ℃, 0.09～0.3MPa.
In above-mentioned continuous process, its volume of recycling catalyst activator is reactor in step (4) 1/5～1/500, be preferably 1/10～1/100; The member that strengthens gas-liquid contact is equipped with in inside, is selected from various High certain pore fillers or static mixer; Its service condition is 50～100 ℃, 1.1～3.5MPa, be preferably 60～90 ℃, 1.3～3.0MPa.
Beneficial effect of the present invention is as follows:
1. the present invention adopts catalyst activator, has activated rhodium catalyst, and control or the polycondensation reaction of minimizing aldehyde are given birth to The acetal that becomes is high boiling point by-products produced, improves catalyst activity, improves the regioselectivity of aldehyde.
2. the film-type evaporation equipment of the present invention's selection is than catalyst solution in the more effective separating reaction liquid of flash vessel With the valeral product. Suitable kestner long-tube evaporator operating condition can reduce or not produce the aldehyde condensation, the protection rhodium catalyst, Improve catalyst activity and extending catalyst service time.
Embodiment
Illustrate content of the present invention below, but protection scope of the present invention is not limited to following examples.
Embodiment 1
In the process of reaction process shown in the accompanying drawing, reactor volume is 1 liter, has the double-deck magnetic stirrer of speed governing, the heating of oil bath chuck.The catalyst activator electrically heated.
The 3.84g triphenylphosphine methyl ethyl diketone rhodium carbonyl that adds 3.5 liters of valeraldehyde uniform dissolution in the flowing reactive system, 369.8g triphenylphosphine catalyst solution.Purge the exchange system air with high purity nitrogen.Feed the H that purifies
2/ CO is than the synthetic gas that is 1.0, is lower than 0.1ppm up to the oxygen level of system.The olefin feedstock reaction that adds 1-butylene purity 95.2wt%, iso-butylene 0.5wt%.Reactor R1 operational condition is controlled at 80～90 ℃, 1.9～2.1MPa.Reaction solution is isolated liquid phase under 60 ℃, 0.4～0.8MPa in gas-liquid reactor V3, send into thin-film evaporator V5 by pump P1, isolates thick product valeral and enter product jar V7 under 40～60 ℃, 0.15MPa.Catalyst solution receives V6, loops back catalyst activator V1 by pump P2 again, and the activatory catalyst solution is got back to reactor and continued hydroformylation reaction.Synthetic gas and tail gas are by the gas chromatograph on-line analysis, and thick product and catalyzer timing sampling are by another gas chromatograph analysis.Trace oxygen analyzer on-line analysis gas oxygen content.Continuous hydroformylation reaction 320h, test-results is listed in the table 1.
Table 1
Embodiment 2
With the identical butene hydroformylation operation experiments method of embodiment 1.Add the olefin feedstock of 1-butylene purity 80.8wt%, iso-butylene 1.5wt%, hydroformylation reaction is 1020 hours continuously, the results are shown in table 1.
Embodiment 3
With the identical butene hydroformylation operation experiments method of embodiment 1.Butene feedstock consists of 1-butylene 55.4wt%, suitable/anti--2-butylene 22.6wt%, butane 19.5wt%, iso-butylene 2.5wt%, and hydroformylation reaction is 50 hours continuously, the results are shown in table 1.
Embodiment 4
With the identical butene hydroformylation experimental technique of embodiment 1, reactor effluent is through gas-liquid separator separates, and the reaction solution of acquisition is with flash distillation and thin-film evaporator separating catalyst solution and valeral product respectively.Adopt Rotary Evaporators to carry out flash distillation, film-type evaporation equipment choosing wiped film evaporator.Light, the heavy constituent liquid phase that steam are analyzed composition with GC.The results are shown in table 2.
Embodiment 5
With the identical butene hydroformylation experimental technique of embodiment 1, adopt identical butene feedstock and reaction conditions, import and export pipeline at activator and connect bypass.After the flowing reactive system operation is stable, open bypass, close activator inlet valve (not drawing in the accompanying drawing), make recycling catalyst solution without activator, flow directly into reactor, hydroformylation reaction is 150 hours continuously; Open the activator inlet valve again, close bypass valve, make recycling catalyst solution through activator, hydroformylation reaction is 150 hours continuously.Experimental result sees Table 3.
Table 2
Table 3
Claims (8)
1, a kind of continuity technological process for preparing valeraldehyde, this process comprises:
A, a reaction zone, in single-stage or multistage stirred autoclave, with organic phosphine rhodium carbonyl complex compound and triphenylphosphine as catalyzer, form under the existence of recycling catalyst solution after being dissolved in the valeral solvent, 1-butylene raw material and control synthetic gas carry out hydroformylation reaction continuously under 70～130 ℃, 1.0～3.0MPa; From the continuous effusive reactor stream fluid of reaction zone, except that the valeraldehyde that contains generation, a spot of isovaleric aldehyde, with the polycondensate of the corresponding butane of alkene and very a spot of amylalcohol and valeral, also contain above-mentioned unreacting material and catalyzer;
B, a disengaging zone comprise single-stage or multi-stage gas-liquid separator, header tank and film-type evaporation equipment, are composed in series; From the effusive reactor stream fluid of above-mentioned reaction zone, cooling, step-down are also carried out sending into header tank after the gas-liquid separation through gas-liquid separator, continuously flow into film-type evaporation equipment again, evaporation, condensation under the synthetic gas protective atmosphere are separated into two stream thighs of thick product and recycling catalyst solution; Thick product mainly contains valeral and C4 hydrocarbon, and recycling catalyst solution contains above-mentioned rhodium complex, triphenylphosphine, valeral and a spot of amylalcohol, aldehyde polycondensate;
C, a region of activation, recycling catalyst solution is sent into activator, after fully contacting, activate with synthetic gas, returns reaction zone again and carries out hydroformylation reaction; Its operational condition is 50～100 ℃, 1.1～3.5MPa.
2, as the said technological process of claim 1, it is characterized in that: at reaction zone, that the 1-butylene raw material contains is suitable on a small quantity/anti--2-butylene, iso-butylene and butane, and 1-butylene content is not less than the butene feedstock that 50wt%, iso-butylene content are not higher than 5wt%.
3, as the said technological process of claim 1, it is characterized in that: at reaction zone, the organic phosphine rhodium carbonyl is selected from RhH (CO) (C
18H
15P)
3Or Rh (CO) (C
5H
7O
2) (C
18H
15P).
4, as the said technological process of claim 1, it is characterized in that: the catalyst solution that organic phosphine rhodium carbonyl, triphenylphosphine and solvent valeral are formed, rhodium concentration is 0.5～5mmol/L, the P/Rh mol ratio is 10～1000.
5, as the said technological process of claim 1, it is characterized in that: in the disengaging zone, film-type evaporation equipment is selected from lift-film evaporator, scraper-type or does not have scrapper thin film evaporator, and its operational condition is 20～100 ℃ of vaporization temperatures, pressure 0.08～0.6MPa.
6, as the said technological process of claim 5, it is characterized in that: in the disengaging zone, film-type evaporation equipment is selected from lift-film evaporator, scraper-type or does not have scrapper thin film evaporator, and its operational condition is that vaporization temperature is that 30～80 ℃, pressure are 0.09～0.3MPa.
7, as the said technological process of claim 1, it is characterized in that: in the region of activation, its volume of activator is 1/5～1/500 of a reactor; The member that is selected from various high certain pore fillers or all kinds static mixer is equipped with in inside, to strengthen the gas-to-liquid contact effect; Its operational condition is 50～100 ℃, 1.1～3.5MPa.
8, as the said technological process of claim 7, it is characterized in that: in the region of activation, its volume of activator is 1/10～1/100 of a reactor; The member that is selected from various high certain pore fillers or all kinds static mixer is equipped with in inside, to strengthen the gas-to-liquid contact effect; Its operational condition is 60～90 ℃, 1.3～3.0MPa.
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| KR101629043B1 (en) * | 2008-07-03 | 2016-06-09 | 다우 테크놀로지 인베스트먼츠 엘엘씨. | Process of controlling heavies in a recycle catalyst stream |
| CN102826969B (en) * | 2011-06-17 | 2015-07-22 | 中国石油化工股份有限公司 | Separation method of olefin hydroformylation reaction liquid-phase discharged material |
| CN107141204B (en) * | 2016-03-01 | 2022-03-15 | 陶氏技术投资有限责任公司 | Hydroformylation process |
| CN108285410A (en) * | 2017-11-28 | 2018-07-17 | 聊城市鲁西化工工程设计有限责任公司 | A kind of mixing hydroformylation of propene synthesis butyraldehyde technique |
| CN110862307A (en) * | 2018-08-27 | 2020-03-06 | 中国石油化工股份有限公司 | Method for preparing aldehyde by mixed carbon-four hydroformylation reaction |
| CN111646884A (en) * | 2019-03-04 | 2020-09-11 | 内蒙古伊泰煤基新材料研究院有限公司 | Hydroformylation method based on Fischer-Tropsch synthesis product |
| CN111217686B (en) * | 2020-01-16 | 2022-12-16 | 江苏诺盟化工有限公司 | Preparation method of n-valeraldehyde and special Venturi ejector |
| CN114773172B (en) * | 2022-06-20 | 2022-10-18 | 中海油天津化工研究设计院有限公司 | Optimization method of process for preparing aldehyde by olefin hydroformylation |
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