CN101768059A - Method for continuously formylatelating monoolefine and hydrogen by adopting static mixing reactor - Google Patents
Method for continuously formylatelating monoolefine and hydrogen by adopting static mixing reactor Download PDFInfo
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- CN101768059A CN101768059A CN200810147926A CN200810147926A CN101768059A CN 101768059 A CN101768059 A CN 101768059A CN 200810147926 A CN200810147926 A CN 200810147926A CN 200810147926 A CN200810147926 A CN 200810147926A CN 101768059 A CN101768059 A CN 101768059A
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Abstract
The invention relates to a production method for continuously formylatelating monoolefine and hydrogen and producing corresponding aldehydess by adopting a static mixing reactor. The method comprises the following steps of: sending an aqueous solution of a water-soluble rhodium-phosphine complex catalyst and partial propionaldehyde in a circulating tank into a static mixing reactor at a certain velocity of flow by a circulating pump; enabling the mixed gases of monoolefine, hydrogen and carbon monoxide to enter the static mixing reactor in the same direction; entering the circulating tank after finishing the reaction; separating and enabling unreacted gases in the tank to enter a tail gas condensate cooler; condensing the aldehydess brought by the gases back to a product tank; enabling liquid entering the circulating tank to stand still and laminate, wherein the aldehydess at the upper layer overflows and enters the product tank; and the catalyst-contained water phase at the lower layer circularly returns to the static mixing reactor by the circulating pump. The invention has the advantages of simple process flows, easy operation control, strong equipment mass transfer strength, high production capability, simple equipment and lower manufacture cost. The method decreases the catalyst amount and reduces the investment cost, thereby being a most suitable process method for formylatelating monoolefine and hydrogen.
Description
Technical field
The present invention relates to the monoolefine is main raw material, is blended under the effect of water-soluble rhodium phosphine complex catalyst with hydrogen and carbon monoxide, as reactor, carries out the production method that hydroformylation is produced corresponding aldehyde with static mixer continuously.
Background technology
Aldehydes such as propionic aldehyde, butyraldehyde, valeral are the important fine chemical products of a class, have consequence in Chemical Manufacture, are widely used in industries such as rubber, paint, plastics, medicine, spices, feed.
At present; the widely used in the world method by the synthetic aldehyde of alkene is the low pressure oxo synthesis; promptly with rhodium phosphine complex catalyst at 90 ℃～120 ℃, 2.1～3.5MPa, hydrogen: carbon monoxide=1: 1～1.5: 1 times; hydrogen, carbon monoxide and alkene carry out hydroformylation reaction; generate corresponding aldehyde, transformation efficiency can reach 80%～99%.
In the low pressure oxo synthesis again because of difference shared oil dissolubility and water-soluble two kinds of methods of rhodium catalyst.U.S. Pat 5,675,041 and Chinese patent CN1168129A in just put down in writing a kind of production method that adopts the ethene hydroformylation system propionic aldehyde of oil soluble rhodium catalyst system.Because this method need add a large amount of solvents, and rhodium catalyst is dissolved in the solvent, after reaction was finished, reaction product propionic aldehyde and catalyzer will separately generally will adopt them the method for rectifying with being dissolved in the organic solvent, had brought difficulty for separation, the purifying of propionic aldehyde.In sepn process, need higher temperature, a large amount of catalyzer are heated under comparatively high temps, also easily cause the inactivation of catalyzer.Adopt the water-soluble rhodium catalyst system, just can avoid above-mentioned oil soluble rhodium catalyst system shortcoming well.Because the aldehyde that generates can only partly dissolve each other with water.Be separated by simple two, just rhodium catalyst soluble in water and organic phase can be separated, avoided the isolating heat-processed of catalyzer and organic phase, be easy to realize recycling of catalyzer, this can significantly reduce catalyzer input amount for the first time, reduce the cost of investment of producing, also simplified technological process simultaneously.
Carry out olefin hydroformylation with the water-soluble rhodium catalyst system and early realized industrialization; the still formula stirred reactor of two parallel connections of usefulness of releasing as union carbide corporation is finished operate continuously; reaction heat borrows still outer circulation pump to derive by outer water cooler; the partly emptying of gas that unreacted is intact partly recycles by recycle compressor.China patent CN1594255A has also reported the flow process similar to union carbide corporation.Having report to say that Sichuan University and Xinjiang Xinfeng Co., Ltd. have carried out the pilot scale work of rare ethene hydroformylation system propionic aldehyde, also is to adopt two placed in-line still formula stirred reactors, finishes the technological process of operate continuously.
There are many shortcomings in the technological process of the tank reactor that above-mentioned band stirs.Because the restriction of stirring arm speed has influenced the dispersion of gas in aqueous catalyst solution, has influenced mass transfer effect, it is just more outstanding that particularly scale is big, the reactor size becomes big back.Because reaction pressure at 2.0～4.0MPa, must have high requirement to reactor, causes equipment manufacturing cost very high, the investment that has strengthened engineering.Use tank reactor, the initial loadings of catalyzer is very big, because the price of rhodium is very expensive, certainly will causes the increase of construction investment, thereby influence the economic advantages of this technology.
Summary of the invention
The invention provides a kind of commercial run that adopts static mixing reactor to carry out the monoolefine hydroformylation continuously.
It is characterized in that adopting the aqueous solution of water miscible rhodium phosphine complex catalyst, enter static mixing reactor with certain flow velocity with recycle pump.Simultaneously monoolefine enters static mixing reactor with after hydrogen, carbon monoxide mix by a certain percentage with the catalyzer equidirectional.The material that enters static mixing reactor is finished hydroformylation of olefin by powerful mixing fast in static mixing reactor.The fluid of finishing reaction is along with the round-robin aqueous catalyst solution enters circulation tank.Special tripping device is housed in circulation tank, unreacted gas in the recycle stock is told, simultaneously with the rapid phase-splitting of oil-water mixture, water enters recycle pump from circulation tank bottom, and oil phase floats on the circulation tank upper strata and the product jar is advanced in overflow.The tail gas of emitting from the product tank deck is admitted to cooler condenser, the aldehydes of being taken out of by the tail gas condensation that here is cooled, and the material that condensation is got off flows into the product jar, and the tail gas of cooler condenser is sent into gas ductwork behind pressure maintaining valve.
Static mixing reactor is a kind of chemical unit equipment of independent type.Itself there are not machinery motion or transmission, flow by fluidic, under the effect of the hybrid element in the static mixing reactor pipe, make fluid constantly change flow direction, add the rotation of fluid self, bump, thereby improve alternate surface in contact greatly at the interface of adjacent elements junction, add static mixer bubble or drop face are brought in constant renewal in, make mass transfer coefficient improve greatly.Because intense mixing also can guarantee the homogeneity of fluid temperature (F.T.), concentration, the generation of minimizing side reaction.Static mixing reactor has good heat-transfer effect.Compare its heat-transfer effect with blank pipe and can improve 5～8 times.Static mixing reactor does not have scale effect substantially, is easy to produce amplify.
Hydroformylation of olefin is a mass transfer limited reaction process, can find out from the kinetics reaction equation, and be zeroth order reaction for concentration of olefin, it is again an exothermal reaction process.For such reaction system, adopt the water-soluble rhodium complex catalyst, use the reactor of static mixer as hydroformylation, optimum beyond doubt.Still formula stirred reactor static mixing reactor has the following advantages relatively:
1, it has higher rate of mass transfer, and equipment volume is dwindled, and makes equipment manufacturing cost reduce;
2, the residence time shortens, and temperature of reaction is even, and side reaction reduces;
3, owing to the profit that adopts water-soluble rhodium complex catalyst reaction solution separates, make catalyzer to recycle, thereby be easy to realize the technical process of serialization, also reduced the usage quantity of catalyzer simultaneously, reduced running cost;
4, there is not scale effect substantially, than the easier amplification of reactor;
5, because very high heat transfer efficient is arranged, make the chuck type, can easily reaction heat be spread out of.
The present invention is a continuous flow procedure, catalyst recirculation is used, the flow velocity of catalyzer in static mixing reactor is 0.2～1.2m/s, reaction mass alkene, hydrogen, carbon monoxide enter static mixing reactor by pump inlet continuously, and their mol ratio is 1: 1.05: 1.05～1: 1.15: 1.15.Reaction product enters circulation tank, and in order to reduce the usage quantity of catalyzer as far as possible, the residence time of reaction solution in circulation tank only is 10～20 seconds.For blended oil and water are separated smoothly, special tripping device is housed in circulation tank, making the liquid that loops back static mixing reactor is the water that contains catalyzer substantially.
Since the temperature in the circulation tank 50～100 ℃ from the reaction end gas that the circulation tank deck is emitted, except small amounts of olefins, hydrogen and carbon monoxide, also have quantitative aldehyde.This tail gas is sent into a cooler condenser, and the refrigerant temperature of this cooler condenser is 5～-50 ℃, with the aldehyde in the condensation recovery tail gas.This material that is recovered is returned to the product jar, and remaining tail gas send the burning of fuel gas pipe network through pressure maintaining valve.If the raw material olefin concentration ratio is higher, the reaction end gas amount is bigger, and when the value of recovery was arranged economically, a then available recycle compressor looped back the static mixing reactor inlet with tail gas, is recycled.Owing to contain a certain amount of alkane in the raw material olefin, and also have a spot of alkane generation in the reaction process,, also need a spot of tail gas is broadcasted to the fuel gas pipe network through pressure maintaining valve in order to prevent the alkane enrichment.Aldehyde in the product jar then can be delivered to the separation and purification system, obtains purified product.For carbon four and above aldehydes, positive isomer must be separated.
The hydroformylation reaction of alkene is a kind of thermopositive reaction, will shift out heat timely in reaction, to reduce the generation of side reaction, adopts the static mixing reactor of chuck type, because it has very high heat transfer coefficient, can effectively reaction heat be spread out of.Do not need additional in addition heat transfer equipment.It can be used as the preheater use of recycle stock when going into operation in addition.
What use in this technology is water miscible rhodium phosphine complex catalyst, and the concentration of rhodium is 1 * 10-4 mol to 1 * 10-2 mol in the aqueous catalyst solution.
The temperature of reaction of hydroformylation can be controlled at 40～120 ℃ in this technology.
The pressure of this technology can be controlled at 1.0～4.0MPa, and the stable control of pressure realizes by the tail gas pressure maintaining valve.
The conversion of olefines rate is 95～99% in this technology, and selectivity is 93～98%.When generating carbon four and above aldehyde, positive structure body: isomer=90: 10～95: 5.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples.
Accompanying drawing is to adopt static mixing reactor to carry out the general flow chart of continuous monoolefine hydroformylation
Coding in the accompanying drawing is respectively: 1, under meter 2, static mixing reactor 3, recycle pump 4, recycle compressor 5, circulation tank 6, cooler condenser 7, product jar
Embodiment
The present invention is not subjected to the restriction of following embodiment, can determine concrete embodiment according to technical scheme of the present invention and practical situation.
Embodiment 1
Rhodium content is the aqueous solution of the rhodium phosphine complex catalyst of 1 * 10-4 mol to 1 * 10-2 mol; send into static mixing reactor through recycle pump; chuck with about 80 ℃ hot water warp let-off static mixing reactors; circulation fluid is preheated to 70 ℃; it is that 99% ethene and volume ratio are ethene then with concentration: hydrogen: the gas mixture of carbon monoxide=form at 1: 1.05: 1.05; send into static mixing reactor in the same way with circulation fluid; under catalyst action, ethene, hydrogen and carbon monoxide generation hydroformylation reaction.When feeding gas mixture, change the hot water that feeds static mixing reactor into water coolant, temperature in the controlling reactor, be stabilized in about 70 ℃.Reacted gas-liquid mixture enters circulation tank, under the effect of special tripping device, and oil and the rapid layering of water, the water that contains catalyzer carries out next one circulation through recycle pump.The propionic aldehyde that reaction generates enters the product jar from the upflow tube of circulation tank.Unreacted gas is by entering the product jar communicating pipe, and most gas send and sends into reactor after material mixed gas mixes through recycle compressor.Enter cooler condenser as tail gas after pressure maintaining valve is sent into the fuel pipe network on a small quantity.Propionic aldehyde under being condensed in cooler condenser returns the product jar.
System pressure maintains 1.8MPa,
The flow rate control of circulation fluid in reaction tubes is at 0.5m/s, and the vapour-liquid ratio of gas mixture and circulation fluid is 280, and the transformation efficiency of reaction is 98.5%, and selectivity is 98%.
Embodiment 2
The use of catalyzer and operating process are with example 1, and only because of the raw material ethylene concentration is low, tail gas is circulation not,
The concentration of ethene is 50%, ethene: hydrogen: carbon monoxide=1: 1.10: 1.10,
Temperature of reaction is 80 ℃, and reaction pressure is 2.2MPa, and the flow velocity of reaction solution in reactor is 0.6m/s,
The vapour-liquid ratio of unstripped gas and circulation fluid is 350,
The transformation efficiency of reaction is 97.8%, and selectivity is 97%.
The use of catalyzer and operating process be with example 1,
The concentration of raw material propylene is 99%, propylene: hydrogen: carbon monoxide=1.0: 1.10: 1.05,
Temperature of reaction is 80 ℃, and reaction pressure is 2.4MPa, and the flow velocity of reaction solution in reactor is 0.5m/s,
The vapour-liquid ratio of unstripped gas and circulation fluid is 250,
Reaction conversion ratio is 98%, and selectivity is 97%.
Embodiment 4
The use of catalyzer and operating process are with example one, and only because of raw material propylene concentration is low, tail gas is circulation not,
The concentration of raw material propylene is 60%, propylene: hydrogen: carbon monoxide=1.0: 1.10: 1.10,
90 ℃ of temperature of reaction, reaction pressure are 2.5MPa, and the flow velocity of reaction solution in reactor is 0.4m/s,
The vapour-liquid ratio of unstripped gas and circulation fluid is 300,
The transformation efficiency of reaction is 97.5%, and selectivity is 96%.
The use of catalyzer and operating process are with example 1, and difference is that the raw material 1-butylene is by being pumped into static mixing reactor.
The concentration of raw material 1-butylene is 99%, 1-butylene: hydrogen: carbon monoxide=1.0: 1.05: 1.05 (mol ratio),
105 ℃ of temperature of reaction, reaction pressure 2.8MPa, reaction solution is 0.6m/s in the air speed of reactor,
The vapour-liquid ratio of unstripped gas and circulation fluid is 200,
The transformation efficiency of reaction is 95%, and selectivity is 95%,
Valeraldehyde content 〉=93% in the product valeral.
Catalyzer use and operating process with embodiment 1, difference is that the raw material 1-butylene is by being pumped into static mixing reactor, tail gas is circulation not.
The concentration of raw material 1-butylene is 70%, and all the other are mainly alkane, 1-butylene: hydrogen: carbon monoxide=1.0: 1.10: 1.10 (mol ratio),
Temperature of reaction is 105 ℃, and reaction pressure is 2.6MPa, and the air speed of reaction solution in reactor is 0.35m/s,
The vapour-liquid ratio of unstripped gas and circulation fluid is 220,
Reaction conversion ratio is 93%, and selectivity is 93%,
Valeraldehyde content 〉=93% in the product valeral.
Claims (10)
1. commercial run that adopts static mixing reactor to carry out the monoolefine hydroformylation continuously.The aqueous solution that it is characterized in that water miscible rhodium phosphine complex catalyst enters static mixing reactor through recycle pump with certain flow velocity.Simultaneously, the gas mixture of monoolefine and hydrogen, carbon monoxide, the also equidirectional static mixing reactor that enters.The material that enters static mixing reactor is by powerful mixing, makes liquid-liquid, liquid-gas high dispersing, and reinforcing mass transfer efficient is finished hydroformylation of olefin fast in static mixing reactor greatly.The fluid of finishing reaction enters circulation tank subsequently, and unreacted gas is separated and enters the tail gas cooler condenser in circulation tank, the aldehydes of being taken out of by tail gas, condensation here is cooled, the material that condensation is got off flows into the product jar, and to improve the yield of product, tail gas is then sent into the fuel pipe network.The liquid that enters circulation tank is under the effect of a special tripping device and layering, the upper strata is an aldehydes, and overflow enters the product jar, and lower floor is the water (containing the part aldehydes) that contains catalyzer, return through recycle pump and to enter into static mixing reactor, thereby finish the whole production working cycle.When the concentration ratio of raw material olefin is higher, the inlet that most tail gas is delivered to static mixing reactor through recycle compressor is used, a small amount of tail gas enters cooler condenser and reclaims aldehyde after pressure maintaining valve is delivered to gas ductwork, and emitting a small amount of tail gas is in order to control the enrichment of alkane.
2. the method for continuous production aldehyde according to claim 1 is characterized in that its flow reactor is the static mixer of tubular type, and used model is SV, SX, SL, SH, SK type, preferred SV, SX type.
3. static mixer according to claim 2 is a strap clamp cover type, and shifting out by the chuck heat-transfer medium of the initial preheating of material and reaction heat finished.
4. the method for continuous production aldehyde according to claim 1 is characterized in that described monoolefine can be an ethene, and generating product through hydroformylation reaction is propionic aldehyde.The reaction pressure of ethene hydroformylation is 0.5MPa～4.0MPa, preferred 1.0MPa～3.0MPa, and temperature of reaction is 40 ℃～100 ℃, preferred 50 ℃～90 ℃.
5. the method for continuous production aldehyde according to claim 1 is characterized in that described monoolefine can be a propylene, and generating product through hydroformylation reaction is butyraldehyde.The reaction pressure of hydroformylation of propene is 1.0MPa～5.0MPa, preferred 2.0MPa～4.0MPa, and temperature of reaction is 70 ℃～140 ℃, preferred 90 ℃～120 ℃.
6. the method for continuous production aldehyde according to claim 1 is characterized in that described monoolefine can be a butylene, and generating product through hydroformylation reaction is valeral.The reaction pressure of butene hydroformylation is 1.0MPa～6.0MPa, preferred 2.0MPa～4.0,5.0MPa, and temperature of reaction is 50 ℃～150 ℃, preferred 100 ℃～130 ℃.
7. according to claim 1,4,5,6 described, the concentration of raw material olefin can preferably get 50%～99% 20%～100%.
8. according to the method for claim 1,2 described continuous production aldehyde, it is characterized in that the aqueous catalyst solution of continuous flow is realized by recycle pump, preferred magnetic drive pump of this pump or canned-motor pump.The flow velocity of fluid in the static mixing reactor pipe is 0.2m/s～1.2m/s, preferred 0.4m/s～1.0m/s.The vapour-liquid ratio (volume) that enters static mixing reactor is 100～800, preferred 400～600.
9. according to right 1, tail gas enters cooler condenser, carries out condensation under-50 ℃～5 ℃, and condensate stream is to the product storage tank.
10. according to claim 1,6 described, the raw material butylene can be in liquid mode through being pumped into static mixing reactor and the aqueous catalyst solution of sending into, hydrogen, a carbon monoxide are finished hydroformylation reaction in static mixing reactor.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110180422A (en) * | 2019-04-12 | 2019-08-30 | 南京汇仁化工设备有限公司 | A kind of static mixer device |
| WO2019223032A1 (en) * | 2018-05-25 | 2019-11-28 | An Lihua | Continuous reaction apparatus and method for using hydroformylation reaction to prepare aldehyde |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6492564B1 (en) * | 1999-06-02 | 2002-12-10 | Oxeno Olefinchemie Gmbh | Process for the catalytically carrying out multiphase reactions, in particular hydroformylations |
| CN1594255A (en) * | 2004-06-25 | 2005-03-16 | 新疆新峰股份有限公司 | Method and reaction still for continuous propionaldehyde production |
-
2008
- 2008-12-19 CN CN200810147926A patent/CN101768059A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6492564B1 (en) * | 1999-06-02 | 2002-12-10 | Oxeno Olefinchemie Gmbh | Process for the catalytically carrying out multiphase reactions, in particular hydroformylations |
| CN1594255A (en) * | 2004-06-25 | 2005-03-16 | 新疆新峰股份有限公司 | Method and reaction still for continuous propionaldehyde production |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019223032A1 (en) * | 2018-05-25 | 2019-11-28 | An Lihua | Continuous reaction apparatus and method for using hydroformylation reaction to prepare aldehyde |
| CN110180422A (en) * | 2019-04-12 | 2019-08-30 | 南京汇仁化工设备有限公司 | A kind of static mixer device |
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Application publication date: 20100707 |