CN102826976A - Method for adjusting ratio of butyraldehyde to isobutyraldehyde in propylene catalytic preparation - Google Patents
Method for adjusting ratio of butyraldehyde to isobutyraldehyde in propylene catalytic preparation Download PDFInfo
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Abstract
The invention relates to a method for adjusting the ratio of butyraldehyde to isobutyraldehyde in propylene catalystic preparation. The method comprises the steps of adjusting feed ratio of synthesis gases to propylene and changing excessive ratio of CO to the corresponding propylene to control the ratio of butyraldehyde to isobutyraldehyde in the product. Through the method provided by the invention, technical staffs in the field can control the ratio of butyraldehyde to isobutyraldehyde in the product to 5-12 during the hydroformylation of propylene conveniently; changes of a rhodium catalyst system in the production plant can be avoided so as to ensure the plant operation for a long period, so that the product composition can be adjusted timely according to the market demand when the long-period operation scheme in the plant is adopted.
Description
Technical field
The present invention relates to field of chemical technology, specifically, relate to a kind of rhodium/triphenylphosphine catalysis that utilizes, propene hydroformylation reaction prepares the control method of the just different ratio of product of butyraldehyde.
Background technology
The hydroformylation reaction of alkene has important industrial significance; Utilize the product and the derived product of this reacted to reach millions of tons every year; Wherein aldehydes and the derived product thereof by olefine in low carbon number production accounts for the overwhelming majority; Especially adopting rhodium/triphenylphosphine is that the so-called oil soluble system of catalyzer is adopted by most of devices, so this production technology receives great attention.
Adopt " homogeneous catalysis " technology of rhodium/phosphine complex catalysis system to be called low pressure oxo process technology again in the industry, the principal character of this type technology be with above-mentioned catalyst dissolution in solvent, make raw material olefin and synthetic gas (H
2/ CO) feeding catalyst solution continuously, control condition is carried out hydroformylation reaction in the liquid phase main body, separate after the reaction, subsequently unreacted raw material and catalyst solution is looped back reactor drum, simultaneously product is sent into follow-up purification unit.Obviously, hydroformylation reaction is in the liquid phase main body, to carry out, and as the CO and the H of raw material
2The alkene that reaches low carbon number is gaseous state under reaction conditions, therefore for guaranteeing that unstripped gas has enough concentration in liquid phase, need make CO, H in the gas phase
2Keep enough pressure with alkene.The concentration of different material is different to the influence of reaction result on the other hand, need come to confirm the composition of these compositions in view of the above.
Existing many documents have carried out good summary and commentary to various technical schemes of the prior art.Representational document is by P.W.N.M.Van Leeuwen and the common chief editor of C.Claver " Rhodium Catalyzed Hydroformylation " book.
The just different ratio of hydroformylation reaction product, promptly the ratio of n-alkanal and isomery aldehyde is important index in the actual production, receives much concern.Though generally speaking, the purposes of n-alkanal is more extensive, and along with the technical progress of petrochemical complex, the Application Areas of isomery aldehyde is also enlarging.Therefore change based on the market demand, the product ratio of adjusting positive isomery aldehyde flexibly is very important.And at present along with the development of petrochemical technology, the maximization of device and the long-term operation of device all are the focuses of paying close attention to, and general device operation continuously is very common more than 5 years.Thereby through regulating the method for just different ratio to changing part, will produce very big influence to whole process, be complicated and uneconomic way.
If a kind of method that can in continuous hydroformylation process, control just different ratio can be provided, will play material impact to the kind of product, further increase economic efficiency.In the prior art, about the existing a lot of narrations of the influence factor that influences the just different ratio of pressure hydrogen formylation reaction.
Wherein, for the hydroformylation reaction that uses catalyzer, catalyst structure is most important to the influence of the just different ratio of product, for example:
A series of biphosphine ligand NAPHOS have been reported in the U.S. Pat 4694109, BISBI, PHENAP.Be applied in oneself the rare hydroformylation reaction of 1-, these parts have shown suitable activity and high regioselectivity, wherein BISBI at very low phosphine/rhodium than (4～8: 1) under the situation, just different ratio can reach 96: 4.
Chinese patent CN200610147735.2 discloses a kind of method; In triaryl phosphine/rhodium catalytic system, added bis-phosphite; Can obviously improve the just different ratio of butyraldehyde in activity and the product of triaryl phosphine/rhodium catalyst, and the life-span of significant prolongation bis-phosphite.
Chinese patent CN200810036777.8 discloses a kind of single phosphorous acid ester, bis-phosphite/rhodium catalytic system; This method is compared the catalyst system of a kind of phosphite ester ligand of independent use; Have advantage aspect stability and the selectivity, and can realize through regulating bis-phosphite adjustable in certain limit with the feasible just different ratio of the ratio of single phosphorous acid ester.
In addition; A kind of technology of hydroformylation reaction is disclosed in the U.S. Pat 3527809; Think that reaction stagnation pressure and CO dividing potential drop have very big influence to reaction, need control reaction through control reaction stagnation pressure and CO dividing potential drop, the document thinks that reaction pressure should be between 14.7psi～450psi; Preferably between 14.7～350psi, 14.7～250psi most preferably.Embodiment has provided pressure when 80～100psi becomes 280～300psi, and the just different ratio of product is reduced to 4.0 from 6.0, and document points out that simultaneously the CO dividing potential drop has great importance to the just different ratio of product, when the CO dividing potential drop reaches stagnation pressure (CO+H
2Dividing potential drop with) 75% o'clock, the just different ratio of product obviously reduces, and H
2Dividing potential drop should between stagnation pressure 25～90% between, preferably between 45～75%.
Provided in the U.S. Pat 4400548 under 130 ℃; Partial pressure of propylene aligns the influence of different ratio and speed of response; Partial pressure of propylene is increased to 58.7psi from 55.30psi, and the speed that generates aldehyde is between 1.67～1.88mol/hr*L, and the just different ratio of product is between 9.9～10.2.
Obviously,, clearly propose crucial influence factor, also the influence of key factor is not quantitatively described though prior art has been paid close attention to the influence of reaction conditions to the just different ratio of product.
To above-mentioned defective, the purpose of this invention is to provide the method that a kind of ratio through the conditioned reaction thing is controlled positive isobutyric aldehyde ratio in the catalytic propylene producing butyladehyde of the rhodium/triphenylphosphine process.
Summary of the invention
Ratio to positive isobutyric aldehyde in the prior art is regulated problem; Especially to control by positive isobutyric aldehyde ratio in the propylene producing butyladehyde process; The purpose of this invention is to provide a kind of method and regulate the simple method of the just different ratio of product, thereby make production process more flexible through the adjustment reactant ratio.
The inventor has furtherd investigate the reaction process of utilizing the propylene production butyraldehyde, has proposed through the charge ratio of adjustment synthetic gas with propylene, and the excessive percentage of change CO and corresponding propylene makes that the ratio of butyraldehyde-n and isobutyric aldehyde is controlled at needed scope in the reaction product.
Say that at length method of the present invention may further comprise the steps:
1), utilizes following model prediction CO and the excessive percentage ratio of corresponding propylene according to the just different ratio of required butyraldehyde product;
N＝B
1R
3+B
2R
2+B
3R+B
4
N is the molar excess percentage in the formula, and R is the required just different ratio of butyraldehyde product, and Bn is a constant, wherein:
B
1＝-8.151×10
-5 B
2＝2.570×10
-3 B
3＝-2.843×10
-2 B
4＝0.1218
2) obtain the inlet amount of CO according to computes:
Said corresponding propylene is meant the propylene that reacts with CO and consume;
3) according to step 2) the excessive percentage ratio that calculates, calculate, adjustment synthetic gas inlet amount, make just different ratio and required just different than consistent butyraldehyde product.
Because what the present invention relates to is the big industrial manufacture process of a kind of successive; The influence factor of reaction result is various, so present method described " unanimity " is meant basically identical, but for a person skilled in the art; Can reach the requirement of this area, realize the object of the invention.
Concerning specific technology and device, step 2) the corresponding propylene described in is to confirm according to the reactivity of propylene, is the measured data of device; Therefore, before carrying out method of the present invention, in fact before described step 1), said method also comprises the utilization ratio of the propylene of the catalytic propylene catalytic preparation of mensuration rhodium/triphenylphosphine butyraldehyde technology, promptly in the productive rate of the butyraldehyde of propylene.
In the raw materials used synthetic gas of above-mentioned reaction, CO and H
2The mol ratio relative fixed, generally its ratio is H
2/ CO=1.01～1.10, synthetic gas source have multiple, and use to commercially available in the laboratory, and technology is used is methods such as petroleum naphtha, water-gas conversion;
Wherein, said propylene producing butyladehyde process is meant propylene and synthetic gas (H
2/ CO) serialization is carried out hydroformylation reaction and is prepared the process of butyraldehyde under rhodium/triphenylphosphine catalyst action.Catalyzer constitute (CO) (PPh of Rh (Acac)
3)/PPh
3Wherein Acac is a methyl ethyl diketone, is the commercial reagent.
The reaction conditions of said propylene producing butyladehyde process is: temperature of reaction 353～393K, CO pressure component: 0.03～0.20MPa, H
2Pressure component: 0.15～0.90MPa, partial pressure of propylene power: 0.08～0.80MPa, the concentration of catalyzer Rh is 100～300ppm, triphenyl phosphorus concentration is 5.0～15.0wt%.
In the step 1), said model is an experimental formula by above-mentioned tandem reaction sequence being tested and test data being carried out mathematical regression and obtained.
Revision test repeatedly shows that it is just different from the result to adopt aforesaid method can in following ranges, obtain ideal: excessive percentile variation range is 0.5%～7%, preferred 0.5%～4%; Butyraldehyde-n is 3～15 with the ratio of isobutyric aldehyde in the then said product, preferred 5～12.
Through adopting method of the present invention, those skilled in the art can realize the regulation and control of just different ratio in 5～12 scopes with product in the propene hydroformylation reaction process easily and flexibly; Avoid the change of rhodium catalytic system in the process units, guarantee the device long-term operation, therefore when device adopts the long-term operation scheme, can adjust product timely and form based on the market demand.
Embodiment
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.Specialize like nothing, the raw material that adopts among the embodiment is commercial.
Embodiment 1
Interlock in the reaction unit of hydroformylation of propene producing butyladehyde of reforwarding row one and to make an experiment.The volume of used reaction kettle is 2L, and opening for feed and the gas phase and the liquid phase discharge port of propylene, synthetic gas and catalyzer is housed on the reaction kettle, on the turnover pipeline measuring instrument and analytical sampling mouth is housed.
Wherein propylene is that purity is 99.5% polymerization-grade propylene; The composition of synthetic gas is H
2/ CO=1.033mol ratio, catalyzer constitute (CO) (PPh of Rh (Acac)
3)/PPh
3Wherein Acac is a methyl ethyl diketone, is the commercial reagent.
Feed continuously synthetic gas and propylene, its mol ratio can change in the scope of CO and the excessive percentage 0.5%～7% of corresponding propylene, the detection product, and the productive rate of butyraldehyde is stabilized in 77.7% (in propylene);
Propylene and the synthetic gas generation butyraldehyde that under rhodium/triphenylphosphine katalysis and 90 ℃ of temperature, pressure 1.9MPa condition, reacts in reactor drum.Change synthetic gas charging proportioning and product is analyzed, can to obtain the excessive percentage ratio of CO just different following than data with product through calculating:
Carrying out mathematical regression according to as above experimental data, to obtain product just different following than predictive model:
N＝-8.151×10
-5R
3+2.570×10
-3R
2-2.843×10
-2R+0.1218
Embodiment 2
Under device identical with embodiment 1 and condition, make an experiment, desire is adjusted into 10: 1 with just different ratio.Can calculate the excessive percentage ratio of CO according to predictive model is 1.30%, and the synthetic gas charging should be 7.64mol/h in the time of can calculating propylene feed and be 4.80mol/h according to analytical results again.Regulate the charging proportioning in view of the above, treat sampling analysis behind the system stability, obtaining the just different ratio of reality is 10.15.
Embodiment 3
Under device identical with embodiment 1 and condition, make an experiment, desire is adjusted into 5: 1 with just different ratio.Can calculate the excessive percentage ratio of CO according to predictive model is 3.37%, and the synthetic gas charging should be 7.80mol/h in the time of can calculating propylene feed and be 4.80mol/h according to analytical results again.Regulate the charging proportioning in view of the above, treat sampling analysis behind the system stability, obtaining the just different ratio of reality is 5.03.
Claims (7)
1. method of regulating the catalytic just different ratio of butyraldehyde product by propylene production butyraldehyde technology of rhodium/triphenylphosphine; It is characterized in that; Through the charge ratio of adjustment synthetic gas and propylene, change the excessive percentage of CO and corresponding propylene in the synthetic gas, control the ratio of butyraldehyde-n and isobutyric aldehyde in the reaction product.
2. method according to claim 1 comprises the steps:
1), utilizes following model prediction CO and the excessive percentage ratio of corresponding propylene according to the just different ratio of required butyraldehyde product;
N＝B
1R
3+B
2R
2+B
3R+B
4
N is the molar excess percentage in the formula, and R is the required just different ratio of butyraldehyde product, and Bn is a constant, wherein:
B
1＝-8.151×10
-5 B
2＝2.570×10
-3 B
3＝-2.843×10
-2 B
4＝0.1218
2) obtain the inlet amount of CO according to computes:
Said corresponding propylene is meant the propylene that reacts with CO and consume, and is the measured data of device;
3) according to step 2) the excessive percentage ratio that calculates, calculate, adjustment synthetic gas inlet amount, make just different ratio and required just different than consistent butyraldehyde product.
3. method according to claim 2 is characterized in that, before said step 1), said method also comprises the utilization ratio of the propylene of the catalytic propylene production butyraldehyde of mensuration rhodium/triphenylphosphine technology.
4. according to any described method of claim 1～3, it is characterized in that said propylene catalytic preparation butyraldehyde is meant that the serialization under rhodium/triphenylphosphine catalyst action of propylene and synthetic gas carries out hydroformylation reaction and prepare the process of butyraldehyde; Wherein catalyzer constitutes (CO) (PPh of Rh (Acac)
3)/PPh
3
5. according to any described method of claim 1～3, it is characterized in that the reaction conditions of propylene catalytic preparation butyraldehyde is: temperature of reaction 353～393K, CO pressure component: 0.03～0.20MPa, H
2Pressure component: 0.15～0.90MPa, partial pressure of propylene power: 0.08～0.80MPa, the concentration of catalyzer Rh is 100～300ppm, TPP concentration is 5.0～15.0wt%.
6. according to the arbitrary described method of claim 1～5, it is characterized in that said excessive percentile variation range is 0.5%～7%, butyraldehyde-n is 15～3 with the ratio of isobutyric aldehyde in the then said product.
7. method according to claim 6 is characterized in that, said excessive percentile variation range is 0.5%～4%, and butyraldehyde-n is 12～5 with the ratio of isobutyric aldehyde in the then said product.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456154A (en) * | 2018-11-14 | 2019-03-12 | 成都欣华源科技有限责任公司 | A method of fatty aldehyde is prepared by hydroformylation reaction |
| CN111646883A (en) * | 2019-03-04 | 2020-09-11 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for preparing aldehyde by hydroformylation of low-carbon olefin |
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2011
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109456154A (en) * | 2018-11-14 | 2019-03-12 | 成都欣华源科技有限责任公司 | A method of fatty aldehyde is prepared by hydroformylation reaction |
| CN111646883A (en) * | 2019-03-04 | 2020-09-11 | 内蒙古伊泰煤基新材料研究院有限公司 | Method for preparing aldehyde by hydroformylation of low-carbon olefin |
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