CN102826970A - Two-stage reaction method and device of hydroformylation of low-carbon alkene - Google Patents
Two-stage reaction method and device of hydroformylation of low-carbon alkene Download PDFInfo
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Abstract
The invention relates to a two-stage reaction method and device for hydroformylation of low-carbon alkene. The method comprises that (1) low-carbon alkene and synthetic gas contact with a solution containing a catalyst in a first reactor equivalent to a full-mixing reaction theoretical stage at the temperature of 80-120 DEG C and pressure of 0.5-5.0MPa to generate aldehyde; and (2) the product flowing out of the first reactor enters a second reactor without separation and continues reacting under the conditions the same as those in the first reactor to obtain an aldehyde product, and supplementary synthetic gas serving a reaction raw material is respectively introduced to the second reactor according to the reaction progress of the alkene raw material, wherein the second reactor is a reactor equivalent to at least two full-mixing reaction theoretical stages. By adopting the two-stage reaction method for hydroformylation of low-carbon alkene provided by the invention, the efficiency of the second-stage reactor is effectively improved; and compared with a double stirring kettle process, a mechanical stirring device of the second reactor is omitted and the process flow is simple.
Description
Technical field
The present invention relates to field of chemical technology, specifically, relate to a kind of two-stage reaction method and device of low-carbon alkene hydroformylation.
Background technology
Utilize olefine in low carbon number historical through the existing years of development of the industrial technology of hydroformylation reaction system aldehyde.Current mainstream technology is that the employing rhodium-phosphine complex is what is called " low pressure oxo process " technology of catalyzer.Its major technique characteristic is: unstripped gas (alkene and synthetic gas (H2/CO)) contacts and reacts with the catalyst solution that contains rhodium-phosphine complex and free organic phosphine coordination body; Select certain condition that reaction is mainly occurred in the liquid phase main body, reaction process is controlled by intrinsic kinetics.Relating to this technique background document can be with reference to " the catalytic hydroformylation reaction of the rhodium " book by the common chief editor of gentle C. Clavel in the P.W.N.M.Van.
For analyzing prior art, the dynamic characteristic of understanding hydroformylation of olefin is very important.The generating rate of principal product and just, the selectivity of isomerized products (so-called just different ratio, note is made n/i) is very important, its influence factor is a lot of and relation is complicated.Wherein, the influence of two the most key factors can be described as: olefin partial pressures and the positive correlation of aldehyde generating rate, and reaction order is about one-level, and n/i is not almost had influence; The CO dividing potential drop is irregular normal distribution relation to the influence of aldehyde generating rate, and is then opposite during the high CO dividing potential drop of positive correlation during promptly low CO dividing potential drop, has peak between the two.The CO dividing potential drop is a negative correlation to the influence of n/i, promptly along with CO dividing potential drop rising n/i descends.About dynamic (dynamical) description also can be with reference to by " the Chim.Ind. (Milan) 1980; paper on 62,572 etc. that is published in such as auspicious in graceful " application of organometallic compound in homogeneous catalytic reaction " book of writing jointly of B. Kao Niersi and W.A. Hull and the P. slips except that above-mentioned document.
At present, the hydroformylation reaction of low-carbon alkene all adopts complete mixing flow formula reactor drum.This is because this type of reactor drum meets the serious practical situation of backmixing of liquid phase in the reaction on the one hand; It can satisfy aforementioned dynamic characteristic to the influence of CO dividing potential drop on the other hand; Promptly in the total overall reaction zone, effectively controlling the CO pressure component is certain value, so that the reaction result that obtains expecting.When selecting this type of reactor drum, adopting continuous flow stirring tank formula (CSTR) gas-liquid reaction device is a kind of preferred way.This is because the transmittance process that the effect of whisking appliance can make reaction follow is strengthened, thereby can make the intrinsic speed of response be selected in higher level.
Yet pointed as the reaction apparatus general theory, the shortcoming that adopts the CSTR reactor drum is that the efficient of separate unit reactor drum is lower.This can find detailed demonstration in relevant textbook.Therefore how improving reaction efficiency is the focus that those skilled in the art pay close attention to; With regard to hydroformylation reaction, two kinds of ways of raising the efficiency are arranged at present, a kind of way is to adopt one section reactive mode; Control lower alkene per pass conversion, unconverted alkene is carried out recycle; Another kind of way is to adopt two-stage reaction method, lets first section unconverted alkene continue reaction at second section, reduces internal circulating load.The visible U.S. Pat 4247486 of typical technology scheme that belongs to the former, US5426238 etc.The technical scheme that belongs to the latter can be with reference to English Patent GB1387657 and Chinese patent CN86101063 etc.
In adopting the technical scheme of one section reaction, for making a large amount of unconverted olefin Returning reactors, need separate and need be reaction product to isolated unconverted olefin supercharging, this will cause the further increase of the complicated and power consumption of technical process.
And the technical scheme of employing two-stage reaction method, the problem that second section reaction efficiency that demand side causes descending with concentration of olefin further descends for addressing this problem, has proposed a kind of two-stage reaction method of hydroformylation in the U.S. Pat 5105018.First section is adopted the CSTR reactor drum, and this conversion zone has the gas phase circulation and the liquid phase recycle system of self.In one section gas phase circulation loop, draw one streams that contains the art converted olefin and send into second section continuation reaction.Second section is adopted plug flow reactor, also has the gas phase and the liquid phase recycle system of self, and wherein the liquid phase recycle system is connected with first section.This patent is pointed out to have adopted plug flow reactor to improve efficient owing to second section.
The problem of this scheme is that two-stage reaction needs the independent recycle system, and the separating unit that needs between other two sections makes flow process complicated.In addition, to second section reaction,, judge so can't whether improve accurately to reaction efficiency owing to only disclose band round-robin reaction result data.
Other a kind of low-carbon alkene hydroformylation two-stage reaction method has been proposed among the Chinese patent CN94193456; The gas phase circulation technology is adopted in first section reaction in the tool, and so-called " slug flow " reactor drum has been adopted in second section reaction, and obviously this scheme has been noticed second section reaction if adopt the complete mixing flow reactor drum; Can cause lower efficient; But in order to realize the imagination of " slug flow ", this Scheme Choice baroque row cast reactor, in addition; Other ways of this scheme adopt gas phase circulation technology etc. as first section, also are the not high ways of efficient.
To above-mentioned defective, the purpose of this invention is to provide a kind of low-carbon alkene hydroformylation two-part reaction method and device.
Summary of the invention
In prior art; The low efficiency problem that the hydroformylation reaction of low-carbon alkene adopts the complete mixing flow reactor drum to be brought; Especially the problem that further descends to efficient in second section reaction of two-stage reaction; According to the dynamic characteristic of the hydroformylation reaction of low-carbon alkene, the purpose of this invention is to provide a kind of method and apparatus of two-stage reaction.
By aforementioned known; Dynamic characteristic according to hydroformylation reaction can draw such judgement with relevant reaction apparatus principle; Promptly the most effectively the hydroformylation reaction method is to adopt the complete mixing flow reactor drum of a plurality of serial operations; Yet this will strengthen investment and process cost because of increasing number of devices undoubtedly.
In view of the above, it is following to propose main points of the present invention:
The method of the hydroformylation second-stage reaction of low-carbon alkene of the present invention comprises
(1) low-carbon alkene and synthetic gas contact with the solution that contains catalyzer under temperature 80-120 ℃ of pressure 0.5-5.0Mpa condition in first reactor drum and generate aldehyde; Wherein said first reactor drum is to be equivalent to a full reactor drum that mixes the reaction theory level; And the transformation efficiency of low-carbon alkene in said first reactor drum is preferably greater than 60% greater than 50%;
(2) product that flows out from first reactor drum gets into second reactor drum without separating, and in the condition and range identical with first reactor drum, continues reaction and obtains the aldehyde product; Wherein, said second reactor drum is to be equivalent at least two full reactor drums that mix the reaction theory level, introduces said second reactor drum as the additional synthetic gas of reaction raw materials respectively by the reaction process of olefin feedstock simultaneously.
Wherein, The said full number that the reaction theory level is meant the complete mixing flow reactor drum of the serial operation of describing in the general chemical reactor textbook in this area of mixing; Be that single complete mixing flow reactor drum provides a theoretical stage; The complete mixing flow reactor drum of two and two above serial operations provides two and two above theoretical stages, and " perfectly mixed reactor " is meant a kind of ideal type of reactor, and " theoretical stage " described in the present invention is meant the ideal response result that can reach according to full blended ideal model.(principal character is: liquid phase does not have temperature and concentration gradient).But with theoretic ideal reactor difference is arranged because actual reaction apparatus is general; Therefore; First reactor drum of the present invention be equivalent to a full reactor drum that mixes the reaction theory level be meant said first reactor drum be those skilled in the art think can be applied to industry or breadboardly can reach a full reactor drum that mixes the reaction theory level, like common stirring tank, high pressure stirring tank, continuous flow stirring tank formula (CSTR) gas-liquid reaction device etc.; Second reactor drum of the present invention be at least two full reactor drums that mix the reaction theory levels be meant said second reactor drum be those skilled in the art think can be applied to industry or breadboardly can reach at least two full reactor drums that mix the reaction theory levels, like multistage bubbling column reactor (Multi-Stage Bubble Columns); This type of reactor drum is belt stirrer not, and is simple in structure, and manufacturing and process cost are low.The relatively low situation of speed of reaction when especially being suitable for second section reaction of hydroformylation.Multistage bubbling column reactor is existing successful Application in industry; Representational example have application in F-T synthesis reaction (consult: Maretto C., " Catalysis today " 2001,66:241-248); And the application in desulphurization reaction (is consulted: Meikap B C.; " Chemical Engineeering J., " 2002,86:331-342).
Therefore; The present invention proposes to adopt following method to realize especially: adopt the first section reactor drum of separate unit complete mixing flow formula reactor drum as hydroformylation; Adopt the second section reactor drum of multistage complete mixing flow formula reactor drum as hydroformylation, with the dynamic characteristic that effectively utilizes this reaction more so that the efficient of reaction be improved.
Especially, said multistage complete mixing flow formula reactor drum is multistage bubbling column reactor.
Said additional synthetic gas is introduced reactor drum respectively by the reaction process of olefin feedstock and is meant at least two synthetic gas opening for feeds are provided; Wherein first opening for feed provides additional raw material of synthetic gas for the unconverted olefin of directly coming from first reactor drum, and other synthetic gas opening for feeds provide raw material of synthetic gas for the material that passes through partial reaction.
Among the present invention, said low-carbon alkene is meant C2-C4 alkene.
The invention has the beneficial effects as follows:
Adopt the two-stage reaction method of the low-carbon alkene hydroformylation of the present invention's proposition; Can improve second section reactor efficiency effectively; Compare with two stirring tank technologies, saved the mechanical stirring device of second reactor drum, this can make equipment, energy consumption and process cost reduce.When final transformation efficiency was identical with two still technologies, the TV efficient of reactor drum can improve; When the TV of reactor drum was identical with two still technologies, the propylene per pass conversion can be improved.Compare and have middle isolating two-stage reaction method with other, the scheme that the present invention proposes, technical process is comparatively simple.
Description of drawings
Fig. 1 is the device synoptic diagram of the embodiment of the invention, and wherein R1 is first reactor drum; E1 is an external cooler; R2 is second reactor drum; E2 is a condensing surface; 1-alkene; 2, the 6-synthetic gas; The 3-catalyst solution; The 4-first reactor drum vapor phase product stream; 5-first reactor drum liquid product stream; The 7-reaction end gas; 8-liquid product stream.The synthetic gas opening for feed number of the second reactor drum side is not limited to three among the figure.
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.
Below in conjunction with accompanying drawing the present invention is described further.
Shown in accompanying drawing 1, alkene (1), synthetic gas (2) and catalyst solution (3) are admitted to the first reactor drum R1.This reactor drum is a continuous flow stirring tank.Hydroformylation reaction in temperature 80-120 ℃, takes place and generates butyraldehyde under the effect of catalyzer in raw material under the pressure 0.5-5MPa condition.An external cooler E1 is used to remove exothermic heat of reaction.Obvious first reactor drum is equivalent to a full reaction theory level of mixing.First reactor drum has a gaseous phase outlet and a liquid phase outlet, causes the second reactor drum R2 in order to the logistics that will contain unreacting material, reaction product and catalyst solution by first reactor drum.Second reactor drum is a multistage bubbling column reactor (being three grades) among the figure.With regard to each level, opening for feed and one group of spiral coil cooling tube that is used to remove exothermic heat of reaction that is used to introduce synthetic gas (6) is set.In reactor drum R2, unconverted raw material continues under the effect of catalyzer, hydroformylation reaction to take place with the synthetic gas that replenishes and generates butyraldehyde.Multistage bubbling column reactor lets reaction reach more than two full effects of mixing the reaction theory level.Be provided with condensing surface E2 on the top of reactor drum R2, the reaction end gas (7) of process condensation is discharged, and liquid product stream (8) is admitted to the subsequent disposal unit.
Embodiment 1
Use a volume as 2L and the autoclave that has a mechanical stirrer as first reactor drum; Use a diameter to be 56mm; Height is 510mm; Not with the tower reactor of mechanical stirrer as second reactor drum, also comprise external cooler and water cooler, form two sections hydroformylation reaction systems thus and carry out the reaction of propylene producing butyladehyde.First reactor drum is provided with opening for feed and the gas phase discharge port and the liquid phase discharge port of propylene, synthetic gas and catalyst solution; The reaction mass part that the liquid phase discharge port is drawn gets into second reactor drum; All the other are got back in first reactor drum after removing reaction heat through external cooler, and the gas phase discharge port directly is connected with the opening for feed of the second reactor drum lower end.
Be horizontally disposed with 6 perforated baffles in second reactor drum, baffle plate is uniform distribution, tower still and every corresponding introducing that the additional synthetic gas of a synthetic gas charging confession is set in baffle plate top vertically in tower.Wherein first opening for feed provides additional raw material of synthetic gas for the unconverted olefin of directly coming from first reactor drum; And other synthetic gas opening for feeds are at first section; Or comprise that further second section material through partial reaction provides raw material of synthetic gas, be provided with a pneumatic outlet and a liquid exit that supplies the extraction liquid-phase product that supplies discharging tail gas in second reactor drum upper end.Second inside reactor is provided with spiral coil cooling tube and supplies shifting out of reaction heat.
On entering/discharging pipeline, be provided with the collection of sampling confession analytic sample.
Two reactor drums move by following operational condition continuously:
| Temperature of reaction (℃) | Reaction pressure (Mpa) | Rhodium concentration (ppm) | Triphenylphosphine concentration (wt%) | |
| First reactor drum | 90 | ?1.9 | ?250 | 12 |
| Second reactor drum | 90 | ?1.8 | ?250 | 12 |
Can calculate through sampling analysis: propylene conversion is that the total conversion rate of 78.0%, two reactor drum is that the TV of 93.5%, two reactor drum is 3.26L in first reactor drum when the first reactor feed propylene is 210g/h.
Comparative Examples 1
Second reactor drum among the embodiment 1 is changed into and the identical mechanical stirring autoclave of first reactor drum, and according to carrying out the serialization hydroformylation reaction of propylene producing butyladehyde with example 1 identical reaction conditions.
Can calculate when the first reactor feed propylene is 210g/h through sampling analysis, propylene conversion is that the TV that 78.0%, two reactor drum total conversion rate is 93.0%, two reactor drum is 4L in first reactor drum.
This shows, the two-stage reaction method that adopts the present invention to propose, the TV that second reactor drum has saved mechanical stirring and reactor drum is decreased to 3.26L by 4L.Calculate the long-pending efficient of overall reactor by this and improved 18.5%.
Comparative Examples 2
Change second reactor drum of embodiment 1 into the churned mechanically 400ml high pressure of being with of three serial operations tank reactor, the identical and TV of the volume of three stirring tanks is near the volume of second reactor drum among the embodiment 1.This reactive system is according to carrying out the serialization hydroformylation reaction of propylene producing butyladehyde with routine 1 the same terms.
Can calculate when the first reactor feed propylene is 210g/h through sampling analysis, propylene conversion is that the propylene total conversion rate of 78.0%, 4 reactor drum is 93.2% in first reactor drum, and the TV of reactor drum and embodiment 1 are close.
This shows that in the two-stage reaction method that the present invention proposes, second reactor drum is equivalent to the stirring tank of three serial operations, promptly be equivalent to three full reaction theory levels of mixing.
Embodiment 2
The height of second reactor drum among the embodiment 1 is increased to 800mm, and diameter is constant, in establish perforated baffle plate number and increase to 10, increase synthetic gas import simultaneously corresponding to every baffle plate.Rest part is constant and according to advancing the serialization hydroformylation reaction of propylene producing butyladehyde with example 1 identical reaction conditions.
Can calculate when the first reactor drum propylene feed amount is 210g/h through sampling analysis; Propylene conversion is 78.0% in first reactor drum; And when adopting two stirring tanks in the TV of two reactor drums and the Comparative Examples 1 under the essentially identical situation of TV, the propylene total conversion rate is increased to 96.8% by 93.0%.
Claims (5)
1. the method for the hydroformylation two-stage reaction of a low-carbon alkene is characterized in that, comprising:
(1) low-carbon alkene and synthetic gas contact with the solution that contains catalyzer under temperature 80-120 ℃ of pressure 0.5-5.0Mpa condition in first reactor drum and generate aldehyde; Wherein said first reactor drum is to be equivalent to a full reactor drum that mixes the reaction theory level, and the transformation efficiency of low-carbon alkene in said first reactor drum is greater than 50%;
(2) product that flows out from first reactor drum gets into second reactor drum without separating, and in the condition and range identical with first reactor drum, continues reaction and obtains the aldehyde product; Wherein, said second reactor drum is to be equivalent at least two full reactor drums that mix the reaction theory level, introduces said second reactor drum as the additional synthetic gas of reaction raw materials respectively by the reaction process of olefin feedstock simultaneously.
2. method according to claim 1 is characterized in that, the said reactor drum that is equivalent to a complete mixed reaction theory level is a stirring tank.
3. method according to claim 1 and 2 is characterized in that, said the reactor drum of at least two theoretical stages can be provided is multistage bubbling column reactor.
4. according to the arbitrary described method of claim 1-3; It is characterized in that; Said additional synthetic gas is introduced reactor drum respectively by the reaction process of olefin feedstock and is meant at least two synthetic gas opening for feeds are provided; Wherein first opening for feed provides additional raw material of synthetic gas for the unconverted olefin of directly coming from first reactor drum, and other synthetic gas opening for feeds provide raw material of synthetic gas for the material that passes through partial reaction.
5. method according to claim 1 is characterized in that, the transformation efficiency of said low-carbon alkene in said first reactor drum is greater than 60%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108273453A (en) * | 2017-11-28 | 2018-07-13 | 聊城市鲁西化工工程设计有限责任公司 | A kind of hydroformylation synthesizer reaction heat taking method |
| CN108586219A (en) * | 2018-06-28 | 2018-09-28 | 南京荣欣化工有限公司 | A kind of method that hydroformylation of olefin prepares aldehyde |
| CN111153782A (en) * | 2019-12-31 | 2020-05-15 | 南京中设石化工程有限公司 | Method for preparing high-carbon aldehyde by hydroformylation of high-carbon olefin |
| US10843992B2 (en) | 2017-06-23 | 2020-11-24 | Dow Technology Investments Llc | Hydroformylation reaction process |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10843992B2 (en) | 2017-06-23 | 2020-11-24 | Dow Technology Investments Llc | Hydroformylation reaction process |
| CN108273453A (en) * | 2017-11-28 | 2018-07-13 | 聊城市鲁西化工工程设计有限责任公司 | A kind of hydroformylation synthesizer reaction heat taking method |
| CN108586219A (en) * | 2018-06-28 | 2018-09-28 | 南京荣欣化工有限公司 | A kind of method that hydroformylation of olefin prepares aldehyde |
| CN111153782A (en) * | 2019-12-31 | 2020-05-15 | 南京中设石化工程有限公司 | Method for preparing high-carbon aldehyde by hydroformylation of high-carbon olefin |
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