CN103130623A - Reaction system and reaction method of gas-liquid double-circulation hydroformylation of preparing butyraldehyde with propylene - Google Patents
Reaction system and reaction method of gas-liquid double-circulation hydroformylation of preparing butyraldehyde with propylene Download PDFInfo
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- CN103130623A CN103130623A CN2011104000740A CN201110400074A CN103130623A CN 103130623 A CN103130623 A CN 103130623A CN 2011104000740 A CN2011104000740 A CN 2011104000740A CN 201110400074 A CN201110400074 A CN 201110400074A CN 103130623 A CN103130623 A CN 103130623A
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Abstract
The invention discloses a reaction system and a reaction method of gas-liquid double-circulation hydroformylation of preparing butyraldehyde with propylene. The reaction system further comprises a second reaction still which is arranged between a first reaction still and a stripping tower. The reaction method comprises introducing part of circulating airflow with the propylene in the first reaction still to the second reaction still to continue to react. The reaction system and the reaction method can effectively solve the problem that exhausted airflow contains the propylene, and improve the utilizing efficiency of the propylene.
Description
Technical field
The present invention relates to petrochemical industry, say further, relate to a kind of two recycle hydrogen formylation reaction systems of solution-air and reaction method of propylene producing butyladehyde.
Background technology
The hydroformylation reaction of propylene has important commercial significance.Utilize product that this reaction produces and derived product to reach millions of tons every year.Therefore updating of its production technology comes into one's own.
Industrial, be to adopt what is called " homogeneous catalysis " technology of rhodium-phosphine catalyst by the mainstream technology of propylene producing butyladehyde, be called again low pressure oxo process technology.The principal character of this class technology is that catalyzer is dissolved in solvent, makes propylene and synthetic gas (H2/CO) contact and react with catalyst solution continuously, then manages to allow reaction product and catalyst solution be separated and obtain the butyraldehyde product.
Existing many known technologies relate to the technological process of propene hydroformylation reaction.For example disclosed what is called " gas phase circulation " technique in US Patent No. 4247486, is characterized in that adopting a large amount of recycle gas that reaction product is shifted out with gaseous phase, and allow catalyst solution stay in reactor.
Disclosed what is called " liquid phase circulation " technique in US Patent No. 4148830 for another example; it is characterized in that reaction product is shifted out together with catalyst solution; with evaporation or distillation means, reaction product and catalyst solution are separated again, at last catalyst solution are looped back hydroformylation reaction district's continuation and use.
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 " RhodiumCatalyzed Hydroformylation " book.
In the hydroformylation process of propylene, improving the efficient of reactor and the utilising efficiency of raw material is the problem that needs special concern.According to the dynamic characteristic of reaction, thereby the propylene pressure that improves in reaction process can make speed of response increase the raising reactor efficiency, but excessive propylene needs the utilising efficiency of recycle guarantee raw material.
Disclose " the two circulations of solution-air " technique of a kind of propylene producing butyladehyde in Chinese patent CN95121416, it is characterized in that keeping higher partial pressure of propylene so that reactor efficiency is guaranteed at reaction zone.On the other hand, allow the supercharging equipment of propylene through the outside in the reactor gas phase carry out recirculation, allow simultaneously propylene in the reactor liquid phase through heating up and air lift is also carried out recirculation, thereby the utilization ratio of propylene is improved.The thick product of reaction after relief air lift carries out separating of product and catalyst solution, makes catalyst recirculation return reaction zone, so realizes the technique of a serialization.
Also having one in the continuous hydroformylation process of propylene, to need problems of concern be the discharging of rare gas element.Described rare gas element generally comprises methane, nitrogen, CO2 and propane etc.These compositions have plenty of raw material drawing-in system together, as in synthetic gas often with a small amount of methane, CO2, nitrogen etc.Some composition is mainly to be produced by side reaction, can generate propane as the hydrogenation reaction of propylene.In the process of a serialization, these inert fractions must emit from system and just can make device realize the stable state operation.
There is an obvious problem in aforementioned " solution-air two circulation " technique, is and improves reactor efficiency and need keep the partial pressure of propylene of reacting higher in gas phase, but can discharge together with propylene for the inert fraction in blowdown system.This will cause the loss of propylene that production cost is increased.Especially for large-scale industrial production, the propylene amount of so being discharged will be appreciable.
For solving the problem of carrying propylene in exhaust jet stream, can find some solutions in the prior art, for example the method for disclosed employing absorption process Propylene recovery in US Patent No. 4210426 and Chinese patent CN90106680 and CN91110549.But the shortcoming of these methods is propane together can be absorbed when absorbing propylene, if carry out making separating of propane and propylene method to become complicated again.
For another example, propose to set up the scheme of second reaction zone in English Patent GB1387657 and Chinese patent CN86101063, but the former is the scheme for the gas phase circulation technology, and the latter emphasizes to use two independent catalyst recirculation systems separately, and this will make flow process become complicated.
Summary of the invention
For solving the larger problem of propylene loss that exists in the gas-liquid binary cycle system in prior art, the invention provides a kind of two recycle hydrogen formylation reaction systems of solution-air and reaction method of propylene producing butyladehyde.Can effectively solve the problem of carrying propylene in exhaust jet stream, process efficiency is improved.
One of purpose of the present invention is to provide a kind of two recycle hydrogen formylation reaction of solution-air system of propylene producing butyladehyde.
Comprise the first reactor and gas stripping column, described reactive system also comprises the second reactor, and the second reactor is arranged between the first reactor and gas stripping column; Described the second reactor is the continuous flow stirring tank.
Two of purpose of the present invention is to provide a kind of two recycle hydrogen formylation reaction methods of solution-air of propylene producing butyladehyde.
Method of the prior art comprises following steps:
(1) raw material propylene and enter together the first reactor from synthetic gas and the catalyst solution of gas stripping column carries out hydroformylation reaction and generates butyraldehyde;
(2) reacted gaseous stream loops back reactor after the condensation compression; The portion gas discharging;
(3) reacted liquid phase stream enters gas stripping column and contacts with raw material of synthetic gas is reverse, synthetic gas is taken the unreacting material that dissolves in liquid phase stream out of and is entered in the lump the first reactor, and the liquid phase stream after air lift is sent into the subsequent disposal system as reacting coarse product;
Characteristics of the present invention are: the circulating current that the part in the first reactor gas phase is contained propylene is introduced the second reactor continuation reaction.
Concrete steps are:
From the gaseous stream of the first reactor extraction, part loops back the first reactor, and part is sent into the second reactor; Proceed hydroformylation reaction generation butyraldehyde from the gaseous stream of the first reactor and additional synthetic gas and catalyst solution in the second reactor; The second reactor extraction gaseous stream is after condensation, and gas phase is as exhaust emissions, liquid-phase reflux to the second reactor;
Enter gas stripping column after the second reactor extraction liquid phase stream and the merging of the first reactor extraction liquid phase stream.
The actual conditions of above-described hydroformylation reaction can use known condition of the prior art, and the temperature of reaction that can preferably adopt reactor in the present invention is 80 ℃-120 ℃, and reaction pressure is 1.0MPa-5.0MPa.
Specific embodiments is as follows:
(1) raw material propylene and enter together the first reactor from synthetic gas and the catalyst solution of gas stripping column is that 80-120 ℃ and pressure are to carry out hydroformylation reaction under the 1.0-5.0Mpa condition to generate butyraldehyde in temperature;
(2) from first one gaseous stream of reactor extraction, send into compressor boost after condensation, part loops back the first reactor afterwards, and part is sent into the second reactor;
(3) from first one liquid phase stream of reactor extraction, contact with synthetic gas and make unconverted unstripped gas put forward to enter in the lump the first reactor through being pumped into gas stripping column, after air lift, liquid phase is sent into the subsequent disposal unit;
(4) sending into together the second reactor from the gaseous stream of the first reactor and the synthetic gas and the catalyst solution that replenish, is that 80-120 ℃ and pressure are to proceed hydroformylation reaction under the condition of 1.0-5.0Mpa to generate butyraldehyde in temperature;
(5) from the second reactor extraction gaseous stream, after condensation gas phase as exhaust emissions, liquid-phase reflux to the second reactor; Enter gas stripping column after the second reactor extraction liquid phase stream and the merging of the first reactor extraction liquid phase stream.
Industrial, when adopting " continuous flow stirring tank " formula reactor (CSTR), need to make one's options between per pass conversion and reactor efficiency.Two kinds of ways are generally arranged:
1, low per pass conversion+circulation (being generally the separate unit reactor).
Advantage is: reactor efficiency is high;
Shortcoming is: circulation has increased expense, and the tail gas loss is large.
2, high per pass conversion+not (or few) circulation (being generally two above reactors in series).
Advantage is: nothing or the expense that circulates less, the tail gas loss is few
Shortcoming is: reactor efficiency is low, especially second reactor.
The present invention allows the part gas phase enter the second reactor on the basis of above-mentioned the 1st kind of selection, under the prerequisite that has kept high reactor efficiency, has solved the large problem of tail gas loss.This way is not better than above-mentioned two kinds of selections in the situation that the circulation expense is high.And " air lift circulation " mode that adopts in this technique a kind of low expense mode just.Therefore, the technical scheme that adopts the present invention to propose can improve the utilization ratio of propylene in the propene hydroformylation reaction process.Specifically, can make in prior art " the two circulations of solution-air " technique that the utilization ratio of propylene is guaranteed.This will bring considerable economic benefit for large-scale Industrial processes.
Description of drawings
The hydroformylation reaction system schematic of propylene producing butyladehyde in Fig. 1 prior art
The hydroformylation reaction system schematic of Fig. 2 propylene producing butyladehyde of the present invention
Description of reference numerals:
110-the first reactor; 210-the second reactor; The 310-gas stripping column;
The 1-propylene; The 2-catalyst solution; The 3-synthetic gas
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment:
As shown in Figure 2; the two recycle hydrogen formylation reaction of a kind of solution-air of propylene producing butyladehyde system; comprise the first reactor 110 and gas stripping column 310, described reactive system comprises that also the second reactor 210, the second reactors 210 are arranged between the first reactor 110 and gas stripping column 310.
Propylene 1 with enter the first reactor 110 together with the synthetic gas of gas stripping column 310 and catalyst solution 2.Described catalyst solution contains rhodium complex and triphenylphosphine ligand.Raw material is that 100 ℃ and pressure are to carry out hydroformylation reaction under the condition of 1.62Mpa to generate butyraldehyde in temperature under catalyst action.The gaseous phase outlet of the first reactor 110 is connected with condenser and compressor, loops back the first reactor 110 through the compressed machine supercharging of condensed gaseous stream rear section, and part enters the second reactor 210; The first reactor liquid-phase outlet is connected with pump and gas stripping column, and liquid phase stream enters gas stripping column 310 through pump, makes the unconverted raw material air lift of wherein dissolving enter the first reactor 110 to gas phase with reverse contact of synthetic gas 3 in tower.After air lift, liquid phase stream is sent into the subsequent disposal operation as thick product.Enter the second reactor 210 from the first reactor 110 outlet extension gaseous streams together with the synthetic gas that replenishes and catalyst solution.Unconverted raw material is to proceed hydroformylation reaction under the 1.62Mpa condition to generate butyraldehyde being 100 ℃ in temperature under the effect of catalyzer with pressure.The gaseous phase outlet of the second reactor 210 is connected with condenser, and condensed gas phase is discharged as reaction end gas, and liquid phase is returned to the second reactor 210.The second reactor 210 liquid-phase outlets are connected with pump, and liquid phase stream is sent into gas stripping column 310 with the liquid phase stream merging from the first reactor.
Gas chromatographic analysis is carried out in reaction end gas logistics and crude product stream sampling.The utilization ratio that can be calculated propylene by analytical results is 98%.
Comparative example:
Propylene 1 with enter the first reactor 110 together with the synthetic gas of gas stripping column 310 and catalyst solution 2.Described catalyst solution contains rhodium complex and triphenylphosphine ligand.Raw material is that 100 ℃ and pressure are to carry out hydroformylation reaction under the condition of 1.62Mpa to generate butyraldehyde in temperature under catalyst action.The gaseous phase outlet of the first reactor 110 is connected with condenser and compressor, through condensed gaseous stream partial discharge, loops back the first reactor 110 after the compressed machine supercharging of part.The liquid-phase outlet of the first reactor 110 is connected with pump and gas stripping column 310.Liquid phase stream enters gas stripping column 310 through pump.The liquid phase stream that is dissolved with unconverted raw material in tower contacts with synthesis gas stream 3 is reverse, and unconverted raw material is entered reactor by air lift to gas phase, and the liquid phase stream after air lift is thick product.Enter the subsequent disposal unit.
Gas chromatographic analysis is carried out in logistics and crude product stream sampling to reaction end gas.The utilization ratio that can be calculated propylene by analytical results is 94%.
This shows, adopt method of the present invention, can improve the utilization ratio of propylene.
Claims (4)
1. the two recycle hydrogen formylation reaction of the solution-air of propylene producing butyladehyde system, comprise the first reactor and gas stripping column, it is characterized in that:
Described reactive system also comprises the second reactor, and the second reactor is arranged between the first reactor and gas stripping column; Described the second reactor is the continuous flow stirring tank.
2. adopt the reaction method of the two circulating reaction systems of solution-air of propylene producing butyladehyde as claimed in claim 1, comprise following steps:
(1) raw material propylene and enter together the first reactor from synthetic gas and the catalyst solution of gas stripping column carries out hydroformylation reaction and generates butyraldehyde;
(2) reacted gaseous stream loops back reactor after the condensation compression; The portion gas discharging;
(3) reacted liquid phase stream enters gas stripping column and contacts with raw material of synthetic gas is reverse, synthetic gas is taken the unreacting material that dissolves in liquid phase stream out of and is entered in the lump the first reactor, and the liquid phase stream after air lift is sent into the subsequent disposal system as reacting coarse product;
It is characterized in that:
The circulating current that part in the first reactor gas phase is contained propylene is introduced the second reactor continuation reaction.
3. reaction method as claimed in claim 2 is characterized in that:
From the gaseous stream of the first reactor extraction, part loops back the first reactor, and part is sent into the second reactor; Proceed hydroformylation reaction generation butyraldehyde from the gaseous stream of the first reactor and additional synthetic gas and catalyst solution in the second reactor; The second reactor extraction gaseous stream is after condensation, and gas phase is as exhaust emissions, liquid-phase reflux to the second reactor;
Enter gas stripping column after the second reactor extraction liquid phase stream and the merging of the first reactor extraction liquid phase stream.
4. reaction method as claimed in claim 2 is characterized in that:
The temperature of reaction of described the second reactor is 80 ℃-120 ℃, and reaction pressure is 1.0MPa-5.0MPa.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015094813A1 (en) | 2013-12-19 | 2015-06-25 | Dow Technology Investments Llc | Hydroformylation process |
| 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 |
| US10407372B2 (en) | 2016-03-18 | 2019-09-10 | Dow Technology Investments Llc | Hydroformylation process |
| CN113387780A (en) * | 2021-07-26 | 2021-09-14 | 济南烟港技术咨询有限公司 | Method and system for producing butyraldehyde by liquid-phase two-stage circulation rhodium-method propylene hydroformylation |
| CN113956289A (en) * | 2021-10-12 | 2022-01-21 | 复旦大学 | Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction |
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| CN1131413A (en) * | 1993-09-20 | 1996-09-18 | 赫希斯特人造丝公司 | Two stage hydroformylation procedure |
| CN101293818A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Two-stage reaction method for mixed butylene hydroformylation |
| CN102826972A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for preparing aldehydes though hydroformylation of olefins |
| CN103012089A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for carbonyl synthesis of propylene |
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Patent Citations (4)
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| CN1131413A (en) * | 1993-09-20 | 1996-09-18 | 赫希斯特人造丝公司 | Two stage hydroformylation procedure |
| CN101293818A (en) * | 2007-04-28 | 2008-10-29 | 中国石油化工股份有限公司 | Two-stage reaction method for mixed butylene hydroformylation |
| CN102826972A (en) * | 2011-06-17 | 2012-12-19 | 中国石油化工股份有限公司 | Method for preparing aldehydes though hydroformylation of olefins |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015094813A1 (en) | 2013-12-19 | 2015-06-25 | Dow Technology Investments Llc | Hydroformylation process |
| US9695098B2 (en) | 2013-12-19 | 2017-07-04 | Dow Technology Investments Llc | Hydroformylation process |
| US10407372B2 (en) | 2016-03-18 | 2019-09-10 | Dow Technology Investments Llc | Hydroformylation process |
| 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 |
| CN113387780A (en) * | 2021-07-26 | 2021-09-14 | 济南烟港技术咨询有限公司 | Method and system for producing butyraldehyde by liquid-phase two-stage circulation rhodium-method propylene hydroformylation |
| CN113956289A (en) * | 2021-10-12 | 2022-01-21 | 复旦大学 | Nitrogen phosphine ligand, preparation method thereof and application thereof in aryl ethylene hydroformylation reaction |
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Application publication date: 20130605 |