CN101955421B - Method for preparing propaldehyde by external circulation extractive distillation method - Google Patents
Method for preparing propaldehyde by external circulation extractive distillation method Download PDFInfo
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- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 238000000034 method Methods 0.000 title claims abstract description 45
- 238000000895 extractive distillation Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
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- 239000002994 raw material Substances 0.000 claims abstract description 46
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000011084 recovery Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
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- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 235000011187 glycerol Nutrition 0.000 claims abstract description 6
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 5
- 239000010948 rhodium Substances 0.000 claims abstract description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000000926 separation method Methods 0.000 claims abstract description 5
- 238000000605 extraction Methods 0.000 claims description 47
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 11
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 11
- 238000009833 condensation Methods 0.000 claims description 7
- 230000005494 condensation Effects 0.000 claims description 7
- 230000004907 flux Effects 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 241000282326 Felis catus Species 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 4
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- 239000000376 reactant Substances 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 6
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 239000005977 Ethylene Substances 0.000 abstract description 3
- 238000010533 azeotropic distillation Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract 2
- 229910002090 carbon oxide Inorganic materials 0.000 abstract 2
- 150000001299 aldehydes Chemical class 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 10
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000839 emulsion Substances 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- ULGZDMOVFRHVEP-RWJQBGPGSA-N Erythromycin Chemical compound O([C@@H]1[C@@H](C)C(=O)O[C@@H]([C@@]([C@H](O)[C@@H](C)C(=O)[C@H](C)C[C@@](C)(O)[C@H](O[C@H]2[C@@H]([C@H](C[C@@H](C)O2)N(C)C)O)[C@H]1C)(C)O)CC)[C@H]1C[C@@](C)(OC)[C@@H](O)[C@H](C)O1 ULGZDMOVFRHVEP-RWJQBGPGSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
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- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 1
- IDEYZABHVQLHAF-UHFFFAOYSA-N 2-methylpent-2-enal Chemical class CCC=C(C)C=O IDEYZABHVQLHAF-UHFFFAOYSA-N 0.000 description 1
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 description 1
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- 229930040373 Paraformaldehyde Natural products 0.000 description 1
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- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- PWGQHOJABIQOOS-UHFFFAOYSA-N copper;dioxido(dioxo)chromium Chemical compound [Cu+2].[O-][Cr]([O-])(=O)=O PWGQHOJABIQOOS-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940124447 delivery agent Drugs 0.000 description 1
- NIJJYAXOARWZEE-UHFFFAOYSA-N di-n-propyl-acetic acid Natural products CCCC(C(O)=O)CCC NIJJYAXOARWZEE-UHFFFAOYSA-N 0.000 description 1
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 1
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- SGGOJYZMTYGPCH-UHFFFAOYSA-L manganese(2+);naphthalene-2-carboxylate Chemical compound [Mn+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 SGGOJYZMTYGPCH-UHFFFAOYSA-L 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
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- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 description 1
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- DBABZHXKTCFAPX-UHFFFAOYSA-N probenecid Chemical compound CCCN(CCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 DBABZHXKTCFAPX-UHFFFAOYSA-N 0.000 description 1
- 229960003081 probenecid Drugs 0.000 description 1
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- 229940084026 sodium valproate Drugs 0.000 description 1
- AEQFSUDEHCCHBT-UHFFFAOYSA-M sodium valproate Chemical compound [Na+].CCCC(C([O-])=O)CCC AEQFSUDEHCCHBT-UHFFFAOYSA-M 0.000 description 1
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- OMOMUFTZPTXCHP-UHFFFAOYSA-N valpromide Chemical compound CCCC(C(N)=O)CCC OMOMUFTZPTXCHP-UHFFFAOYSA-N 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing propaldehyde by an external circulation extractive distillation method, which takes the mixture of synthesis gas and ethylene as a raw material, wherein the weight ratio of the synthesis gas to the ethylene is 2.0-10.0:1; the synthesis gas is the mixed gas of hydrogen and carbon oxide; the mass flow rate of the hydrogen to the carbon oxide is 1:2.5.28; the raw material and organic extracting agent glycerin respectively enter into a reaction extractive distillation device, rhodium complex is taken as catalyst, and heating is carried out; the product at the top of a tower is condensed to obtain gas-liquid mixture; the gas-liquid mixture is performed with the gas-liquid separation, the gas is recycled to the raw material, the liquid is aldehyde;mixed liquor at the bottom of the tower is fed to a recovery tower; and the catalyst and the organic extracting agent `are recovered and recycled. The method uses one reaction extractive distillationdevice to finish the preparation and purification of the propaldehyde, the concentration of the propaldehyde can reach 99.5%, and the yield can reach more than 98.5%. The process flow is simple, the purity and productivity of the propaldehyde are both high, and the energy consumption is saved by about 40% compared with that of the method combing reaction and azeotropic distillation.
Description
Technical field
The present invention relates to the method that a kind of outer circulation overflow reaction, extraction rectification method prepares propionic aldehyde, in same reaction, extraction rectifier unit, finish the synthetic and purification of propionic aldehyde.
Background technology
Propionic aldehyde is a kind of important Chemicals and industrial chemicals, and at rubber, plastics, paint, medicine, particularly the aspect such as agricultural chemicals and feed is of many uses.Take cobalt naphthenate, manganese naphthenate, neutralized verdigris, cupric chromate etc. as catalyzer, about temperature 60 C, the propionic acid that propionic aldehyde carries out atmospheric pressure oxidation reaction production is a kind of important fine chemicals, also is the important intermediate of producing other fine chemicals, and purposes is very extensive.China's propionic aldehyde output is relatively low, can not satisfy the demand of propionic aldehyde series product processing, has affected the development of derived product, along with the development of the industries such as medicine, food, and will be increasing to the demand of propionic aldehyde, propionic acid and derivative thereof.Propionic aldehyde and Paraformaldehyde 96 are raw material, under alkaline condition the heating make 1,1, the 1-trimethylolethane can be used to make varnish, Synolac, amino-alkyd baking finiss and vibrin, synthetic drying oil etc.Propionic aldehyde and formaldehyde reaction get the dihydroxymethyl propionic aldehyde, can make dimethylol propionic acid with hydrogen peroxide oxidation again, and it is mainly as the good stable agent of polyaminoester emulsion, and the emulsion shelf lives can be by less than extending to half a year more than 1 year after adding.
By the propyl alcohol that propionic aldehyde gets through Hydrogenation, in medicine industry, can be used for producing probenecid, Sodium Valproate, erythromycin, valpramide, BCA BCA, proglumide, 2,5-dinicotinic acid dipropyl etc.Propionic aldehyde is a kind of important organic synthesis intermediate through the 2-methyl 2-pentenals that condensation obtains, and is widely used in organic synthesis.In addition, propionic aldehyde also is widely used in the monomer of producing aliphatic hydrocarbon, polyoxide, amine etc., as plastics, rubber processing aids, dye additive, polymer chain delivery agent and emulsion stabilizer etc.
Propionic aldehyde has been developed many kinds of preparation methods since 20th century, realized suitability for industrialized production the eighties.Industrial process mainly contains oxo synthesis, propyl alcohol oxidation style, propylene oxide isomerization method, propenal hydrogenation method and by-product method at present.Wherein oxo synthesis is the main method of present industrial production propionic aldehyde.In carbonylation processes, the complex catalysts such as proposition employing rhodium carry out the aqueous catalysis reaction, the mixing raw material gas of ethene etc. passes in the liquid phase of reaction, extraction rectifier unit continuously, under constantly stirring, generated propionic aldehyde by catalyzed reaction and enter continuously in the water separation of oil device with the immiscible material of catalyzer etc., isolated aqueous-phase reflux is to the reaction, extraction rectifier unit, and isolated oil phase is thick propionic aldehyde, adopts component distillation to process thick propionic aldehyde and obtains 98% propionic aldehyde.Adopt ethene, synthetic gas and complex catalyst to carry out the aqueous catalysis reaction, reaction time is long, and the propionic aldehyde water content that obtains needs just can obtain 99.5% propionic aldehyde through azeotropic distillation and other dewatering.In a word, highly purified propionic aldehyde preparation, operation is many, the cycle is long, energy consumption is large.
Summary of the invention
The objective of the invention is to overcome the deficiency of traditional method, a kind of new propionic aldehyde production technology is provided: outer circulation reaction, extraction rectification method prepares the method for propionic aldehyde, finish preparation and the purification of propionic aldehyde in a tower, the purity of propionic aldehyde is reached more than 99.5%, the yield of propionic aldehyde reaches more than 98.5%.
The technical scheme of finishing the foregoing invention task is: take a certain proportion of ethene and synthetic gas as raw material, employing glycerine is that organic extractant, rhodium complex are catalyzer, and the concentration of the propionic aldehyde of preparation can reach more than 99.5%.Concrete flow process is:
A kind of outer circulation reaction, extraction rectification method prepares the method for propionic aldehyde, the steps include:
Raw material is the mixture of synthetic gas and ethene, and wherein the mass ratio of synthetic gas and ethene is 2.0-10.0:1; Described synthetic gas is the mixed gas of hydrogen and carbon monoxide; Wherein the mass flux ratio of hydrogen and carbon monoxide is 1:2.5-2.8;
Raw material and organic extractant glycerine enter respectively reaction, extraction rectifier unit (be also referred to as the reaction, extraction rectifying tower, or be called for short tower), and rhodium complex is catalyzer, heating;
This reaction, extraction rectifier unit top product obtains gas-liquid mixture through after the condensation;
Described gas-liquid mixture is through gas-liquid separation, and gas circulation is to raw material, and liquid is propionic aldehyde;
Mixed solution is sent into catalyzer and organic extractant recovery tower at the bottom of the reaction, extraction rectifier unit, reclaims catalyzer and organic extractant, and recycles.
Flow in the raw material in the ethene adding tower is 14-16mL/min.
The application recommends following optimization data: in the raw material, the mass ratio of synthetic gas/ethene is 2.2:1, and in the synthetic gas, the mass rate of hydrogen/carbon monoxide is made as 1:2.67, the mass ratio of raw material/organic extractant circular flow is made as 1:2, and the mass ratio of catalyzer/organic extractant reaches 1.5:20.
Ethene adds the interior flow of tower all by 15mL/min in the raw material.
Say that more specifically and more optimally reactions steps of the present invention is as follows:
Raw material adds from the underfeed mouth through volume pump, and the reaction, extraction rectifier unit is through temperature control heating jacket heated for controlling temperature, and organic extractant (glycerine) and catalyzer are from adding more than the packing section; Synthetic gas, ethene fully contact with organic extractant and catalyzer adverse current and generate the product propionic aldehyde in the reaction, extraction rectifier unit; Product propionic aldehyde and excessive unstripped gas process reaction, extraction rectifier unit evaporator overhead condenser condensation through gas-liquid separator separates, obtain 99.5% above propionic aldehyde, and residual gas is circulated to raw material.Organic extractant, catalyzer and a small amount of reactant two polyacetals and water form together discharge hole for discharge at the bottom of the reaction, extraction rectifier unit, through lift pump, deliver to organic extractant and catalyst recovery tower; Recovery tower is a rectifying tower; Recovery tower is through the heating of temperature control heating jacket, and low-boiling point material is discharged from the cat head discharge port, is collected by condensing collector after condenser condenses; Discharging obtains at the bottom of catalyzer and the organic extractant tower, delivers to organic extractant and catalyst feeds, recycle through recycle pump.
Advantage of the present invention is: can finish preparation and the purification of propionic aldehyde with a tower.The concentration of propionic aldehyde can reach 99.5%, and yield reaches more than 98.5%.This technical process is simple, and the purity of propionic aldehyde and productive rate are all very high, and energy consumption has also been saved about 40% than the method for reaction and azeotropic distillation combination.
Description of drawings
Fig. 1 is the process flow sheet that outer circulation reaction, extraction rectification method prepares propionic aldehyde, wherein: wherein 1, volume pump; 2, lift pump; 3, condenser; 4, condensing collector; 5, reaction, extraction rectifier unit; 6, temperature control heating jacket; 7, lift pump; 8, condenser; 9, condensing collector; 10, solvent recovery tower; 11, temperature control heating jacket.
Fig. 2, Fig. 3, Fig. 4 and Fig. 5 are respectively the mass ratio of mass ratio, temperature of reaction ethene/synthetic gas of mass ratio, the catalyzer/organic solvent of synthetic gas/ethene to the curve of propionic aldehyde content influence.
Embodiment
The mass ratio of synthetic gas/ethene is on the impact of propionic aldehyde yield, with reference to Fig. 2:
The tower reactor temperature is controlled at about 83 ℃.The mass ratio of catalyzer/organic solvent is 1.5:20, the mass ratio of raw material/organic solvent circular flow is made as 1:2, by Fig. 2 result as seen: along with the mass ratio increase of synthetic gas/ethene, propionic aldehyde content increases gradually, when the mass ratio of synthetic gas/ethene reaches 2.2:1, the content of propionic aldehyde is little, so according to the reaction needed of reality, the mass ratio of getting synthetic gas/ethene is 2.2:1.
The mass ratio of catalyzer/organic solvent is on the impact of propionic aldehyde yield, with reference to Fig. 3:
The selective reaction temperature is 83 ℃.When the mass ratio of getting synthetic gas/ethene is 2.2:1, the mass ratio of raw material/organic solvent circular flow is made as 1:2, by Fig. 3 result as seen: under the condition of the mass ratio of different catalysts/organic solvent, when the mass ratio of catalyzer/organic solvent reached 1.5:20, the productive rate of propionic aldehyde remained unchanged substantially.So the mass ratio of catalyzer/organic solvent is got 1.5:20.
Temperature of reaction is on the impact of propionic aldehyde yield, with reference to Fig. 4:
The temperature of cat head is controlled at about 48 ℃.When the mass ratio of getting synthetic gas/ethene is 2.2:1, the mass ratio of catalyzer/organic solvent is 1.5:20, the mass ratio of raw material/organic solvent circular flow is made as 1:2, by Fig. 4 result as seen: under the different temperature of reaction, the content of propionic aldehyde has certain variation, according to the reaction needed of reality, the selective reaction temperature is 83 ℃.
The mass ratio of raw material/organic solvent is on the impact of propionic aldehyde yield, with reference to Fig. 5:
The temperature of cat head is controlled at about 48 ℃, and correspondingly, the reactor bottom temperature is controlled at about 83 ℃.When the mass ratio of getting synthetic gas/ethene is 2.2:1, the mass ratio of catalyzer/organic solvent is 1.5:20, the mass ratio of raw material/organic solvent circular flow is made as four of 1:1,1:1.5,1:2,1:2.5, by Fig. 5 result as seen: different speed of circulation is than lower, content to propionic aldehyde has certain influence, according to the reaction needed of reality, select the mass ratio of raw material/organic solvent circular flow to be made as 1:2.
Step is: raw material 1. (ethene and synthetic gas) enters the reaction, extraction rectifier unit through 1 volume pump through opening for feed, and the opening for feed of raw material is located at the 31st column plate place of reaction, extraction rectifier unit; Reaction, extraction device 5 is through 6 temperature control heating jacket heated for controlling temperatures, and catalyzer and organic extractant (being collectively referred to as reagent 2.) add from the middle part of reaction, extraction rectifier unit, and its opening for feed is located at the 6th column plate place of reaction, extraction rectifier unit.Reaction, extraction rectifier unit 5 Raw gases fully contact with organic extractant and extraction agent adverse current and generate the product propionic aldehyde.Dimerization propionic aldehyde and the water of product propionic aldehyde and excessive reaction raw materials, trace, through the organic extractant extracting and separating, product propionic aldehyde and excessive synthesis gas are discharged from device top discharge port because relatively volatile.Device top gas body is through condenser condenses, and condensing collector is collected and obtained 3., and 1. uncondensed gas is circulated to raw material.4. organic extractant, catalyzer and a small amount of dimerization propionic aldehyde and water have formed together from the device discharge hole for discharge, through lift pump 7, arrive solvent recovery tower 10.Solvent recovery tower is a rectifying tower.Recovery tower 10 is through 11 heating of temperature control heating jacket, and 5. low-boiling point material discharges from the cat head discharge port, is collected by condensing collector 9 after condenser 8 condensations; 6. discharging obtains at the bottom of catalyzer and the organic extractant tower, delivers to organic extractant and catalyst feeds, recycle through recycle pump.
The operational condition of table 1 outer circulation reaction, extraction rectification process
| The charging parameter | The reaction, extraction rectifier unit | Solvent recovery tower |
| Column bottom temperature ( OC) | 80－82 | 102-115 |
| Tower top temperature ( OC) | 47－49 | 49－87 |
| Reflux ratio, R | 3－4 | 3－4 |
| Stage number, N | 35 | 41 |
| Reaction-ure feeding mouth (N f） | 31 | 23 |
| Catalyzer and organic extractant opening for feed (N S） | 6 | － |
Table 2 reaction, extraction rectifying separating resulting
The mass ratio of synthetic gas and ethene is 2.0:1 in the raw material;
The mass flux ratio of hydrogen and carbon monoxide is 1:2.5 in the synthetic gas;
The flow that ethene adds in the tower in the raw material is pressed 14mL/min.
The mass ratio of synthetic gas and ethene is 2.4:1 in the raw material;
The mass flux ratio of hydrogen and carbon monoxide is 1:2.8 in the synthetic gas;
The flow that ethene adds in the tower in the raw material is pressed 16mL/min.
Embodiment 4, and is substantially the same manner as Example 1, but following change is arranged:
The mass ratio of synthetic gas and ethene is 2.0:1 in the raw material;
The mass flux ratio of hydrogen and carbon monoxide is 1:2.8 in the synthetic gas;
The flow that ethene adds in the tower in the raw material is pressed 14mL/min.
The mass ratio of synthetic gas and ethene is 2.4:1 in the raw material;
The mass flux ratio of hydrogen and carbon monoxide is 1:2.5 in the synthetic gas;
The flow that ethene adds in the tower in the raw material is pressed 16mL/min.
Claims (7)
1. an outer circulation reaction, extraction rectification method prepares the method for propionic aldehyde, it is characterized in that operation steps is:
Raw material is the mixture of synthetic gas and ethene, and wherein the mass ratio of synthetic gas and ethene is 2.0-10.0:1; Described synthetic gas is the mixed gas of hydrogen and carbon monoxide; Wherein the mass flux ratio of hydrogen and carbon monoxide is 1:2.5-2.8;
Raw material and organic extractant glycerine enter respectively the reaction, extraction rectifier unit, and rhodium complex is catalyzer, heating;
This reaction, extraction rectifier unit top product obtains gas-liquid mixture through after the condensation;
Described gas-liquid mixture is through gas-liquid separation, and gas circulation is to raw material, and liquid is propionic aldehyde;
Mixed solution is sent into catalyzer and organic extractant recovery tower at the bottom of the reaction, extraction rectifier unit, reclaims catalyzer and organic extractant, and recycles.
2. outer circulation reaction, extraction rectification method according to claim 1 prepares the method for propionic aldehyde, it is characterized in that, the flow in the raw material in the ethene adding tower is 14-16mL/min.
3. outer circulation reaction, extraction rectification method according to claim 1 prepares the method for propionic aldehyde, it is characterized in that, wherein the mass ratio of synthetic gas and ethene is 2.0-2.4:1.
4. outer circulation reaction, extraction rectification method according to claim 3 prepares the method for propionic aldehyde, it is characterized in that, in the described raw material, the mass ratio of synthetic gas/ethene is 2.2:1, in the synthetic gas, the mass rate of hydrogen/carbon monoxide is made as 1:2.67, and the mass ratio of raw material/organic extractant circular flow is made as 1:2, and the mass ratio of catalyzer/organic extractant reaches 1.5:20.
According to claim 1 and 2 or 3 or 4 described outer circulation reaction, extraction rectification methods prepare the method for propionic aldehyde, it is characterized in that to add the flow in the tower be 15mL/min to ethene in the raw material.
6. outer circulation reaction, extraction rectification method according to claim 5 prepares the method for propionic aldehyde, it is characterized in that the concrete operations of described each step are as follows:
Raw material adds from the underfeed mouth through volume pump, and the reaction, extraction rectifier unit is through temperature control heating jacket heated for controlling temperature, and organic extractant glycerine and catalyzer are from adding more than the packing section; Synthetic gas, ethene fully contact with organic extractant and catalyzer adverse current and generate the product propionic aldehyde in the reaction, extraction rectifier unit; Product propionic aldehyde and excessive unstripped gas process reaction, extraction rectifier unit evaporator overhead condenser condensation through gas-liquid separator separates, obtain 99.5% above propionic aldehyde, and residual gas is circulated to raw material; Organic extractant, catalyzer and a small amount of reactant two polyacetals and water form together discharge hole for discharge at the bottom of the reaction, extraction rectifier unit, through lift pump, deliver to organic extractant and catalyst recovery tower; Recovery tower is a rectifying tower; Recovery tower is through the heating of temperature control heating jacket, and low-boiling point material is discharged from the cat head discharge port, is collected by condensing collector after condenser condenses; Discharging obtains at the bottom of catalyzer and the organic extractant tower, delivers to organic extractant and catalyst feeds, recycle through recycle pump.
7. outer circulation reaction, extraction rectification method according to claim 6 prepares the method for propionic aldehyde, it is characterized in that the reaction conditions of described each step such as following table:
The operational condition of table 1 outer circulation reaction, extraction rectification process
。
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