CN114478215B - A method and device for continuously preparing aldehydes and alcohols - Google Patents

A method and device for continuously preparing aldehydes and alcohols Download PDF

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CN114478215B
CN114478215B CN202011166630.8A CN202011166630A CN114478215B CN 114478215 B CN114478215 B CN 114478215B CN 202011166630 A CN202011166630 A CN 202011166630A CN 114478215 B CN114478215 B CN 114478215B
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reactor
cobalt
product
distillation column
temperature
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CN114478215A (en
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王海京
宗保宁
刘凌涛
甄栋兴
丁晖殿
罗一斌
夏春谷
郧栋
许传芝
刘祺壬
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Lanzhou Institute of Chemical Physics LICP of CAS
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/49—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide
    • C07C45/50—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reaction with carbon monoxide by oxo-reactions
    • C07C45/505—Asymmetric hydroformylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
    • B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
    • B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/14—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group
    • C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/78—Separation; Purification; Stabilisation; Use of additives
    • C07C45/786—Separation; Purification; Stabilisation; Use of additives by membrane separation process, e.g. pervaporation, perstraction, reverse osmosis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
    • B01J2231/32—Addition reactions to C=C or C-C triple bonds
    • B01J2231/321—Hydroformylation, metalformylation, carbonylation or hydroaminomethylation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt

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  • Water Supply & Treatment (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

本发明涉及一种通过氢甲酰化反应连续制备醇的方法和装置，其中包括：(A)将钴‑膦络合物催化剂溶液与烯烃通入氢甲酰化反应器，在合成气环境下进行氢甲酰化反应；(B)对反应粗产物进行分离，轻组分中得到醇、醛和烷烃混合产物，重组分中得到含钴‑膦络合物催化剂的物料；(C)含钴‑膦催化剂的物料大部分返回预反应器入口循环使用；少部分进入后处理反应器，在合成气的气氛下进行后处理；(D)对后处理反应器的流出物料进行蒸馏分离，塔顶得到醇等产物，塔底残余物料排出反应器。本发明方法对含重质物的外甩物料进行后处理，大幅降低外甩物料量，减少废液排放，有利于环保，具有工业化前景。

The present invention relates to a method and apparatus for continuously preparing alcohol by hydroformylation reaction, including: (A) a cobalt-phosphine complex catalyst solution and an olefin are passed into a hydroformylation reactor, and a hydroformylation reaction is carried out under a synthesis gas environment; (B) the crude reaction product is separated, and a mixed product of alcohol, aldehyde and alkane is obtained in the light component, and a material containing a cobalt-phosphine complex catalyst is obtained in the heavy component; (C) most of the material containing the cobalt-phosphine catalyst is returned to the entrance of the pre-reactor for recycling; a small part enters a post-processing reactor and is post-processed under a synthesis gas atmosphere; (D) the effluent material of the post-processing reactor is distilled and separated, and products such as alcohol are obtained at the top of the tower, and the residual material at the bottom of the tower is discharged from the reactor. The inventive method post-processes the externally thrown material containing heavy objects, greatly reduces the amount of externally thrown materials, reduces waste liquid discharge, is beneficial to environmental protection, and has industrial prospects.

Description

Method and device for continuously preparing aldehyde and alcohol
Technical Field
The invention relates to preparation of an oxygen-containing compound, in particular to a method and a device for preparing aldehyde and alcohol through olefin hydroformylation.
Background
The hydroformylation of olefins with carbon monoxide and hydrogen is carried out in the presence of a catalyst, and the hydroformylation process comprises contacting an olefinically unsaturated compound with carbon monoxide and hydrogen in the presence of a catalyst under reaction conditions to produce one or more aldehydes, alcohols. The catalyst used in the hydroformylation reaction in industrial production is typically a cobalt (Co) based or rhodium (Rh) based catalyst.
CN102123978a discloses a process for the hydroformylation of an alpha-olefin to produce two or more aldehydes comprising an normal aldehyde and one or more isomeric aldehydes, the target molar ratio of the normal aldehyde to the one or more isomeric aldehydes being in the selectable range of 3/1 to 60/1. The process uses a transition metal-ligand complex catalyst comprising symmetrical calixarene bisphosphite ligands.
CN108586219A discloses a method for preparing aldehyde by hydroformylation of olefin, which comprises the following steps of continuously preparing aldehyde by hydroformylation of C2-C4 olefin, carbon monoxide and hydrogen under the action of a catalyst in a first reaction kettle, heating the aldehyde in a second reaction kettle at the temperature of between 70 and 80 ℃ and introducing inert gas into the second reaction kettle, communicating the first reaction kettle with the second reaction kettle, introducing the aldehyde prepared by the first reaction kettle into the second reaction kettle, introducing the aldehyde into the second reaction kettle in the third step under the conditions of equal pressure and different temperatures, and introducing the aldehyde secondarily.
Rhodium complexes are more reactive than cobalt catalysts and can react at milder temperatures and pressures. However, the rhodium catalyst has poor high-temperature performance, has certain difficulty in being used for higher olefin carbonylation, has good catalytic effect on the olefin at the opposite end, has poor activity on the internal olefin, is oil-soluble and difficult in product separation, so that the post-treatment is complex, rhodium is rare as a noble metal resource, the price is high, and the recycling cost is high.
CN1257140C discloses a continuous process for the hydroformylation of olefins having 6 to 20 carbon atoms, wherein a) a cobalt (II) brine solution is contacted with hydrogen and carbon monoxide sufficiently to form a hydroformylation active cobalt catalyst, then an aqueous phase comprising the cobalt catalyst is contacted with the olefin and optionally an organic solvent and hydrogen and carbon monoxide sufficiently in at least one reaction zone, where the cobalt catalyst is extracted into the organic phase and the olefin is hydroformylated, b) the effluent from the reaction zone is treated with oxygen in the presence of an acidic cobalt (II) brine solution, wherein the cobalt catalyst is decomposed to form cobalt (II) salts and these materials are back extracted into the aqueous phase, and subsequently the phases are separated, C) the cobalt (II) brine solution is recycled to step a) in unchanged form. The method has complex technical process.
DE59704070D1 discloses a process for preparing alcohols having from 7 to 18 carbon atoms, comprising hydroformylating the corresponding olefins with synthesis gas in the presence of an organic phase of a cobalt-containing catalyst at a temperature of from 50 to 220℃and a pressure of from 100 to 400 bar, followed by hydrogenation of the aldehydes thus obtained, wherein an aqueous cobalt salt solution is reacted with synthesis gas in the presence of an organic solvent which is not miscible with water or only a small amount with water to form a cobalt catalyst, and the cobalt catalyst formed is extracted from the aqueous phase with an organic extractant which is not miscible with water or only a small amount with water to prepare the organic phase of the cobalt-containing catalyst. The formation of the cobalt catalyst, the extraction of the cobalt catalyst formed in the organic phase and the hydroformylation of the corresponding olefin are carried out in a one-step process. The reaction time of the method is generally more than 10 hours, the reaction pressure of the cobalt hydroformylation catalyst is high, such as about 25MPa, and the device fixed investment is large.
In the hydroformylation reaction process, along with continuous recycling of the catalyst materials, the content of heavy matters in the recycled materials can be slowly increased to influence the normal operation of the device, so that after the materials are recycled for a certain time, part of the heavy materials containing the catalyst need to be thrown out of the reactor, and the thrown material is treated according to waste liquid, so that great pressure is caused to environmental protection. The amount of the material thrown out also determines the industrial implementation prospect of the hydroformylation process.
Disclosure of Invention
The invention provides a method for continuously preparing aldehyde and/or alcohol through olefin hydroformylation, which has the advantages of simple process flow, high olefin conversion rate, high target product yield, capability of greatly reducing waste liquid discharge and good industrial application prospect.
The invention also provides a device for continuously preparing aldehyde and alcohol.
In a first aspect, the present invention provides a method for continuously preparing aldehyde or alcohol, comprising the steps of:
(A) Introducing cobalt-phosphine complex catalyst solution and olefin into a hydroformylation reactor, and carrying out hydroformylation reaction in a synthesis gas environment;
(B) Separating the reaction crude product to obtain an alcohol, aldehyde and alkane mixed product from the light component, and obtaining a material containing cobalt-phosphine complex catalyst from the heavy component;
(C) The majority of the material containing cobalt-phosphine catalyst is returned to the inlet of the reactor for recycling, and the minority of the material is fed into the post-treatment reactor for post-treatment in the atmosphere of the synthesis gas;
(D) And (3) distilling and separating the effluent of the post-treatment reactor, obtaining products such as alcohol at the top of the tower, and discharging the residual materials at the bottom of the tower out of the reactor.
The inventor finds that the content of heavy matters in the circulating materials can be slowly increased along with the continuous recycling of the materials containing the catalyst in the research, and analysis shows that the content of macromolecular carbonyl-containing byproducts in the heavy materials is obviously increased. The inventor of the present application proposes that this part of the material is sent to a post-treatment reactor, synthesis gas is introduced but olefin is not introduced, and post-treatment is performed under the condition of hydroformylation reaction, and unexpectedly, the macromolecular heavy byproducts in the material are decomposed again into products such as alcohol, etc., which not only further increases the yield of the target product, but also obviously reduces the amount of the material thrown outwards, thereby obviously reducing the discharge of waste liquid and alleviating the environmental protection problem of the hydroformylation process.
According to the process of the invention, the catalyst solution may also be pretreated in a pretreatment reactor, which may be an autoclave or a tubular reactor, prior to the hydroformylation reaction. The pretreatment is carried out in a synthetic gas atmosphere, the temperature of the pretreatment reactor is 50-150 ℃, preferably 75-130 ℃, more preferably 90-120 ℃, the pressure is 1-12 MPa, preferably 3-10 MPa, more preferably 5-8 MPa, and the pretreatment time is 0.1-10 hours, preferably 1-3 hours. The pretreatment of the catalyst is beneficial to the formation of active units of the cobalt-phosphine catalyst, reduces the decomposition of the catalyst, improves the activity and stability of the catalyst, and prolongs the service life of the catalyst.
If pretreatment is performed, the cobalt phosphine complex catalyst-containing material may be recycled to the pretreatment reactor inlet for reuse.
According to the process of the invention, when the material containing cobalt-phosphine complex catalyst is returned to the inlet of the hydroformylation reactor and/or the pretreatment reactor, small amounts of fresh catalyst may be added as required.
According to the method of the present invention, in the step (a), the mass concentration of cobalt in the cobalt-phosphine complex catalyst solution is 0.05% -3%, preferably 0.2% -2%, more preferably 0.5% -1.5%, and most preferably 0.6% -1%.
In the cobalt-phosphine complex catalyst solution, the mass ratio of cobalt and phosphorus of the cobalt-containing raw material to the phosphine ligand can be 1 (0.1-3), preferably 1 (0.2-2), and more preferably 1 (0.3-1).
The cobalt-containing raw material can be cobalt salt or cobalt oxide, wherein the cobalt salt can be inorganic cobalt acid or organic cobalt acid, such as one or more selected from cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt levulinate, cobalt formate, cobalt octacarbonyl and cobalt naphthenate.
The phosphine ligand may be one or more of various ligands known in the art, such as phosphite, triphenylphosphine, trialkylphosphine, di- (triphenylphosphine), alkylphenylphosphine, etc., preferably triphenylphosphine or tributylphosphine.
The cobalt-phosphine complex catalyst solution may be prepared according to a well-known method, for example, by dissolving a cobalt-containing raw material and a phosphine ligand in a solvent, charging CO, H 2 gas to a pressure of 1-6MPa, preferably 2-4MPa, and performing a reaction at 80-180 ℃, preferably 100-150 ℃ for 0.5-24 hours, preferably 1-15 hours, more preferably 3-10 hours to obtain a cobalt-phosphine catalyst solution.
The solvent in the cobalt-phosphine complex catalyst solution may be various solvents known in the art, such as olefin, alkane, alcohol, etc., preferably contains various types of alcohols of C1 to C20, and in addition, the solvent may contain a product or a raw material.
The solvent is preferably a strong-solubility mixed solvent. The strongly soluble mixed solvent may contain (1) a higher alcohol having 8 to 16 carbon atoms, (2) a hydroxyaldehyde having 16 to 30 carbon atoms in total, and/or an aldol condensate having 16 to 30 carbon atoms in total, in a mass ratio of 1 to 2 of 1:0.05 to 4, preferably 1:0.1 to 3, more preferably 1:0.2 to 2. The adoption of the mixed solvent with strong solubility can improve the concentration of the catalyst, reduce the reaction temperature and improve the total yield of the alcohol and the aldehyde.
The aldol condensate is obtained by reacting a C8-C16 aldehyde with a C8-C16 higher alcohol, and the total carbon number of the aldol condensate is C16-C32, preferably C18-C27.
The aldol condensate can be prepared by a conventional method, for example, taking C8-C16 aldehyde and C8-C16 higher alcohol as raw materials, wherein the molar ratio of the aldehyde to the higher alcohol is 1 (0.7-2), adding an acidic catalyst such as sulfuric acid and methyl benzene sulfonic acid, reacting for 0.4-3 hours at the temperature of 10-50 ℃ under normal pressure, and distilling and separating a reaction crude product.
The hydroxyaldehydes are obtained by reacting two or three molecules of C8-C16 aldehyde, and the total carbon number of the obtained hydroxyaldehydes is C16-C32, preferably C18-C27.
The hydroxyaldehyde can be prepared by a conventional method, for example, C8-C16 aldehyde is used as a raw material, dilute alkali (such as 5% -10% sodium hydroxide solution) is used as a catalyst, the reaction is carried out for 0.1-3 hours at normal pressure and low temperature (such as 0-10 ℃), and the crude reaction product is distilled and separated to obtain the hydroxyaldehyde.
According to the method, the olefin in the step (A) is C1-C30 olefin, preferably C6-C20 olefin, the olefin can be linear olefin and/or branched olefin, and the branched number of the branched olefin can be more than or equal to 1. The invention is particularly suitable for mixtures of carbon octaolefins containing one or more of 2, 4-trimethyl-1-pentene, 2, 4-trimethyl-2-pentene and the like. The three-methyl multi-branched olefin has high steric hindrance, and the hydroformylation difficulty is higher than that of the few-branched olefin.
The synthesis gas is a mixed gas of carbon monoxide and hydrogen, wherein the molar ratio of the carbon monoxide to the hydrogen is 4:1-1:4, preferably 3:1-1:3, and more preferably 2:1-1:2.
According to the method of the invention, the hydroformylation reactor is a tubular reactor, olefin, synthesis gas and solution containing catalyst flow in from the lower part of the tubular reactor, and reaction products flow out from the upper part of the tubular reactor. Or can flow in from the upper part of the tubular reactor and the reaction product flows out from the lower part of the tubular reactor. After the reaction is finished, part of alcohol, aldehyde, alkane and olefin raw materials are distilled out from the reaction crude product, the residual catalyst-containing solution is circulated to a pre-reactor for pretreatment, and the pretreated catalyst solution is sent to a hydroformylation reactor inlet and re-enters the reactor for use.
The temperature of the hydroformylation reactor is 60-250 ℃, preferably 100-220 ℃, more preferably 100-180 ℃, most preferably 110-140 ℃, the number of the reactors can be two or more, the reactors are used in series, preferably the two reactors are connected in series, the temperatures of the reactors can be the same or different, the reaction temperature can be high before, low after or high before, low after, if the primary reaction temperature is higher than the secondary reaction temperature, the residence time of the catalyst in a higher reaction temperature area can be reduced, and the decomposition of the catalyst can be reduced. The reaction pressure may be 1MPa to 12MPa, preferably 2MPa to 10MPa, more preferably 5MPa to 8MPa. The reaction time is 1 to 40 hours, preferably 3 to 20 hours, more preferably 5 to 10 hours.
The synthesis gas can flow into the pretreatment reactor and/or the lower part of the hydroformylation reactor, and can also flow into the lower parts of a plurality of hydroformylation reactors, and in addition, the ratio of CO to H 2 in the synthesis gas flowing into different reactors can be the same or different, so that the ratio of olefin to CO to H 2 in each reactor can be conveniently adjusted to be optimal, and higher conversion rate and more preference are facilitated. The molar ratio of the synthesis gas to the olefin is 1 to 12, preferably 3 to 6 to 1.
The mass ratio of catalyst solution to olefin is (0.1-10) 1, preferably (2-5) 1.
According to the method of the present invention, in the step (B), the crude product may be separated by gas-liquid separation and then by distillation.
The gas-liquid separation can be performed under the condition of not reducing the temperature in the gas-liquid separation tank, and the gas-liquid separation temperature is 0 ℃ to 100 ℃, preferably 20 ℃ to 80 ℃, and more preferably 20 ℃ to 40 ℃.
The gas phase material flow obtained after the vapor-liquid separation is basically synthesis gas, and after condensation and/or absorption, the residual synthesis gas can be recycled to a pre-reactor and/or a reactor inlet for reuse.
The liquid phase material flow after gas-liquid separation can be distilled and separated through a distillation device, the top discharge is the mixed product containing alcohol, alkane and aldehyde, and the bottom is the heavy material containing cobalt-phosphine complex catalyst.
The distillation separation device may be a distillation separation device which is easily conceived by those skilled in the art, such as a vacuum still, a rectifying tower, or a thin film evaporator. Wherein the pressure of the vacuum distillation kettle or the rectifying tower is less than or equal to 10 -2 MPa, preferably less than or equal to 10 -3 MPa, more preferably less than or equal to 10 - 4 MPa, the reflux ratio is 1-10:1, the temperature of the tower kettle is 70-200 ℃, the pressure of the thin film evaporator is less than or equal to 10mmHg, preferably less than or equal to 6mmHg, more preferably less than or equal to 1mmHg, the temperature of the heating surface is 35-150 ℃, preferably 40-100 ℃, more preferably 45-70 ℃, and the residence time is 1-30 minutes, preferably 1-10 minutes, more preferably 1-2 minutes.
Preferably, the mixture obtained from the top of the distillation apparatus may also be fed to a product distillation column for further separation. The product distillation column may be an atmospheric distillation column or a rectification column to obtain alkanes, high purity alcohols and aldehydes. The pressure can be normal pressure, the reflux ratio is 1-10:1, and the temperature of the tower kettle is 100-300 ℃, preferably 150-200 ℃.
Preferably, the product distillation can be performed in two times through the first product distillation tower and the second product distillation tower, and light components such as alkane and the like are distilled out first, and products such as alcohol, aldehyde and the like are distilled out. Heavy materials discharged from the lower part of the second product distillation tower enter a post-treatment reactor.
Preferably, if the target product is to obtain more alcohol, the resulting mixture of alcohol and aldehyde may also be hydrotreated to convert the aldehyde to alcohol.
According to the method of the invention, in the step (C), the post-treatment reactor is a tubular reactor, heavy materials containing the catalyst can flow in from the lower part of the tubular reactor and flow out from the upper part of the tubular reactor or flow in from the upper part of the tubular reactor and flow out from the lower part of the tubular reactor, and meanwhile, the synthesis gas is introduced into the reactor but no olefin is introduced, so that the heavy materials are further decomposed into products such as alcohol, aldehyde and the like.
The post-treatment reactor is a tubular reactor, the reaction temperature is 60-250 ℃, preferably 100-200 ℃, more preferably 120-190 ℃, the reaction pressure is 1-12 MPa, preferably 3-10 MPa, more preferably 5-8 MPa, and the residence time is 0.5-20 hours, preferably 1-7 hours.
The amount of the heavy material entering the post-treatment reactor can be determined according to the activity of the catalyst, the yield of the product and the like. The post-treatment reactor can be synchronously operated with the hydroformylation reaction, can be started after the hydroformylation reaction is carried out for a period of time, and can be started intermittently.
According to the method of the invention, in the step (D), the material subjected to post-treatment enters an external material throwing distillation tower, which can be an atmospheric distillation tower or a rectifying tower, products such as alcohol and the like are distilled out from the top of the tower, and the products are discharged or returned to the product distillation tower. And obtaining residual heavy materials at the bottom of the tower, and discharging the residual heavy materials by external throwing. The distillation column pressure may be atmospheric and the reflux ratio 1-10:1, the column bottoms temperature 100 ℃ to 300 ℃, preferably 150 ℃ to 200 ℃.
In a second aspect, the invention also provides a device for continuously preparing aldehyde and alcohol by hydroformylation of olefin, which comprises a pretreatment reactor, a tubular reactor, a gas-liquid separator, a distillation separation device, a post-treatment reactor, an external material throwing distillation column, a catalyst solution, a synthesis gas and olefin feeding pipeline, a pipeline for conveying reaction products from the tubular reactor to the gas-liquid separator, a pipeline for conveying liquid phase streams from the lower part of the gas-liquid separator to the distillation separation device, a pipeline for returning separated synthesis gas from the upper part of the gas-liquid separator to the pretreatment reactor and/or the tubular reactor, a pipeline for discharging mixed products from the upper part of the distillation device, a pipeline for conveying catalyst-containing materials from the lower part of the distillation separation device to the post-treatment reactor, a pipeline for returning catalyst-containing materials from the lower part of the distillation separation device to the pretreatment reactor and/or the tubular reactor, a connecting pipeline of the post-treatment reactor and the external material throwing distillation column, and a discharging pipeline from the upper part and the lower part of the external material throwing distillation column.
According to a preferred embodiment of the invention, the catalyst solution flows in from the bottom of the pretreatment reactor and flows out from the upper part of the pretreatment reactor, the pretreated catalyst solution and olefin flow in from the bottom of the tubular reactor, the upper part flows out, the reaction crude product enters a gas-liquid separator, wherein residual synthesis gas after gas is collected by a cold bath to collect condensate is recycled to the pretreatment reactor or the hydroformylation reactor for reuse, liquid enters a distillation separation device, the mixed product is distilled out from the upper part, most of the residual catalyst solution is recycled to the pretreatment reactor for recycling, a small amount of heavy material enters from the lower part of the post-treatment reactor, the upper part flows out, the post-treated material enters an external throwing distillation column, products such as alcohol are obtained from the upper part of the distillation column, and the heavy material-containing external throwing material is discharged from the lower part.
Preferably, the product distillation column is further comprised, preferably comprising a first product distillation column and a second product distillation column, a line for the mixed product to enter the first product distillation column from the upper part of the distillation separation device, a connection line between the first product distillation column and the second product distillation column, a connection line for the lower part of the second product distillation column and the lower part of the finishing reactor, and a discharge line for the upper parts of the first product distillation column and the second product distillation column.
The product distillation column may be a still or a rectifying column.
Preferably, a line for replenishing the pre-reactor and/or each reactor with synthesis gas or catalyst and an inlet line for replenishing the post-treatment reactor with synthesis gas are also included.
Preferably, the tubular reactor consists of two or more tubular reactors in series.
Wherein, the distillation separation device can be a distillation kettle, a rectifying tower or a thin film evaporator.
Wherein, the external material throwing distillation tower can be a distillation still or a rectification tower. Preferably, the distilled alcohol and other products are returned to the first product distillation column.
Preferably, a hydrogenation apparatus may be further included, and alcohols and aldehydes obtained from the product distillation column and the external flighted distillation column may be further hydrogenated, and alcohols with high yields may be obtained.
The invention has the following advantages:
1. the external throwing material containing heavy matters is subjected to post-treatment, and the heavy byproducts are decomposed into products such as alcohol again, so that the external throwing material quantity is obviously reduced, the waste liquid emission is reduced, the environment is protected, and the method has an industrial prospect.
2. The catalyst pretreatment process can obviously reduce the decomposition of the cobalt-phosphine catalyst, is beneficial to the formation of active units of the cobalt-phosphine catalyst, improves the activity and stability of the catalyst, and prolongs the service life of the catalyst.
3. The adoption of the solvent with strong solubility can improve the concentration of the catalyst, reduce the reaction temperature, improve the total yield of alcohol and aldehyde and reduce the generation of alkane.
4. The product separation process is simple, and the selectivity of alcohol and aldehyde is high.
5. The method is suitable for wide olefin raw materials, is particularly suitable for multi-branched olefin hydroformylation reactions with large steric hindrance, and has low reaction pressure and obviously reduced device investment and processing cost.
Drawings
Fig. 1 is a preferred embodiment of the present invention. Wherein:
1 pretreatment reactor, 2 tubular reactor, 3 tubular reactor, 4 gas-liquid separator, 5 distillation separation device, 6 first product distillation tower, 7 second product distillation tower, 8 post-treatment reactor and 9 external material throwing distillation tower.
Detailed Description
The invention is further illustrated by the following examples, but is not limited thereto.
The olefin feed in the examples was commercial carbon octaolefin consisting of 75.1% 2, 4-trimethyl-1-pentene, 21.2% 2, 4-trimethyl-2-pentene and the balance being a multi-branched olefin.
Catalyst preparation example 1
Cobalt naphthenate and triphenylphosphine are dissolved in isononanol, the cobalt content in the solution is 0.075wt% and the phosphorus content is 0.06wt%, air is replaced by synthesis gas H2/CO (2:1), CO and H2 gas are filled to the pressure of 2MPa, and the cobalt-phosphine catalyst solution A1 is obtained after 140 ℃ reaction for 12H under 400 rpm stirring. The catalyst is shown in the composition table 1.
Catalyst preparation example 2
Cobalt naphthenate and triphenylphosphine are added into a strong-solubility solution (isononanol solution containing aldol 38.1 wt%) with cobalt content of 0.7wt% and phosphorus content of 0.4wt%, air is replaced by synthesis gas H2/CO (2:1), CO and H2 gases are filled to the pressure of 2MPa, and the mixture is reacted for 12 hours at 140 ℃ under stirring of 400 revolutions per minute, so that cobalt-phosphine catalyst solution A2 is obtained. The catalyst is shown in the composition table 1.
Catalyst preparation example 3
Cobalt naphthenate and triphenylphosphine are added into a strong-solubility solution (isononanol solution containing 23.1wt% of aldol and 39.8wt% of aldol condensate), wherein the cobalt content is 0.6 percent and the phosphorus content is 0.3 percent, air is replaced by synthesis gas H2/CO (2:1), CO and H2 gases are filled to the pressure of 2MPa, and the mixture is reacted for 12 hours at 140 ℃ under 400 revolutions per minute stirring, so as to obtain cobalt-phosphine catalyst solution A3. The catalyst is shown in the composition table 1.
Catalyst preparation example 4
Cobalt naphthenate and triphenylphosphine are dissolved in isononanol, the cobalt content in the solution is 0.07wt% and the phosphorus content is 0.04wt%, air is replaced by synthesis gas H2/CO (2:1), CO and H2 gas are filled to the pressure of 2MPa, and the cobalt-phosphine catalyst solution A4 is obtained after 140 ℃ reaction for 12 hours under 400 rpm stirring. The catalyst is shown in the composition table 1.
Example 1
The carbon octaolefin and the catalyst solution A1 are respectively fed into a reactor and a pretreatment reactor from a storage tank by a high-pressure metering pump, the catalyst solution and the synthetic gas (the molar ratio of CO/H2 is 1:2) flow into the tubular pretreatment reactor from the bottom and flow out from the upper part, the cobalt concentration in the catalyst solution is 0.075%, the temperature of the pretreatment reactor is 100 ℃, the pressure is 8MPa, the residence time is 1 hour, the pretreated catalyst solution and the carbon octaolefin flow into the bottom of the hydroformylation reactor from 73g to 30g, the upper part flows out, the hydroformylation reactor is formed by connecting two tubular reactors in series, the reaction temperature is measured by a thermocouple inserted into the center of the reactor, the molar ratio of the synthetic gas and the olefin is 3:1, the reaction temperature of the hydroformylation reactor is 180 ℃, the reaction temperature is 175 ℃, the pressure is 8MPa, the residence time is 8 hours, the raw material conversion after the reaction is 99%, the chromatographic analysis is carried out on the product, and the composition of the product is shown in Table 2.
The crude reaction product enters a gas-liquid separator, wherein residual synthesis gas after gas is condensed through a cold bath is recycled to a pretreatment reactor for reuse, liquid enters a thin film evaporator, the pressure of the thin film evaporator is 6mmHg, the temperature of a heating surface is 85 ℃, and the residence time is 0.7 min, and after the product is distilled out of the thin film evaporator, the residual catalyst solution is recycled to the pretreatment reactor for recycling. The product distilled by the film evaporator enters a product rectifying tower, and is rectified at normal pressure and reflux ratio of 2:1, the temperature of a tower kettle is below 194 ℃, light components such as alkane and the like are distilled, and the product isononanol is distilled at normal pressure and reflux ratio of 1:1, the temperature of the tower kettle is 194 ℃, and the purity is 98%.
After multiple circulation, a small amount of heavy material enters a post-treatment reactor from the lower part, flows out from the upper part, further decomposes the heavy material into products such as isononanol and the like under the reaction temperature of 120 ℃ and 6MPa and the synthetic gas atmosphere, samples are taken for chromatographic analysis after the reaction for 1 hour, the content of the heavy material mainly containing carbonyl is reduced by 61%, the post-treated material enters a rectifying tower, the reflux ratio is 1:1 under normal pressure, the temperature of the tower kettle is 194 ℃, isononanol is distilled out, and the residual material is thrown out.
Example 2
The carbon octaolefin and the catalyst solution A2 are respectively fed into a reactor and a pretreatment reactor from a storage tank by a high-pressure metering pump, the catalyst solution and the synthetic gas (the molar ratio of CO/H2 is 1:2) flow into the tubular pretreatment reactor from the bottom and flow out from the upper part, the cobalt concentration in the catalyst solution is 0.7%, the temperature of the pretreatment reactor is 100 ℃, the pressure is 8MPa, the residence time is 1 hour, the pretreated catalyst solution and the carbon octaolefin flow into the bottom of a hydroformylation reactor according to 73g:44g, the upper part flows out, the hydroformylation reactor is formed by connecting two tubular reactors in series, the reaction temperature is measured by a thermocouple inserted into a sleeve in the center of the reactor, the molar ratio of the synthetic gas and the olefin is 3:1, the synthetic gas enters the reactor from the lower part of the pretreatment reactor, the reaction temperature of the hydroformylation reactor is 120 ℃, the reaction temperature of the reaction is 2 ℃, the pressure is 8MPa, the residence time is 8 hours, the conversion rate of the C8 olefins is 97.3%, and the product is subjected to chromatographic analysis, and the composition of the product is shown in Table 2.
The crude reaction product enters a gas-liquid separator, wherein residual synthesis gas after gas is condensed through a cold bath is recycled to a pretreatment reactor for reuse, liquid enters a thin film evaporator, the pressure of the thin film evaporator is 4mmHg, the temperature of a heating surface is 70 ℃, and the retention time is 1 minute, and after the product is distilled out of the thin film evaporator, the residual catalyst solution is recycled to the pretreatment reactor for recycling. The product distilled by the film evaporator enters a product rectifying tower, and is rectified at normal pressure and reflux ratio of 1:1, tower kettle temperature is below 194 ℃, light components such as alkane and the like are distilled, and is rectified at normal pressure and reflux ratio of 1:2, tower kettle temperature is 194 ℃, and the product isononanol is distilled, and has purity of 98%.
After multiple circulation, a small amount of heavy material enters from the lower part of the post-treatment reactor, flows out from the upper part, decomposes the heavy material into products such as isononanol and the like under the reaction temperature of 160 ℃ and 7MPa and the synthetic gas atmosphere, samples and carries out chromatographic analysis after reacting for 7 hours, the content of the heavy material mainly containing carbonyl is reduced by 91 percent, the post-treated material enters into a rectifying tower, the reflux ratio of the material to the rectifying tower is 1:1 under normal pressure, the temperature of the tower bottom is 194 ℃, and the residual material is thrown outwards after the products such as isononanol and the like are distilled out.
Example 3
The carbon octaolefin and the catalyst solution A3 are respectively fed into a reactor and a pretreatment reactor from a storage tank by a high-pressure metering pump, the catalyst solution and the synthetic gas (the molar ratio of CO/H2 is 1:1.5) flow into the tubular pretreatment reactor from the bottom and flow out from the upper part, the cobalt concentration in the catalyst solution is 0.6%, the temperature of the pretreatment reactor is 120 ℃, the pressure is 8MPa, the residence time is 1 hour, the pretreated catalyst solution and the carbon octaolefin flow into the bottom of the hydroformylation reactor according to 73g:44g, the upper part flows out, the hydroformylation reactor consists of two tubular reactors in series, the reaction temperature is measured by a thermocouple inserted into the center of the reactor and sleeved pipe, the molar ratio of the synthetic gas and the olefin is 6:1, the synthetic gas enters the reactor from the lower part of the pretreatment reactor, the reaction temperature of the hydroformylation reactor is 140 ℃, the pressure is 8MPa, the residence time is 4 hours, the C8 olefin conversion rate is 96.3%, and the product is subjected to chromatographic analysis, and the composition of the product is shown in Table 2.
The crude reaction product enters a gas-liquid separator, wherein residual synthesis gas after gas passes through a cold bath to collect condensate is recycled to a pretreatment reactor for reuse, liquid enters a thin film evaporator, the pressure of the thin film evaporator is 0.6mmHg, the temperature of a heating surface is 50 ℃, and the retention time is 1 minute, and after the product is distilled out of the thin film evaporator, the residual catalyst solution is recycled to the pretreatment reactor for recycling. The product distilled by the film evaporator enters a product rectifying tower, and is rectified at normal pressure and reflux ratio of 2:1, the temperature of a tower kettle is below 194 ℃, light components such as alkane and the like are distilled, and the product isononanol is distilled at normal pressure and reflux ratio of 1:1, the temperature of the tower kettle is 194 ℃, and the purity is 98%.
After multiple circulation, a small amount of heavy material enters from the lower part of the post-treatment reactor, flows out from the upper part, decomposes the heavy material into products such as isononanol and the like under the reaction temperature of 160 ℃ and 7MPa, and after 2 hours of reaction, chromatographic analysis shows that the content of the heavy material mainly containing carbonyl is reduced by 79 percent, the post-treated material enters into a rectifying tower, the reflux ratio of the material to the rectifying tower is 1:1 under normal pressure, the temperature of the tower bottom is 194 ℃, and the residual material is thrown out after the products such as isononanol and the like are distilled out.
Example 4
The carbon octaolefin and the catalyst solution A4 are respectively fed into a reactor and a pretreatment reactor from a storage tank by a high-pressure metering pump, the catalyst solution and the synthetic gas (the molar ratio of CO/H2 is 1:1.5) flow into the tubular pretreatment reactor from the bottom and flow out from the upper part, the cobalt concentration in the catalyst solution is 0.07%, the temperature of the pretreatment reactor is 100 ℃, the pressure is 8MPa, the residence time is 1 hour, the pretreated catalyst solution and the carbon octaolefin flow into the bottom of the hydroformylation reactor from 73g to 40g, the upper part flows out, the hydroformylation reactor is formed by connecting two tubular reactors in series, the reaction temperature is measured by a thermocouple inserted into the center of the reactor, the molar ratio of the synthetic gas to the olefin is 4.5:1, the temperature of the hydroformylation reactor is 180 ℃, the temperature of the reaction is 177 ℃, the pressure is 8MPa, the residence time is 8 hours, the raw material conversion rate after the reaction is 97.9%, the chromatographic analysis is carried out on the product, and the composition of the product is shown in Table 2.
The crude reaction product enters a gas-liquid separator, wherein residual synthesis gas is recycled to a pre-reactor for reuse after gas passes through a cold bath to collect condensate, liquid enters a thin film evaporator, the pressure of the thin film evaporator is 0.9mmHg, the temperature of a heating surface is 60 ℃, and the retention time is 1 minute, and after the product is distilled out of the thin film evaporator, the residual catalyst solution is recycled to the pre-reactor for recycling. The product distilled by the film evaporator enters a product rectifying tower, the light components such as alkane and the like are distilled at normal pressure and the reflux ratio of 3:1, the temperature of the tower kettle is lower than 193 ℃, the product isononanol is distilled at normal pressure and the reflux ratio of 2:1, the temperature of the tower kettle is 193 ℃, and the purity is 98%.
After multiple circulation, a small amount of heavy material enters from the lower part of the post-treatment reactor, flows out from the upper part of the post-treatment reactor, further decomposes the heavy material into products such as isononanol and the like under the reaction temperature of 180 ℃ and 8MPa, takes a sample for chromatographic analysis after 2 hours of reaction, reduces the content of the heavy material mainly containing carbonyl by 81%, and the post-treated material enters into a rectifying tower at normal pressure with the reflux ratio of 1:1, the temperature of a tower kettle is 193 ℃, the products such as isononanol and the like are distilled out, and the residual material is thrown out.
TABLE 1
TABLE 2

Claims (35)

1. A method for continuously preparing aldehyde and alcohol comprises the steps of pretreating cobalt-phosphine complex catalyst solution in a pretreatment reactor, wherein the pretreatment is performed in a synthesis gas atmosphere, the temperature of the pretreatment reactor is 50-150 ℃, the pressure is 1-12 MPa, the pretreatment time is 0.1-10 hours, the pretreatment reactor is a tubular reactor, and the method further comprises the following steps:
(A) Introducing cobalt-phosphine complex catalyst solution and olefin into a hydroformylation reactor, and carrying out hydroformylation reaction in a synthesis gas environment;
(B) Separating the reaction crude product to obtain an alcohol, aldehyde and alkane mixed product in a light component, and obtaining a cobalt-phosphine catalyst-containing material in a heavy component;
(C) The method comprises the steps of recycling most of the material containing the cobalt-phosphine catalyst back to an inlet of a pretreatment reactor, introducing synthesis gas but not introducing olefin into the pretreatment reactor for aftertreatment, wherein the aftertreatment reactor is a tubular reactor, the reaction temperature is 60-250 ℃, the reaction pressure is 1-12 MPa, and the residence time is 0.5-20 hours;
(D) And (3) distilling and separating the effluent of the post-treatment reactor, obtaining a product at the top of the tower, and discharging the residual material at the bottom of the tower out of the reactor.
2. The method according to claim 1, wherein the pretreatment reactor is at a temperature of 75 ℃ to 130 ℃ and a pressure of 3MPa to 10MPa, and the pretreatment time is 1 to 3 hours.
3. The method according to claim 1, wherein the pretreatment reactor is at a temperature of 90 ℃ to 120 ℃ and a pressure of 5mpa to 8mpa, and the pretreatment time is 1 to 3 hours.
4. The process of claim 1 wherein the olefin is a C1-C30 olefin.
5. The process of claim 1 wherein the olefin is a C6-C20 olefin.
6. The process according to claim 1, wherein the olefin is a mixture of carbon octaolefins containing one or more of 2, 4-trimethyl-1-pentene and 2, 4-trimethyl-2-pentene.
7. The method according to claim 1, wherein the molar ratio of carbon monoxide to hydrogen in the synthesis gas is 4:1-1:4.
8. The process of claim 1 wherein the cobalt-phosphine complex catalyst solution has a cobalt mass concentration of 0.05% to 3%.
9. The method according to claim 1, wherein the mass concentration of cobalt in the cobalt-phosphine complex catalyst solution is 0.2% -2%.
10. The process of claim 1 wherein the cobalt-phosphine complex catalyst solution has a cobalt to phosphorus mass ratio of cobalt containing feedstock to phosphine ligand of 1 (0.1-3).
11. The process of claim 1 wherein the cobalt-phosphine complex catalyst solution has a cobalt to phosphorus mass ratio of cobalt containing feedstock to phosphine ligand of 1 (0.2-2).
12. The process of claim 10 wherein the cobalt-containing feedstock is a cobalt salt or cobalt oxide.
13. The process of claim 10 wherein the cobalt-containing feedstock is selected from one or more of cobalt carbonate, cobalt nitrate, cobalt acetate, cobalt levulinate, cobalt formate, cobalt octacarbonyl, and cobalt naphthenate.
14. The process according to claim 10, wherein the phosphine ligand is selected from one or more of phosphite, triphenylphosphine, trialkylphosphine, di- (triphenylphosphine), alkylphosphine.
15. The process according to claim 1, wherein the solvent in the cobalt-phosphine complex catalyst solution is a strongly soluble mixed solvent comprising (1) a higher alcohol having 8 to 16 carbon atoms, (2) hydroxyaldehydes having 16 to 30 total carbon atoms, and/or aldol condensates having 16 to 30 total carbon atoms, and the mass ratio of component (1) to component (2) is 1:0.05 to 4.
16. The process according to claim 15, wherein the mass ratio of component (1) to component (2) is 1:0.1-3.
17. The process according to claim 1, wherein the hydroformylation reactor temperature is from 100 ℃ to 250 ℃, the reaction pressure is from 1mpa to 12mpa, and the reaction time is from 1 to 40 hours.
18. The process of claim 1 wherein the hydroformylation reactor temperature is 110 ℃ to 220 ℃, the reaction pressure is 2mpa to 10mpa, and the reaction time is3 to 20 hours.
19. The process of claim 1 wherein the hydroformylation reactor temperature is 110 ℃ to 140 ℃, the reaction pressure is 5mpa to 8mpa, and the reaction time is 3 to 20 hours.
20. The process of claim 1 wherein the reactor is a series of two reactors, one having a greater than two temperatures.
21. The process according to claim 1, wherein the molar ratio of synthesis gas to olefin is 1 to 12 and the mass ratio of catalyst solution to olefin is 0.1 to 10 to 1.
22. The process according to claim 1, wherein the molar ratio of synthesis gas to olefin is (3-6) 1 and the mass ratio of catalyst solution to olefin is (2-5) 1.
23. The process of claim 1 wherein the crude product of step (B) is separated by gas-liquid separation followed by distillation to obtain a mixed product from the top of the distillation apparatus.
24. The process according to claim 23, wherein the gas-liquid separation is carried out without lowering the temperature in the gas-liquid separation tank, and the gas-liquid separation temperature is 0 ℃ to 100 ℃.
25. The method according to claim 23, wherein the distillation separation device is a vacuum distillation still, a distillation column or a thin film evaporator, the pressure of the vacuum distillation still or the distillation column is less than or equal to 10 -2 MPa, the reflux ratio is 1-10:1, the temperature of the column still is 70-200 ℃, the pressure of the thin film evaporator is less than or equal to 10mmHg, the temperature of the heating surface is 35-150 ℃, and the residence time is 1-30 minutes.
26. The process of claim 23 wherein the mixed product is fed to a product distillation column for further separation, said product distillation column being an atmospheric distillation column or a rectification column, the bottoms temperature being in the range of 100 ℃ to 300 ℃.
27. The process of claim 26 wherein the product distillation is performed in two passes through a first product distillation column and a second product distillation column, the heavy material exiting the lower portion of the second product distillation column entering the finishing reactor.
28. The method according to claim 1, wherein the post-treatment reactor has a reaction temperature of 100 ℃ to 200 ℃ and a reaction pressure of 3MPa to 10MPa, and the residence time is 0.5 to 20 hours.
29. The method according to claim 1, wherein the post-treatment reactor has a reaction temperature of 120 ℃ to 190 ℃ and a reaction pressure of 5mpa to 8mpa and a residence time of 1 to 7 hours.
30. The method according to claim 1, wherein the material subjected to the post-treatment enters an external material throwing distillation tower, and the temperature of the tower bottom is 100-300 ℃.
31. An apparatus for continuously producing aldehydes and alcohols according to the method of claim 1, wherein the apparatus comprises a pretreatment reactor, a tubular reactor, a gas-liquid separator, a distillation separation device, a post-treatment reactor, an external feed-off distillation column, and feed lines for catalyst solution, synthesis gas and olefins, a line for transferring reaction products from the tubular reactor to the gas-liquid separator, a line for transferring a liquid-phase stream from the lower part of the gas-liquid separator to the distillation separation device, a line for returning separated synthesis gas from the upper part of the gas-liquid separator to the pretreatment reactor and/or the tubular reactor, a line for discharging the mixed product from the upper part of the distillation device, a line for transferring catalyst-containing material from the lower part of the distillation separation device to the post-treatment reactor, a line for returning catalyst-containing material from the lower part of the distillation separation device to the pretreatment reactor and/or the tubular reactor, a line for replenishing synthesis gas to the post-treatment reactor but not replenishing olefins, a connecting line for the post-treatment reactor to the external feed-off distillation column, and a line for discharging the mixed product from the upper part and the lower part of the distillation column.
32. The apparatus of claim 31, further comprising a product distillation column and its connection lines to the distillation separation means, and product distillation column upper and lower discharge lines.
33. The apparatus according to claim 31 or 32, further comprising a first product distillation column and a second product distillation column, and a line for transporting the mixed product from the upper part of the distillation separation apparatus to the first product distillation column, a connecting line between the first product distillation column and the second product distillation column, a connecting line between the lower part of the second product distillation column and the lower part of the finishing reactor, and a discharge line at the upper parts of the first product distillation column and the second product distillation column.
34. The apparatus of claim 31, further comprising a line for replenishing the pretreatment reactor, the tubular reactor with synthesis gas or catalyst.
35. The apparatus of claim 31, wherein the tubular reactor is comprised of a plurality of tubular reactors in series.
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