CN111646884A - Hydroformylation method based on Fischer-Tropsch synthesis product - Google Patents
Hydroformylation method based on Fischer-Tropsch synthesis product Download PDFInfo
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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
-
- 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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Abstract
The invention relates to an olefin hydroformylation process based on a Fischer-Tropsch synthesis product, which comprises the following steps: (1) contacting the Fischer-Tropsch synthesis product and synthesis gas with a catalyst solution in a reaction zone at the reaction temperature of 20-150 ℃ and the reaction pressure of 1.0-8.0MPa to generate aldehyde; gas phase material flow in the reaction area is condensed by a condenser and then flows back to the reaction area, and non-condensable gas is used as tail gas to enter a tail gas collecting system. (2) And (3) sending the liquid phase material flow of the reaction zone into a separation zone, separating the product aldehyde from the catalyst solution, circulating the separated catalyst solution back to the reaction zone, and discharging the product aldehyde from the top of the separation zone and collecting the product aldehyde. The Fischer-Tropsch synthesis product of the process can directly participate in hydroformylation reaction without pretreatment, so that the process flow is simplified, the reaction conversion rate is high, and the economic benefit is greatly improved.
Description
Technical Field
The invention relates to a hydroformylation method, in particular to a hydroformylation method based on Fischer-Tropsch synthesis products.
Background
In 1938, Roelen (1897) was a German scientist who discovered hydroformylation of olefins (also known as OXO-Synthesis), i.e., hydroformylation of olefins with carbon monoxide and hydrogen over a catalyst:
the products of the method are distributed in aldehydes and alcohols with different carbon numbers, the hydroformylation reaction gradually develops into one of the most important reactions of industrial homogeneous catalysis, and millions of tons of carbonyl products are synthesized by the method every year around the world. The raw materials of the reaction are cheap and easy to obtain, the atom economy condition is met, and the product aldehyde can be conveniently further converted into various alcohols and acids so as to synthesize high-added-value fine chemicals such as pharmaceutical active molecules, spices and the like.
Patent CN1516685A discloses a process for the preparation of a higher linear alcohol composition by reacting carbon monoxide with hydrogen under fischer-tropsch reaction conditions in the presence of a cobalt-containing fischer-tropsch catalyst; separating at least one hydrocarbon fraction containing from 10 wt% to 50 wt% olefins from the product, and reacting the hydrocarbon fraction with carbon monoxide and hydrogen under hydroformylation conditions in the presence of a hydroformylation catalyst based on a cobalt source and one or more alkyl phosphines to produce a higher linear alcohol composition.
Patent CN101208286B discloses a process for producing aldehydes/alcohols and alkyl benzenes by subjecting a hydrocarbon feed stream containing olefins and paraffins to a hydroformylation reaction to obtain a hydroformylation product containing aldehydes/alcohols and paraffins. The raw material is long-chain hydrocarbon from low-temperature Fischer-Tropsch products C10-C18 at the temperature of lower than 280 ℃, and the raw material needs to be subjected to deoxidization treatment before being used as the raw material of the hydroformylation reaction.
CN102826973A discloses a method for preparing aldehyde by hydroformylation of low carbon olefin, wherein the raw material is selected from one of ethylene, propylene and butylene, and those skilled in the art can understand that the raw material is chemical grade, rather than fischer-tropsch synthesized olefin without separation.
The adopted petroleum cracking product contains a large amount of components, which can cause adverse reactions such as catalyst poisoning, and the like, and the product generally needs to be pretreated before hydroformylation reaction to obtain the olefin with higher purity. For example, the initial raw materials of the present preparation process of butanol, octanol or pentanol based on olefin hydroformylation are all propylene or butene in polymer grade or chemical grade, and the raw materials need to be refined through desulfurization, denitrification and the like. The hydroformylation reaction using single polymerization grade/chemical grade olefin as raw material must go through the previous separation and purification process to obtain single olefin product, and then starts the hydroformylation reaction, and the process is relatively complicated and costly.
CN104478641A discloses a process for preparing low-carbon olefin and co-producing low-carbon mixed aldehyde by coal-based synthesis gas, which comprises the steps of preparing low-carbon olefin by Fischer-Tropsch synthesis from coal-based synthesis gas, separating out light components of C3 and below, and then feeding the light components into a hydroformylation synthesis aldehyde reaction kettle to perform mixed hydroformylation of ethylene and propylene. Although the invention tries to use the Fischer-Tropsch synthesis product for hydroformylation reaction, the invention still does not jump out of the traditional nest socket for single olefin reaction, the low-carbon olefin prepared by Fischer-Tropsch synthesis is firstly separated, and only hydroformylation of ethylene and propylene is realized.
Disclosure of Invention
The invention aims to provide an olefin hydroformylation process based on a Fischer-Tropsch synthesis product, the total content of propylene and butylene in the initial raw material of the process is up to more than 70 wt%, almost no sulfur or nitrogen exists, pretreatment is not needed, the process can be directly used for hydroformylation reaction, and the generated aldehyde can be used for further preparing butanol, octanol and pentanol. Which comprises the following steps:
(1) contacting the Fischer-Tropsch synthesis product and synthesis gas with a catalyst solution in a reaction zone at the reaction temperature of 20-150 ℃ and the reaction pressure of 1.0-8.0MPa to generate aldehyde; gas phase material flow in the reaction area is condensed by a condenser and then flows back to the reaction area, and non-condensable gas is used as tail gas to enter a tail gas collecting system.
(2) And (3) sending the liquid phase material flow of the reaction zone into a separation zone, separating the product aldehyde from the catalyst solution, circulating the separated catalyst solution back to the reaction zone, and discharging the product aldehyde from the top of the separation zone and collecting the product aldehyde.
Preferably, the reaction temperature in the step (1) is 75-105 ℃, and the reaction pressure is 1.5-4 MPa.
Preferably, the content of propylene in the Fischer-Tropsch synthesis product is 1-99%, and the content of butylene is 1-99%. The content of the propylene and the butylene is 70 to 99 percent, and almost no sulfur and nitrogen are contained.
Preferably, the reaction zone in step (1) is a single reactor or a plurality of the same or different reactors connected together, wherein the reactor can be selected from a tank reactor or a tower reactor.
Preferably, the liquid phase stream in step (2) comprises unreacted alkene, alkane, product aldehyde, solvent and catalyst; the gas phase stream comprises H2CO, unreacted alkene, alkane, product aldehyde and inert components;
preferably, the separation of the product aldehyde and the catalyst solution in step (2) is carried out by methods commonly used in hydroformylation reactions, including distillation, flash distillation, or other separation methods.
Preferably, the catalyst in the catalyst solution may be a commonly used cobalt carbonyl compound, rhodium compound and/or complex known to those skilled in the art.
Preferably, the catalyst ligand may be selected from any one or more of trialkylphosphines, triarylphosphines, alkyldiarylphosphines, dialkylarylphosphines, dicycloalkylarylphosphines, cycloalkyldiarylphosphines, triaralkylphosphines, tricycloalkylphosphines, alkyl and/or aryl diphosphines, cycloalkyl and/or aryl diphosphines, monoorganic phosphonites, diorganophosphonites, triorganic phosphonites and organophosphonates.
Preferably, the catalyst solvent may be selected from one or more of pentane, naphtha, kerosene, cyclohexane, toluene, xylene, acetophenone, benzonitrile, polybutyral, and the like.
Compared with the prior art, the method has the advantages that the Fischer-Tropsch synthesis product is used as the raw material for hydroformylation, so that the raw material selection of hydroformylation is expanded, the application range of the Fischer-Tropsch synthesis product is widened, the Fischer-Tropsch synthesis product can directly participate in hydroformylation reaction without pretreatment, the process flow is simplified, the reaction conversion rate is high, and the economic benefit is greatly improved. The process makes a breakthrough in raw material selection from the aspect of raw materials of hydroformylation reaction, breaks through the conventional thinking, combines the Fischer-Tropsch synthesis product with the hydroformylation reaction, reduces the cost, improves the quality of chemicals and obtains excellent technical effects.
Drawings
FIG. 1 is a scheme showing the hydroformylation of Fischer-Tropsch synthesis product hydrocarbons to produce aldehydes
FIG. 2 is a diagram of an apparatus for preparing aldehydes by hydroformylation of Fischer-Tropsch synthesis product hydrocarbons
Wherein the reference numerals are as follows:
1. a Fischer-Tropsch synthesis product; 2. synthesis gas; 3. a primary catalyst solution; 4. liquid phase products; 5. a first pipeline; 6. a product aldehyde; 7. a second pipeline; 8. a catalyst solution; 9. a third pipeline; 10. a fourth pipeline; 11. a fifth pipeline; 12. a non-condensable gas;
201. a reactor; 202. a rotary falling film evaporator; 203. a first condenser; 204. a storage tank; 205. a first pump; 206. a cooler; 207. a second pump; 208. second condenser
Detailed Description
The process of the present invention is further described below with reference to FIGS. 1 and 2.
Example 1
A Fischer-Tropsch synthesis product-based olefin hydroformylation process comprises the following steps:
(1) the Fischer-Tropsch synthesis product 1 from the storage tank enters the reactor 201 through pipelines with the synthesis gas 2 and the catalyst solution 3 at a flow rate of 64 g/h. The reactor 201 was a 500ml pressure-resistant stirred tank reactor, the pressure inside the reactor was controlled to 2.2MPa by a gas phase outlet back pressure valve (not shown in FIG. 2), and the reactor temperature was controlled to 97 ℃ by an oil bath (not shown in FIG. 2). The concentration of the liquid phase catalyst in the reactor 201 was 200ppm calculated as metallic rhodium, and the solution also contained triphenylphosphine ligand in an amount of about 10% by mass. Raw materialsThe reaction is carried out under the action of the catalyst solution, the reaction gas-phase product is condensed and refluxed to the reactor 201 through the second condenser 208, and the residual non-condensable gas 12 enters the tail gas treatment system through a pipeline. Wherein the content of propylene and butylene in the Fischer-Tropsch synthesis product 1 is 70 percent, and CO and H in the synthesis gas2The molar ratio is 1: 1, and the molar ratio of the synthesis gas to the olefin is 1: 0.8.
(2) The liquid reaction product 4 was sent via a line via a first pump 205 to a rotary falling-film evaporator 202 having a diameter of 0.15m, the evaporator 202 being controlled at a pressure of 0.15MPa by means of a back-pressure valve (not shown in FIG. 2) and at a temperature of 120 ℃ by means of an oil bath (not shown in FIG. 2). The product aldehyde is extracted from the top of the evaporator 202, condensed by the first condenser 203 and then enters the storage tank 204 through the pipeline 7. The catalyst solution 8 is fed to the bottom of the evaporator 202, and is cooled by the cooler 206 through a line, and then circulated to the reactor 201 by the second pump 207.
The operation is carried out according to the process flow and the operation conditions, the total feeding amount of the Fischer-Tropsch synthesis product is 1mol/h, after the material flow is stable, the product in the storage tank 204 is measured and analyzed, the total aldehyde yield is 0.97mol/h, and the total conversion rate of the low-carbon olefin in the Fischer-Tropsch synthesis product is calculated to reach 97%.
Example 2
A Fischer-Tropsch synthesis product-based olefin hydroformylation process comprises the following steps:
(1) the Fischer-Tropsch synthesis product 1 from the storage tank enters the reactor 201 through pipelines with the synthesis gas 2 and the catalyst solution 3 at a flow rate of 64 g/h. The reactor 201 was a 500ml pressure-resistant stirred tank reactor, the pressure inside the reactor was controlled to 1.8MPa by a gas phase outlet back pressure valve (not shown in FIG. 2), and the reactor temperature was controlled to 97 ℃ by an oil bath (not shown in FIG. 2). The concentration of the liquid phase catalyst in the reactor 201 was 200ppm calculated as metallic rhodium, and the solution also contained triphenylphosphine ligand in an amount of about 10% by mass. The raw materials react under the action of the catalyst solution, the reaction gas-phase product is condensed and refluxed to the reactor 201 through the second condenser 208, and the residual non-condensable gas 12 enters the tail gas treatment system through a pipeline. Wherein the content of propylene and butylene in the Fischer-Tropsch synthesis product 1 is 70 percent, and CO and H in the synthesis gas2The molar ratio is 1: 1, and the molar ratio of the synthesis gas to the olefin is 1: 0.8.
(2) The liquid reaction product 4 was sent via a line via a first pump 205 to a rotary falling-film evaporator 202 having a diameter of 0.15m, the evaporator 202 being controlled at a pressure of 0.15MPa by means of a back-pressure valve (not shown in FIG. 2) and at a temperature of 120 ℃ by means of an oil bath (not shown in FIG. 2). The product aldehyde is extracted from the top of the evaporator 202, condensed by the first condenser 203 and then enters the storage tank 204 through the pipeline 7. The catalyst solution 8 is fed to the bottom of the evaporator 202, and is cooled by the cooler 206 through a line, and then circulated to the reactor 201 by the second pump 207.
The operation is carried out according to the process flow and the operation conditions, the total feeding amount of the Fischer-Tropsch synthesis product is 1mol/h, after the material flow is stable, the product in the storage tank 204 is measured and analyzed, the total aldehyde yield is 0.968mol/h, and the total conversion rate of the low-carbon olefin in the Fischer-Tropsch synthesis product is calculated to reach 96.8%.
Example 3
A Fischer-Tropsch synthesis product-based olefin hydroformylation process comprises the following steps:
(1) the Fischer-Tropsch synthesis product 1 from the storage tank enters the reactor 201 through pipelines with the synthesis gas 2 and the catalyst solution 3 at a flow rate of 64 g/h. The reactor 201 was a 500ml pressure-resistant stirred tank reactor, the pressure inside the reactor was controlled to 2.2MPa by a gas phase outlet back pressure valve (not shown in FIG. 2), and the reactor temperature was controlled to 105 ℃ by an oil bath (not shown in FIG. 2). The concentration of the liquid phase catalyst in the reactor 201 was 200ppm calculated as metallic rhodium, and the solution also contained triphenylphosphine ligand in an amount of about 10% by mass. The raw materials react under the action of the catalyst solution, the reaction gas-phase product is condensed and refluxed to the reactor 201 through the second condenser 208, and the residual non-condensable gas 12 enters the tail gas treatment system through a pipeline. Wherein the content of propylene and butylene in the Fischer-Tropsch synthesis product 1 is 70 percent, and CO and H in the synthesis gas2The molar ratio is 1: 1, and the molar ratio of the synthesis gas to the olefin is 1: 0.8.
(2) The liquid reaction product 4 was sent via a line via a first pump 205 to a rotary falling-film evaporator 202 having a diameter of 0.15m, the evaporator 202 being controlled at a pressure of 0.15MPa by means of a back-pressure valve (not shown in FIG. 2) and at a temperature of 120 ℃ by means of an oil bath (not shown in FIG. 2). The product aldehyde is extracted from the top of the evaporator 202, condensed by the first condenser 203 and then enters the storage tank 204 through the pipeline 7. The catalyst solution 8 is fed to the bottom of the evaporator 202, and is cooled by the cooler 206 through a line, and then circulated to the reactor 201 by the second pump 207.
The operation is carried out according to the process flow and the operation conditions, the total feeding amount of the Fischer-Tropsch synthesis product is 1mol/h, after the material flow is stable, the product in the storage tank 204 is measured and analyzed, the total aldehyde yield is 0.98mol/h, and the total conversion rate of the low-carbon olefin in the Fischer-Tropsch synthesis product is calculated to reach 98%.
Comparative example 1
A Fischer-Tropsch synthesis product-based olefin hydroformylation process comprises the following steps:
(1) chemical grade propylene 1 from a storage tank is fed into the reactor 201 through a pipeline with synthesis gas 2 and catalyst solution 3 at a flow rate of 42 g/h. The reactor 201 was a 500ml pressure-resistant stirred tank reactor, the pressure inside the reactor was controlled to 2.2MPa by a gas phase outlet back pressure valve (not shown in FIG. 2), and the reactor temperature was controlled to 97 ℃ by an oil bath (not shown in FIG. 2). The concentration of the liquid phase catalyst in the reactor 201 was 200ppm calculated as metallic rhodium, and the solution also contained triphenylphosphine ligand in an amount of about 10% by mass. The raw materials react under the action of the catalyst solution, the reaction gas-phase product is condensed and refluxed to the reactor 201 through the second condenser 208, and the residual non-condensable gas 12 enters the tail gas treatment system through a pipeline. Wherein, CO and H in the synthesis gas2The molar ratio is 1: 1, and the molar ratio of the synthesis gas to the propylene is 1: 0.8.
(2) The liquid reaction product 4 was sent via a line via a first pump 205 to a rotary falling-film evaporator 202 having a diameter of 0.15m, the evaporator 202 being controlled at a pressure of 0.15MPa by means of a back-pressure valve (not shown in FIG. 2) and at a temperature of 120 ℃ by means of an oil bath (not shown in FIG. 2). The product aldehyde is extracted from the top of the evaporator 202, condensed by the first condenser 203 and then enters the storage tank 204 through the pipeline 7. The catalyst solution 8 is fed to the bottom of the evaporator 202, and is cooled by the cooler 206 through a line, and then circulated to the reactor 201 by the second pump 207.
The operation is carried out according to the process flow and the operation conditions, the chemical-grade propylene feeding amount is 1mol/h, after the material flow is stable, the product in the storage tank 204 is measured and analyzed, the aldehyde yield is 0.985mol/h, and the conversion rate of the chemical-grade propylene is calculated to be 98.5%.
It can be seen that the olefin hydroformylation process using the fischer-tropsch synthesis product is substantially equivalent to the existing chemical grade propylene hydroformylation process in aldehyde yield and olefin conversion under similar process conditions, which is sufficient to show the superiority of the corresponding process of the present invention.
Although the present invention has been described in further detail with reference to the above embodiments, it should be understood by those skilled in the art that the present invention is not limited to the above embodiments, and various obvious changes, rearrangements and substitutions can be made by those skilled in the art without departing from the scope of the invention.
Claims (8)
1. A fischer-tropsch synthesis product based hydroformylation process comprising the steps of:
(1) contacting the Fischer-Tropsch synthesis product and synthesis gas with a catalyst solution in a reaction zone at the reaction temperature of 20-150 ℃ and the reaction pressure of 1.0-8.0MPa to generate aldehyde; gas phase material flow in the reaction zone is condensed by a condenser and then flows back to the reaction zone, and non-condensable gas is used as tail gas and enters a tail gas collection system;
(2) sending the liquid phase material flow of the reaction zone into a separation zone, separating the product aldehyde and the catalyst solution, circulating the separated catalyst solution back to the reaction zone, and collecting the product aldehyde after being discharged from the top of the separation zone;
wherein, the content of propylene in the Fischer-Tropsch synthesis product is 1 to 99 percent, and the content of butylene is 1 to 99 percent. The content of the propylene and the butylene is 70 to 99 percent, and almost no sulfur and nitrogen are contained.
2. The fischer-tropsch synthesis product based hydroformylation process of claim 1, wherein: in the step (1), the reaction temperature is 75-105 ℃, and the reaction pressure is 1.5-4 MPa.
3. The fischer-tropsch synthesis product based hydroformylation process of claim 1, wherein: the reaction zone in the step (1) is a single reactor or a plurality of same or different reactors which are connected together, wherein the reactor can be a kettle reactor or a tower reactor.
4. The fischer-tropsch synthesis product based hydroformylation process of claim 1, wherein: the liquid phase material flow in the step (2) comprises unreacted olefin, alkane, product aldehyde, solvent and catalyst; the gas phase stream comprises H2CO, unreacted alkene, alkane, product aldehyde and inert components.
5. The fischer-tropsch synthesis product based hydroformylation process of claim 1, wherein: the separation of the product aldehyde and the catalyst solution in the step (2) is carried out by the common method in the hydroformylation reaction, and comprises rectification, flash evaporation or other separation methods.
6. A Fischer-Tropsch synthesis product based hydroformylation process according to any one of claims 1 to 5, wherein: the catalyst in the catalyst solution is a cobalt carbonyl compound, a rhodium compound and/or a complex.
7. The fischer-tropsch synthesis product based hydroformylation process of claim 6, wherein: the catalyst ligand is selected from any one or more of trialkyl phosphine, triaryl phosphine, alkyl diaryl phosphine, dialkyl aryl phosphine, dicycloalkyl aryl phosphine, cycloalkyl diaryl phosphine, triaralkyl phosphine, tricycloalkyl phosphine, alkyl and/or aryl diphosphine, cycloalkyl and/or aryl diphosphine, mono-organic phosphonite, di-organic phosphonite, tri-organic phosphonite and organic phosphonate.
8. The fischer-tropsch synthesis product based hydroformylation process of claim 6, wherein: the catalyst solvent is selected from one or more of pentane, naphtha, kerosene, cyclohexane, toluene, xylene, acetophenone, benzonitrile, polybutyral and the like.
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| CN114773172A (en) * | 2022-06-20 | 2022-07-22 | 中海油天津化工研究设计院有限公司 | Optimization method of process for preparing aldehyde by hydroformylation of olefin |
| CN116102412A (en) * | 2023-02-14 | 2023-05-12 | 国家能源集团宁夏煤业有限责任公司 | Method for preparing aldehyde by hydroformylation of Fischer-Tropsch mixed olefin |
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