CN111548267A - Process device and process method for preparing cyclopentanol from cyclopentene - Google Patents
Process device and process method for preparing cyclopentanol from cyclopentene Download PDFInfo
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- CN111548267A CN111548267A CN202010566211.7A CN202010566211A CN111548267A CN 111548267 A CN111548267 A CN 111548267A CN 202010566211 A CN202010566211 A CN 202010566211A CN 111548267 A CN111548267 A CN 111548267A
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Abstract
The invention discloses a process device and a process method for preparing cyclopentanol from cyclopentene, which comprise a reactor, a catalytic distillation tower, a hydrogenation reactor, a gas-liquid separation tank and a distillation tower which are connected in sequence; carrying out pre-reaction on cyclopentene and organic acid in a reactor, and carrying out catalytic distillation reaction in a catalytic distillation tower to obtain a heavy component containing organic acid cyclopentyl ester; and (3) carrying out hydrogenation reaction on the heavy component of the organic acid cyclopentyl ester and hydrogen in a hydrogenation reactor to generate cyclopentanol, organic alcohol and unreacted hydrogen, and sequentially carrying out gas-liquid separation and distillation separation on the product to obtain the organic alcohol and the cyclopentanol. The invention has high cyclopentene conversion rate, high cyclopentanol yield and low equipment and operation cost.
Description
Technical Field
The invention relates to a process device and a process method for preparing cyclopentanol from cyclopentene, and belongs to the technical field of chemical processes.
Background
Cyclopentanol is an important chemical raw material, and the traditional preparation method comprises the following steps: the cyclopentanol is prepared by decarboxylation and hydrogenation of adipic acid as raw material. Because the method has great environmental pollution, people begin to develop other cyclopentanol preparation technologies. Firstly, attention is paid to a cyclopentene hydration method, and the hydration method is divided into a direct hydration method and an indirect hydration method, wherein the direct hydration method has the defects of low cyclopentene conversion rate and difficult industrialization; the sulfuric acid used in the indirect hydration method has the defects of higher requirement on equipment and increased cost.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a process device and a process method for preparing cyclopentanol from cyclopentene aiming at the defects in the prior art, and the invention has the advantages of high cyclopentene conversion rate, high cyclopentanol yield and low equipment and operation cost.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention firstly provides a process unit for preparing cyclopentanol from cyclopentene, which comprises a reactor, a catalytic distillation tower, a hydrogenation reactor, a gas-liquid separation tank and a distillation tower which are connected in sequence, and is characterized in that:
the reactor, the top is equipped with feed inlet A, the bottom is equipped with discharge gate A, wherein: the feed inlet A is connected with a device capable of providing cyclopentene and/or organic acid;
catalytic distillation tower, the top be equipped with the light component export, the middle part is equipped with feed inlet B, the bottom is equipped with discharge gate B, wherein: the light component outlet is connected with a feed inlet A of the reactor; the feed inlet B is connected with a discharge outlet A of the reactor;
hydrogenation ware, the top be equipped with feed inlet C, the bottom is equipped with discharge gate C, lateral wall upper portion is equipped with the hydrogen import, wherein: the feed inlet C is connected with a discharge outlet B of the catalytic distillation tower; the hydrogen inlet is connected with a device capable of providing hydrogen;
gas-liquid separation jar, the top is equipped with the gas phase export, the middle part is equipped with feed inlet D, the bottom is equipped with discharge gate D, wherein: the feed inlet D is connected with a discharge hole C of the hydrogenation reactor; the gas phase outlet is connected with the hydrogen inlet of the hydrogenation reactor;
distillation column, the top be equipped with the export of light component organic alcohol, the middle part is equipped with feed inlet E, the bottom is equipped with discharge gate E, wherein: the light component organic alcohol outlet is connected with an organic alcohol collecting device, and the feed inlet E is connected with the discharge outlet D of the gas-liquid separation tank; and the discharge hole E is connected with a device for recovering cyclopentanol.
In the technical scheme, the reactor is internally provided with a catalyst A, and the catalyst A is an acid resin catalyst, specifically any one of a macroporous acid resin catalyst, a mesoporous acid resin catalyst and a gel acid resin catalyst.
In the above technical scheme, the catalytic distillation tower is internally provided with a catalyst B, and the catalyst B is an acidic resin catalyst, specifically, any one of a macroporous acidic resin catalyst, a mesoporous acidic resin catalyst and a gel acidic resin catalyst.
In the technical scheme, a catalyst C is filled in the hydrogenation reactor, and the catalyst C is a (commercially available) ester hydrogenation catalyst.
In the technical scheme, the reactor, the catalytic distillation tower, the hydrogenation reactor, the gas-liquid separation tank and the distillation tower are all commercially available equipment in the field or conventional or traditional equipment.
The invention also provides a process method for preparing cyclopentanol from cyclopentene, which comprises the following steps:
(1) pre-reaction: cyclopentene and organic acid enter the reactor from the feed inlet A, react under the catalytic action of catalyst A in the reactor to get organic acid cyclopentyl ester, the reaction product is organic acid cyclopentyl ester, unreacted cyclopentene, unreacted organic acid that the reaction produces, the reaction product is discharged from the discharge outlet A and enters the catalytic distillation column from the feed inlet B;
(2) catalytic distillation reaction: enabling the reaction product obtained in the step (1) to enter a catalytic distillation tower, enabling unreacted cyclopentene and unreacted organic acid to continuously react under the catalytic action of a catalyst B in the catalytic distillation tower to continuously obtain organic acid cyclopentyl ester, obtaining light components containing cyclopentene and organic acid at the tower top after catalytic distillation, and obtaining heavy components containing organic acid cyclopentyl ester at the tower bottom; the light component is discharged from a light component outlet at the top of the tower and returns to the reactor from a feed inlet A for cyclic utilization; heavy components are discharged from a discharge hole B and enter the hydrogenation reactor from a feed hole C;
(3) hydrogenation reaction: the heavy component containing the organic acid cyclopentyl ester obtained in the step (2) enters a hydrogenation reactor, hydrogen is introduced into the hydrogenation reactor from a hydrogen inlet, the organic acid cyclopentyl ester and the hydrogen are subjected to hydrogenation reaction under the catalytic action of a catalyst C in the hydrogenation reactor to obtain cyclopentanol and organic alcohol, and the reaction products are the cyclopentanol and the organic alcohol generated by the reaction and unreacted hydrogen; the reaction product is discharged from the discharge hole C and enters the gas-liquid separation tank from the feed hole D;
(4) gas-liquid separation: separating the product obtained in the step (3) in a gas-liquid separation tank to obtain light component hydrogen at the tower top and heavy components containing cyclopentanol and organic alcohol at the tower bottom; hydrogen is discharged from the gas phase outlet and is returned to the hydrogenation reactor from the hydrogen inlet for cyclic utilization; discharging heavy components containing cyclopentanol and organic alcohol from a discharge hole D and feeding the heavy components into the distillation tower from a feed hole E;
(5) distillation and separation: the heavy component containing cyclopentanol and organic alcohol obtained in the step (4) enters a distillation tower for separation, a light component containing organic alcohol is obtained at the tower top, and a heavy component containing cyclopentanol is obtained at the tower bottom; and (4) discharging the organic alcohol from a light component organic alcohol outlet at the top of the tower, and then harvesting, and discharging the cyclopentanol from a discharge hole E at the bottom of the tower, and then harvesting.
In the above technical scheme, in the step (1), the organic acid is any one of formic acid, acetic acid and propionic acid.
In the technical scheme, in the step (1), the molar ratio of the organic acid to the cyclopentene is 1.2-8: 1.
in the technical scheme, in the step (1), the space velocity of the reactor fed from the feed inlet A is 0.5-5 h-1。
In the above technical scheme, in the step (1), the catalyst a is an acidic resin catalyst, specifically, any one of a macroporous acidic resin catalyst, a mesoporous acidic resin catalyst, and a gel acidic resin catalyst.
In the technical scheme, in the step (1), the reaction temperature of the reactor is 40-120 ℃, preferably 50-100 ℃, and the reaction pressure is 0.1-1 MPa.
In the technical scheme, in the step (2), the space velocity of the catalytic distillation tower fed from the feed inlet B is 0.5-5 h-1。
In the above technical scheme, in the step (2), the catalyst B is an acidic resin catalyst, specifically, any one of a macroporous acidic resin catalyst, a mesoporous acidic resin catalyst, and a gel acidic resin catalyst.
In the technical scheme, in the step (2), the reaction temperature of the reaction section of the catalytic distillation tower is 50-180 ℃, and the reaction pressure is-0.1-2 MPa.
In the technical scheme, in the step (3), the molar ratio of the hydrogen to the organic acid is 8-25: 1, preferably the molar ratio is 10-20: 1.
in the technical scheme, in the step (3), the space velocity of the feeding of the hydrogenation reactor from the feeding hole C is 0.2-8 h-1Preferably 0.5 to 2 hours-1。
In the above technical scheme, in the step (3), the catalyst C is a (commercially available) ester hydrogenation catalyst.
In the technical scheme, in the step (3), the reaction temperature of the hydrogenation reactor is 150-300 ℃, and preferably 180-260 ℃; the reaction pressure is 3-8 MPa, preferably 4-6 MPa.
In the technical scheme, in the step (4), the temperature of the gas-liquid separation tank is 15-80 ℃, and the pressure is 0-1 MPa. .
In the technical scheme, in the step (5), the temperature at the top of the distillation tower is 40-140 ℃, the pressure is 0-1 MPa, the temperature at the bottom of the distillation tower is 162-200 ℃, and the pressure is 0-1 MPa.
The technical scheme of the invention has the advantages that: the cyclopentene and the organic acid are synthesized into the organic acid cyclopentyl ester, then the organic alcohol and the cyclopentanol are obtained through hydrogenation, and finally the cyclopentanol is separated through the distillation tower.
Drawings
FIG. 1 is a schematic diagram of a process for preparing cyclopentanol from cyclopentene according to the present invention;
FIG. 2 is a schematic diagram showing the overall structure of the process apparatus for preparing cyclopentanol from cyclopentene according to the present invention;
wherein, 1, a reactor; 2. a catalytic distillation column; 3. a hydrogenation reactor; 4. a gas-liquid separation tank; 5. a distillation column.
Detailed Description
The following detailed description of the embodiments of the present invention is provided, but the present invention is not limited to the following descriptions:
the invention firstly provides a process unit for preparing cyclopentanol from cyclopentene, which comprises a reactor 1, a catalytic distillation tower 2, a hydrogenation reactor 3, a gas-liquid separation tank 4 and a distillation tower 5 which are connected in sequence, as shown in figure 2:
reactor 1, the top is equipped with feed inlet A, the bottom is equipped with discharge gate A, wherein: the feed inlet A is connected with a device capable of providing cyclopentene and/or organic acid;
gas-liquid separation jar 4, the top is equipped with the gas phase export, the middle part is equipped with feed inlet D, the bottom is equipped with discharge gate D, wherein: the feed inlet D is connected with a discharge hole C of the hydrogenation reactor; the gas phase outlet is connected with the hydrogen inlet of the hydrogenation reactor;
In the technical scheme, the reactor is internally provided with a catalyst A, and the catalyst A is an acid resin catalyst, specifically any one of a macroporous acid resin catalyst, a mesoporous acid resin catalyst and a gel acid resin catalyst.
In the above technical scheme, the catalytic distillation tower is internally provided with a catalyst B, and the catalyst B is an acidic resin catalyst, specifically, any one of a macroporous acidic resin catalyst, a mesoporous acidic resin catalyst and a gel acidic resin catalyst.
In the technical scheme, a catalyst C is filled in the hydrogenation reactor, and the catalyst C is a (commercially available) ester hydrogenation catalyst.
In the technical scheme, the reactor, the catalytic distillation tower, the hydrogenation reactor, the gas-liquid separation tank and the distillation tower are all commercially available equipment in the field or conventional or traditional equipment.
The invention also provides a process method for preparing cyclopentanol from cyclopentene, which comprises the following steps, with a flow chart shown in figure 1:
(1) pre-reaction: cyclopentene and organic acid enter the reactor from the feed inlet A, react under the catalytic action of catalyst A in the reactor to get organic acid cyclopentyl ester, the reaction product is organic acid cyclopentyl ester, unreacted cyclopentene, unreacted organic acid that the reaction produces, the reaction product is discharged from the discharge outlet A and enters the catalytic distillation column from the feed inlet B;
(2) catalytic distillation reaction: enabling the reaction product obtained in the step (1) to enter a catalytic distillation tower, enabling unreacted cyclopentene and unreacted organic acid to continuously react under the catalytic action of a catalyst B in the catalytic distillation tower to continuously obtain organic acid cyclopentyl ester, obtaining light components containing cyclopentene and organic acid at the tower top after catalytic distillation, and obtaining heavy components containing organic acid cyclopentyl ester at the tower bottom; the light component is discharged from a light component outlet at the top of the tower and returns to the reactor from a feed inlet A for cyclic utilization; heavy components are discharged from a discharge hole B and enter the hydrogenation reactor from a feed hole C;
(3) hydrogenation reaction: the heavy component containing the organic acid cyclopentyl ester obtained in the step (2) enters a hydrogenation reactor, hydrogen is introduced into the hydrogenation reactor from a hydrogen inlet, the organic acid cyclopentyl ester and the hydrogen are subjected to hydrogenation reaction under the catalytic action of a catalyst C in the hydrogenation reactor to obtain cyclopentanol and organic alcohol, and the reaction products are the cyclopentanol and the organic alcohol generated by the reaction and unreacted hydrogen; the reaction product is discharged from the discharge hole C and enters the gas-liquid separation tank from the feed hole D;
(4) gas-liquid separation: separating the product obtained in the step (3) in a gas-liquid separation tank to obtain light component hydrogen at the tower top and heavy components containing cyclopentanol and organic alcohol at the tower bottom; hydrogen is discharged from the gas phase outlet and is returned to the hydrogenation reactor from the hydrogen inlet for cyclic utilization; discharging heavy components containing cyclopentanol and organic alcohol from a discharge hole D and feeding the heavy components into the distillation tower from a feed hole E;
(5) distillation and separation: the heavy component containing cyclopentanol and organic alcohol obtained in the step (4) enters a distillation tower for separation, a light component containing organic alcohol is obtained at the tower top, and a heavy component containing cyclopentanol is obtained at the tower bottom; and (4) discharging the organic alcohol from a light component organic alcohol outlet at the top of the tower, and then harvesting, and discharging the cyclopentanol from a discharge hole E at the bottom of the tower, and then harvesting.
The invention is illustrated below with reference to specific examples:
example 1:
a process method for preparing cyclopentanol from cyclopentene comprises the following steps:
(1) pre-reaction: cyclopentene and formic acid (the molar ratio of formic acid to cyclopentene is 1.2: 1) enter the reactor from the feed inlet A, and the space velocity is 0.5h-1(ii) a Reacting under the catalytic action of a KC119 type acidic resin catalyst in a reactor to obtain cyclopentyl formate, wherein reaction products are generated by the reaction, unreacted cyclopentene and unreacted formic acid, and are discharged from a discharge hole A and enter a catalytic distillation tower from a feed hole B; the reaction temperature of the reactor was 40 ℃ and the pressure was 0.1 MPa.
(2) Catalytic distillation reaction: the reaction product obtained in step (1) (space velocity of 0.5 h)-1) The reaction product enters a catalytic distillation tower, unreacted cyclopentene and unreacted formic acid continue to react under the catalytic action of a KC119 type acidic resin catalyst in the catalytic distillation tower to continuously obtain cyclopentyl formate, light components containing cyclopentene and formic acid are obtained at the tower top after catalytic distillation, and heavy components containing cyclopentyl formate are obtained at the tower bottom; the light component is discharged from a light component outlet at the top of the tower and returns to the reactor from a feed inlet A for cyclic utilization; heavy components are discharged from a discharge hole B and enter the hydrogenation reactor from a feed hole C; the reaction temperature of the catalytic distillation tower is 50 ℃, and the reaction pressure is 1 MPa.
(3) Hydrogenation reaction: the heavy component containing cyclopentyl formate obtained in the step (2) (with the space velocity of 0.2 h)-1) And (2) entering the hydrogenation reactor, and simultaneously introducing hydrogen into the hydrogenation reactor from a hydrogen inlet, wherein the molar ratio of the cyclopentyl formate to the hydrogen (the molar ratio of the hydrogen to the cyclopentyl formate is 8: 1) performing hydrogenation reaction under the catalytic action of RK-22 oxalate hydrogenation catalyst (produced by Dalikey technologies, Ltd.) in a hydrogenation reactor to obtain cyclopentanol and methanolThe products are cyclopentanol and methanol generated by the reaction and unreacted hydrogen; the reaction product is discharged from the discharge hole C and enters the gas-liquid separation tank from the feed hole D; the reaction temperature of the hydrogenation reactor is 150 ℃, and the reaction pressure is 3 MPa.
(4) Gas-liquid separation: separating the product obtained in the step (3) in a gas-liquid separation tank to obtain light component hydrogen at the top of the tower and heavy components containing cyclopentanol and methanol at the bottom of the tower; hydrogen is discharged from the gas phase outlet and is returned to the hydrogenation reactor from the hydrogen inlet for cyclic utilization; discharging heavy components containing cyclopentanol and methanol from a discharge hole D and feeding the heavy components into the distillation tower from a feed hole E; the temperature of the gas-liquid separation tank is 15 ℃, and the pressure is 0 MPa.
(5) Distillation and separation: the heavy component containing cyclopentanol and methanol obtained in the step (4) enters a distillation tower for separation, a light component containing methanol is obtained at the top of the tower, and a heavy component containing cyclopentanol is obtained at the bottom of the tower; and (3) discharging the methanol from a light component organic alcohol outlet at the top of the tower, and then harvesting, and discharging the cyclopentanol from a discharge hole E at the bottom of the tower, and then harvesting. And in the distillation tower, the temperature at the top of the tower is 40 ℃, the pressure is 0MPa, the temperature at the bottom of the tower is 162 ℃, and the pressure is 0 MPa.
In this example, the conversion of cyclopentene was 90% and the yield of cyclopentanol was 89.9%.
Example 2:
a process method for preparing cyclopentanol from cyclopentene comprises the following steps:
(1) pre-reaction: cyclopentene and acetic acid (the molar ratio of the acetic acid to the cyclopentene is 4: 1) enter the reactor from the feed inlet A, and the space velocity is 2.5h-1(ii) a Reacting under the catalytic action of a KC104 type acidic resin catalyst in a reactor to obtain cyclohexyl acetate, wherein reaction products are cyclopentyl acetate, unreacted cyclopentene and unreacted acetic acid which are generated by the reaction, and are discharged from a discharge hole A and enter a catalytic distillation tower from a feed hole B; the reaction temperature of the reactor was 50 ℃ and the pressure was 0.5 MPa.
(2) Catalytic distillation reaction: the reaction product obtained in step (1) (space velocity of 2.5 h)-1) Entering a catalytic distillation tower, and allowing unreacted cyclopentene and unreacted acetic acid to enter the catalytic distillation towerContinuously reacting under the catalytic action of an inner KC119 type macroporous acidic resin catalyst to continuously obtain cyclopentyl acetate, and after catalytic distillation, obtaining a light component containing cyclopentene and acetic acid at the tower top and a heavy component containing cyclopentyl acetate at the tower bottom; the light component is discharged from a light component outlet at the top of the tower and returns to the reactor from a feed inlet A for cyclic utilization; heavy components are discharged from a discharge hole B and enter the hydrogenation reactor from a feed hole C; the reaction temperature of the catalytic distillation tower is 80 ℃, and the reaction pressure is-0.1 MPa.
(3) Hydrogenation reaction: the heavy component containing cyclopentyl acetate obtained in the step (2) (with space velocity of 0.5 h)-1) And (2) introducing hydrogen into the hydrogenation reactor from a hydrogen inlet, wherein the molar ratio of the cyclopentyl acetate to the hydrogen (the molar ratio of the hydrogen to the cyclopentyl acetate is 10: 1) performing hydrogenation reaction under the catalytic action of RK-22 oxalate hydrogenation catalyst (produced by Dalike technology Co., Ltd.) in a hydrogenation reactor to obtain cyclopentanol and ethanol, wherein the reaction products are cyclopentanol and ethanol generated by the reaction and unreacted hydrogen; the reaction product is discharged from the discharge hole C and enters the gas-liquid separation tank from the feed hole D; the reaction temperature of the hydrogenation reactor is 180 ℃, and the reaction pressure is 4 MPa.
(4) Gas-liquid separation: separating the product obtained in the step (3) in a gas-liquid separation tank to obtain light component hydrogen at the tower top and heavy components containing cyclopentanol and ethanol at the tower bottom; hydrogen is discharged from the gas phase outlet and is returned to the hydrogenation reactor from the hydrogen inlet for cyclic utilization; discharging heavy components containing cyclopentanol and ethanol from a discharge hole D and feeding the heavy components into the distillation tower from a feed hole E; the temperature of the gas-liquid separation tank is 20 ℃, and the pressure is 0.2 MPa.
(5) Distillation and separation: the heavy component containing cyclopentanol and ethanol obtained in the step (4) enters a distillation tower for separation, a light component containing ethanol is obtained at the tower top, and a heavy component containing cyclopentanol is obtained at the tower bottom; and the ethanol is collected after being discharged from a light component organic alcohol outlet at the top of the tower, and the cyclopentanol is collected after being discharged from a discharge hole E at the bottom of the tower. And in the distillation tower, the temperature at the top of the tower is 140 ℃, the pressure is 1MPa, the temperature at the bottom of the tower is 200 ℃, and the pressure is 1 MPa.
In this example, the conversion of cyclopentene was 95% and the yield of cyclopentanol was 94.9%.
Example 3:
a process method for preparing cyclopentanol from cyclopentene comprises the following steps:
(1) pre-reaction: cyclopentene and propionic acid (the molar ratio of propionic acid to cyclopentene is 6: 1) enter the reactor from the feed inlet A, and the space velocity is 4h-1(ii) a Reacting under the catalytic action of a KIP213 type gel acidic resin catalyst in a reactor to obtain cyclopentyl propionate, wherein the reaction products are generated by the reaction, unreacted cyclopentene and unreacted propionic acid, and are discharged from a discharge hole A and enter a catalytic distillation tower from a feed hole B; the reaction temperature of the reactor was 100 ℃ and the pressure was 0.8 MPa.
(2) Catalytic distillation reaction: the reaction product obtained in step (1) (space velocity of 4 h)-1) The reaction product enters a catalytic distillation tower, unreacted cyclopentene and unreacted propionic acid continue to react in a KC119 type macroporous acidic resin catalyst in the catalytic distillation tower to obtain cyclopentyl propionate, light components containing cyclopentene and propionic acid are obtained at the tower top after catalytic distillation, and heavy components containing cyclopentyl propionate are obtained at the tower bottom; the light component is discharged from a light component outlet at the top of the tower and returns to the reactor from a feed inlet A for cyclic utilization; heavy components are discharged from a discharge hole B and enter the hydrogenation reactor from a feed hole C; the reaction temperature of the catalytic distillation tower is 100 ℃, and the reaction pressure is 0 MPa.
(3) Hydrogenation reaction: the heavy component containing the cyclopentyl propionate obtained in the step (2) (with the space velocity of 2 h)-1) And (2) entering the reaction mixture into a hydrogenation reactor, and simultaneously introducing hydrogen into the hydrogenation reactor from a hydrogen inlet, wherein the molar ratio of the cyclopentyl propionate to the hydrogen (the molar ratio of the hydrogen to the cyclopentyl propionate is 20: 1) performing hydrogenation reaction under the catalytic action of RK-22 oxalate hydrogenation catalyst (produced by Dalike technology Co., Ltd.) in a hydrogenation reactor to obtain cyclopentanol and propanol, wherein the reaction products are cyclopentanol and propanol generated by the reaction and unreacted hydrogen; the reaction product is discharged from the discharge hole C and enters the gas-liquid separation tank from the feed hole D; the reaction temperature of the hydrogenation reactor is 260 ℃, and the reaction pressure is 6 MPa.
(4) Gas-liquid separation: separating the product obtained in the step (3) in a gas-liquid separation tank to obtain light component hydrogen at the tower top and heavy components containing cyclopentanol and propanol at the tower bottom; hydrogen is discharged from the gas phase outlet and is returned to the hydrogenation reactor from the hydrogen inlet for cyclic utilization; discharging heavy components containing cyclopentanol and propanol from a discharge hole D and feeding the heavy components into the distillation tower from a feed hole E; the temperature of the gas-liquid separation tank is 50 ℃, and the pressure is 0.5 MPa.
(5) Distillation and separation: the heavy component containing cyclopentanol and propanol obtained in the step (4) enters a distillation tower for separation, a light component containing propanol is obtained at the tower top, and a heavy component containing cyclopentanol is obtained at the tower bottom; and the ethanol is collected after being discharged from a light component organic alcohol outlet at the top of the tower, and the cyclopentanol is collected after being discharged from a discharge hole E at the bottom of the tower. The temperature of the top of the distillation tower is 50 ℃, the pressure is 0.5MPa, the temperature of the bottom of the distillation tower is 180 ℃, and the pressure is 0.5 MPa.
In this example, the conversion of cyclopentene was 98% and the yield of cyclopentanol was 97.8%.
Example 4:
a process method for preparing cyclopentanol from cyclopentene comprises the following steps:
(1) pre-reaction: cyclopentene and acetic acid (the molar ratio of the acetic acid to the cyclopentene is 8: 1) enter the reactor from the feed inlet A, and the space velocity is 5h-1(ii) a Reacting under the catalytic action of a KIP213 type gel acidic resin catalyst in a reactor to obtain cyclohexyl acetate, wherein reaction products are cyclopentyl acetate, unreacted cyclopentene and unreacted acetic acid generated by the reaction, and are discharged from a discharge hole A and enter a catalytic distillation tower from a feed hole B; the reaction temperature of the reactor was 120 ℃ and the pressure was 1 MPa.
(2) Catalytic distillation reaction: the reaction product obtained in step (1) (space velocity of 5 h)-1) Entering a catalytic distillation tower, continuously reacting unreacted cyclopentene and unreacted acetic acid under the catalytic action of a KIP213 type gel acidic resin catalyst in the catalytic distillation tower to continuously obtain cyclopentyl acetate, performing catalytic distillation to obtain a light component containing cyclopentene and acetic acid at the tower top, and obtaining a light component containing cyclopentyl acetate at the tower bottomHeavy components; the light component is discharged from a light component outlet at the top of the tower and returns to the reactor from a feed inlet A for cyclic utilization; heavy components are discharged from a discharge hole B and enter the hydrogenation reactor from a feed hole C; the reaction temperature of the catalytic distillation tower is 180 ℃, and the reaction pressure is 2 MPa.
(3) Hydrogenation reaction: the heavy component containing cyclopentyl acetate obtained in the step (2) (with the space velocity of 8 h)-1) And (2) introducing hydrogen into the hydrogenation reactor from a hydrogen inlet, wherein the molar ratio of the cyclopentyl acetate to the hydrogen (the molar ratio of the hydrogen to the cyclopentyl acetate is 25: 1) performing hydrogenation reaction under the catalytic action of RK-22 oxalate hydrogenation catalyst (produced by Dalike technology Co., Ltd.) in a hydrogenation reactor to obtain cyclopentanol and ethanol, wherein the reaction products are cyclopentanol and ethanol generated by the reaction and unreacted hydrogen; the reaction product is discharged from the discharge hole C and enters the gas-liquid separation tank from the feed hole D; the reaction temperature of the hydrogenation reactor is 300 ℃, and the reaction pressure is 8 MPa.
(4) Gas-liquid separation: separating the product obtained in the step (3) in a gas-liquid separation tank to obtain light component hydrogen at the tower top and heavy components containing cyclopentanol and ethanol at the tower bottom; hydrogen is discharged from the gas phase outlet and is returned to the hydrogenation reactor from the hydrogen inlet for cyclic utilization; discharging heavy components containing cyclopentanol and ethanol from a discharge hole D and feeding the heavy components into the distillation tower from a feed hole E; the temperature of the gas-liquid separation tank is 80 ℃, and the pressure is 1 MPa.
(5) Distillation and separation: the heavy component containing cyclopentanol and ethanol obtained in the step (4) enters a distillation tower for separation, a light component containing ethanol is obtained at the tower top, and a heavy component containing cyclopentanol is obtained at the tower bottom; and the ethanol is collected after being discharged from a light component organic alcohol outlet at the top of the tower, and the cyclopentanol is collected after being discharged from a discharge hole E at the bottom of the tower. The temperature of the top of the distillation tower is 80 ℃, the pressure is 0.8MPa, the temperature of the bottom of the distillation tower is 190 ℃, and the pressure is 0.8 MPa.
In this example, the conversion of cyclopentene was 99% and the yield of cyclopentanol was 98.8%.
The above examples are only for illustrating the technical concept and features of the present invention, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A process method for preparing cyclopentanol from cyclopentene is characterized by comprising the following steps:
(1) pre-reaction: cyclopentene and organic acid enter the reactor from the feed inlet A, react under the catalytic action of catalyst A in the reactor to get organic acid cyclopentyl ester, the reaction product is organic acid cyclopentyl ester, unreacted cyclopentene, unreacted organic acid that the reaction produces, the reaction product is discharged from the discharge outlet A and enters the catalytic distillation column from the feed inlet B;
(2) catalytic distillation reaction: enabling the reaction product obtained in the step (1) to enter a catalytic distillation tower, enabling unreacted cyclopentene and unreacted organic acid to continuously react under the catalytic action of a catalyst B in the catalytic distillation tower to continuously obtain organic acid cyclopentyl ester, obtaining light components containing cyclopentene and organic acid at the tower top after catalytic distillation, and obtaining heavy components containing organic acid cyclopentyl ester at the tower bottom; the light component is discharged from a light component outlet at the top of the tower and returns to the reactor from a feed inlet A for cyclic utilization; heavy components are discharged from a discharge hole B and enter the hydrogenation reactor from a feed hole C;
(3) hydrogenation reaction: the heavy component containing the organic acid cyclopentyl ester obtained in the step (2) enters a hydrogenation reactor, hydrogen is introduced into the hydrogenation reactor from a hydrogen inlet, the organic acid cyclopentyl ester and the hydrogen are subjected to hydrogenation reaction under the catalytic action of a catalyst C in the hydrogenation reactor to obtain cyclopentanol and organic alcohol, and the reaction products are the cyclopentanol and the organic alcohol generated by the reaction and unreacted hydrogen; the reaction product is discharged from the discharge hole C and enters the gas-liquid separation tank from the feed hole D;
(4) gas-liquid separation: separating the product obtained in the step (3) in a gas-liquid separation tank to obtain light component hydrogen at the tower top and heavy components containing cyclopentanol and organic alcohol at the tower bottom; hydrogen is discharged from the gas phase outlet and is returned to the hydrogenation reactor from the hydrogen inlet for cyclic utilization; discharging heavy components containing cyclopentanol and organic alcohol from a discharge hole D and feeding the heavy components into the distillation tower from a feed hole E;
(5) distillation and separation: the heavy component containing cyclopentanol and organic alcohol obtained in the step (4) enters a distillation tower for separation, a light component containing organic alcohol is obtained at the tower top, and a heavy component containing cyclopentanol is obtained at the tower bottom; and (4) discharging the organic alcohol from a light component organic alcohol outlet at the top of the tower, and then harvesting, and discharging the cyclopentanol from a discharge hole E at the bottom of the tower, and then harvesting.
2. The process of claim 1, wherein in step (1), the organic acid is any one of formic acid, acetic acid or propionic acid; the molar ratio of the organic acid to the cyclopentene is 1.2-8: 1; the catalyst A is an acidic resin catalyst.
3. The process of claim 1, wherein in step (1), the space velocity of the reactor fed through the feed inlet A is 0.5-5 h-1(ii) a The reactor has the reaction temperature of 40-120 ℃ and the reaction pressure of 0.1-1 MPa.
4. The process of claim 1, wherein in the step (2), the space velocity of the feed from the feed inlet B of the catalytic distillation tower is 0.5-5 h-1(ii) a The catalyst B is an acidic resin catalyst; the catalytic distillation tower has a reaction temperature of 50-180 ℃ and a reaction pressure of-0.1-2 MPa in a reaction section.
5. The process of claim 1, wherein in step (3), the molar ratio of hydrogen to organic acid is 8-25: 1; the catalyst C is an ester hydrogenation catalyst.
6. The process method according to claim 1, wherein in the step (3), the space velocity of the feeding of the hydrogenation reactor from the feeding hole C is 0.2-8 h-1(ii) a The reaction temperature of the hydrogenation reactor is 150-300 ℃, and the reaction pressure is 3-8 MPa.
7. The process method according to claim 1, wherein in the step (4), the temperature of the gas-liquid separation tank is 15-80 ℃, and the pressure is 0-1 MPa.
8. The process according to claim 1, wherein in the step (5), the temperature at the top of the distillation column is 40 to 140 ℃, the pressure is 0 to 1MPa, the temperature at the bottom of the distillation column is 162 to 200 ℃, and the pressure is 0 to 1 MPa.
9. The utility model provides a process units of cyclopentene preparation cyclopentanol, includes reactor (1), catalytic distillation tower (2), hydrogenation ware (3), gas-liquid separation jar (4) and distillation column (5) that connect gradually, its characterized in that:
reactor (1), the top is equipped with feed inlet A, the bottom is equipped with discharge gate A, wherein: the feed inlet A is connected with a device capable of providing cyclopentene and/or organic acid;
catalytic distillation tower (2), the top is equipped with the light component export, the middle part is equipped with feed inlet B, the bottom is equipped with discharge gate B, wherein: the light component outlet is connected with a feed inlet A of the reactor; the feed inlet B is connected with a discharge outlet A of the reactor;
hydrogenation ware (3), the top is equipped with feed inlet C, the bottom is equipped with discharge gate C, lateral wall upper portion is equipped with the hydrogen import, wherein: the feed inlet C is connected with a discharge outlet B of the catalytic distillation tower; the hydrogen inlet is connected with a device capable of providing hydrogen;
gas-liquid separation jar (4), the top is equipped with the gas phase export, the middle part is equipped with feed inlet D, the bottom is equipped with discharge gate D, wherein: the feed inlet D is connected with a discharge hole C of the hydrogenation reactor; the gas phase outlet is connected with the hydrogen inlet of the hydrogenation reactor;
distillation column (5), the top is equipped with the export of light component organic alcohol, and the middle part is equipped with feed inlet E, and the bottom is equipped with discharge gate E, wherein: the light component organic alcohol outlet is connected with an organic alcohol collecting device, and the feed inlet E is connected with the discharge outlet D of the gas-liquid separation tank; the discharge hole E is connected with a device for collecting cyclopentanol;
the reactor (1) is internally provided with a catalyst A, the catalytic distillation tower (2) is internally provided with a catalyst B, and the hydrogenation reactor (3) is internally provided with a catalyst C.
10. The process arrangement of claim 9, wherein: the catalyst A is an acidic resin catalyst; the catalyst B is an acidic resin catalyst; the catalyst C is an ester hydrogenation catalyst.
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| CN114621084A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Process for preparing cyclic hydrocarbon oxide and co-producing alcohol compound |
| CN115806477A (en) * | 2021-09-14 | 2023-03-17 | 中国科学院大连化学物理研究所 | Method and device for producing cyclopentanone product |
| CN116354792A (en) * | 2023-04-03 | 2023-06-30 | 福州大学 | Method for preparing cyclopentanol from cyclopentene and working method thereof |
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