CN117986074A - Production method and production device of low-carbon-ring-shaped hydrocarbon - Google Patents
Production method and production device of low-carbon-ring-shaped hydrocarbon Download PDFInfo
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- CN117986074A CN117986074A CN202211373608.XA CN202211373608A CN117986074A CN 117986074 A CN117986074 A CN 117986074A CN 202211373608 A CN202211373608 A CN 202211373608A CN 117986074 A CN117986074 A CN 117986074A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 10
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 10
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 9
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 116
- 239000002994 raw material Substances 0.000 claims abstract description 104
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 66
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000000926 separation method Methods 0.000 claims abstract description 59
- 238000005336 cracking Methods 0.000 claims abstract description 48
- 239000003085 diluting agent Substances 0.000 claims abstract description 48
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 239000007788 liquid Substances 0.000 claims abstract description 29
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 238000009833 condensation Methods 0.000 claims abstract description 17
- 230000005494 condensation Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003701 inert diluent Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims description 38
- 238000011084 recovery Methods 0.000 claims description 34
- 238000010790 dilution Methods 0.000 claims description 23
- 239000012895 dilution Substances 0.000 claims description 23
- 239000012071 phase Substances 0.000 claims description 22
- 239000007789 gas Substances 0.000 claims description 21
- 239000007791 liquid phase Substances 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 8
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 239000012535 impurity Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000009834 vaporization Methods 0.000 description 3
- 230000008016 vaporization Effects 0.000 description 3
- 238000003776 cleavage reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- BGTOWKSIORTVQH-UHFFFAOYSA-N cyclopentanone Chemical compound O=C1CCCC1 BGTOWKSIORTVQH-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- -1 carbon ring hydrocarbon Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Classifications
-
- 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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/009—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping in combination with chemical reactions
-
- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/001—Feed or outlet devices as such, e.g. feeding tubes
-
- 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
- B01J4/00—Feed or outlet devices; Feed or outlet control devices
- B01J4/008—Feed or outlet control devices
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/22—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by depolymerisation to the original monomer, e.g. dicyclopentadiene to cyclopentadiene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/03—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of non-aromatic carbon-to-carbon double bonds
- C07C5/05—Partial hydrogenation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/09—Purification; Separation; Use of additives by fractional condensation
-
- 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
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/002—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the feeding side being of particular interest
-
- 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
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/005—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices the outlet side being of particular interest
-
- 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
- B01J2204/00—Aspects relating to feed or outlet devices; Regulating devices for feed or outlet devices
- B01J2204/007—Aspects relating to the heat-exchange of the feed or outlet devices
-
- 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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00002—Chemical plants
- B01J2219/00004—Scale aspects
- B01J2219/00006—Large-scale industrial plants
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/08—Systems containing only non-condensed rings with a five-membered ring the ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
- C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Analytical Chemistry (AREA)
- Water Supply & Treatment (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The application discloses a production method and a production device of low-carbon ring-shaped hydrocarbon, wherein the production method comprises a reaction stage and a separation stage; the reaction stage comprises: preheating a raw material I containing cyclopentadiene I and hydrogen I, introducing the raw material I into a cracking reactor, performing cracking reaction to obtain a cracking reaction product, performing heat exchange on the cracking reaction product and the raw material I to obtain a hydrogenation raw material, mixing the hydrogenation raw material with a diluent, and introducing the mixture into the hydrogenation reactor to perform hydrogenation reaction to obtain a hydrogenation reaction product; the separation stage comprises: and (3) carrying out gas-liquid separation and three-stage rectification treatment on the hydrogenation reaction product to sequentially obtain hydrogen II, cyclopentadiene II, cyclopentene and cyclopentane. The method can be used for the production method for preparing the cyclopentene by partial hydrogenation of cyclopentadiene, has continuous process and simple flow, saves high-grade cold energy consumption by fractional condensation, controls reaction temperature rise by adding the inert diluent of the cyclic reaction, and is suitable for industrialized large-scale continuous operation.
Description
Technical Field
The application relates to a production method and a production device of low-carbon ring-shaped hydrocarbon, belonging to the technical field of chemical industry.
Background
Cyclopentene is an important pharmaceutical and chemical intermediate and synthetic raw material, can be used for preparing high-added-value products such as cyclopentanol, cyclopentanone, cyclopentane and the like, can be further synthesized into halogenated cycloalkanes for preparing pesticides, and can be used for preparing polycycloolefin high-molecular polymers. At present, the cyclopentene synthesis route is mainly based on cyclopentadiene partial catalytic hydrogenation, but corresponding industrial scale preparation methods are reported, so that the continuous research and exploration are necessary.
Disclosure of Invention
The invention provides a production method for preparing cyclopentene by partial hydrogenation of cyclopentadiene, which has continuous process and simple flow, saves high-grade cold energy consumption by fractional condensation, controls hydrogenation reaction temperature rise by adopting a method of circulating inert diluent, and is suitable for industrialized large-scale continuous operation.
In one aspect of the present application, there is provided a process for producing a low-carbon-ring-like hydrocarbon comprising cyclopentene, cyclopentane;
The production method comprises a reaction stage and a separation stage;
The reaction stage comprises: preheating a raw material I containing cyclopentadiene I and hydrogen I, introducing the raw material I into a cracking reactor, performing cracking reaction to obtain a cracking reaction product, performing heat exchange on the cracking reaction product and the raw material I to obtain a hydrogenation raw material, mixing the hydrogenation raw material with a diluent, introducing the mixture into the hydrogenation reactor to perform hydrogenation reaction to obtain a hydrogenation reaction product;
The separation stage comprises: and (3) carrying out gas-liquid separation and three-stage rectification treatment on the hydrogenation reaction product to sequentially obtain hydrogen II, cyclopentadiene II, cyclopentene and cyclopentane.
And the pyrolysis reaction product exchanges heat with the raw material I to reach the reaction temperature, so that the pyrolysis waste heat is recycled, and the cold energy consumption is reduced.
Optionally, the raw material I also comprises hydrogen II and cyclopentadiene II;
In the raw material I, the molar ratio of cyclopentadiene to hydrogen is 0.1-5, wherein the molar quantity of cyclopentadiene is calculated by the total molar quantity of cyclopentadiene I and cyclopentadiene II, and the molar quantity of hydrogen is calculated by the total molar quantity of hydrogen I and hydrogen II.
Alternatively, the molar ratio of cyclopentadiene to hydrogen is independently selected from any of 0.1, 1,2, 3,4, 5 or a range between any two of the above.
Optionally, the preheating includes a first stage preheating and a second stage preheating;
the first stage of preheating is that the raw material I exchanges heat with the cracking reaction product to obtain a heat exchanged raw material II, wherein the raw material II is a superheated gas phase mixture;
The temperature of the superheated gas phase mixture is 100-200 ℃, and the vaporization temperature of the cracking raw material in the raw material I is controlled to be lower than 100 ℃ by pre-mixing hydrogen.
The second stage of preheating is to heat the raw material II;
Preferably, the raw material I also comprises dicyclopentadiene;
The cracking reaction product comprises cyclopentadiene III obtained by cracking dicyclopentadiene.
Alternatively, the temperature of the superheated gas-phase mixture is independently selected from any value or range of values between any two of the above values of 100 ℃, 132 ℃, 150 ℃,200 ℃.
Optionally, the reaction temperature of the cracking reaction is 200-500 ℃;
the reaction temperature of the hydrogenation reaction is 50-200 ℃, and the reaction pressure is 0.1-3 MPaA.
Alternatively, the reaction temperature of the cleavage reaction is independently selected from any value of 200 ℃, 350 ℃, 400 ℃, 500 ℃ or a range of values between any two points.
Alternatively, the reaction temperature of the hydrogenation reaction is independently selected from any value of 50 ℃, 110 ℃, 150 ℃, 200 ℃ or a range of values between any two points.
Alternatively, the reaction pressure of the hydrogenation reaction is independently selected from any of 0.1MPaA, 0.14MPaA, 0.5MPaA, 1MPaA, 2MPaA, 3MPaA or a range between any two of the above.
Optionally, the molar ratio of the diluent to the cyclopentadiene is 1.5-5:1, wherein the molar amount of the cyclopentadiene is calculated by the total molar amount of cyclopentadiene I, cyclopentadiene II and cyclopentadiene III in the hydrogenation raw material.
Alternatively, the diluent to cyclopentadiene molar ratio is independently selected from 1.5: 1. 2: 1. 2.9: 1. 4: 1.5:1 or a range between any two points.
Optionally, the diluent is an inert diluent; the temperature rise of the reaction hydrogenation reaction is controlled by an inert diluent.
Optionally, the inert diluent is selected from at least one of cyclohexane, benzene, heptane.
Optionally, the inert diluent is cyclohexane.
Optionally, the gas-liquid separation includes: and sequentially carrying out gas-liquid separation in the first stage and gas-liquid separation in the second stage on the hydrogenation reaction product to obtain hydrogen II and condensate after separation, wherein the hydrogen II is recycled. The hydrogenation reaction product reduces the cold energy required by hydrogen recovery through fractional condensation.
Alternatively, the gas-liquid separation obtains hydrogen, part of which is discharged as exhaust gas and part (hydrogen II) is circulated. The ratio of the circulation amount to the discharge amount is 0.5-5.
Optionally, the temperature of the hydrogenation reaction product after cooling is 0-100 ℃.
Optionally, the condensation temperature of the gas-liquid separation in the first stage is 0-60 ℃, and the separation pressure is 0-0.3 MpaA.
The condensation temperature of the gas-liquid separation in the second stage is-60 to-10 ℃, and the separation pressure is 0-0.3 MpaA.
Alternatively, the condensation temperature of the first stage gas-liquid separation is independently selected from any value of 0 ℃, 20 ℃, 42 ℃, 60 ℃ or a range of values between any two points.
Optionally, the separation pressure of the first stage gas-liquid separation is independently selected from any of 0MpaA, 0.1MpaA, 0.14MpaA, 0.2MpaA, 0.3MpaA, or a range of values between any two of the above.
Optionally, the condensation temperature of the second stage gas-liquid separation is independently selected from any of-60 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃ or a range of values between any two of the above.
Optionally, the separation pressure of the second stage gas-liquid separation is independently selected from any value of 0MpaA, 0.11MpaA, 0.15MpaA, 0.2MpaA, 0.3MpaA or a range of values between any two of the above.
Optionally, the three-stage rectification process comprises:
introducing the condensate into a recovery tower for rectification separation I, obtaining cyclopentadiene II in a liquid phase from the side wall of the tower, and obtaining a distillate from the bottom of the tower;
Introducing the distillate into a product tower for rectification separation II, obtaining cyclopentene at the top of the tower, and obtaining a mixture containing cyclopentane and a diluent at the bottom of the tower;
introducing the mixture containing cyclopentane and the diluent into a dilution tower for rectification separation III, obtaining cyclopentane at the top of the tower and obtaining the diluent at the bottom of the tower;
The diluent is mixed with the hydrogenation raw material and is introduced into a hydrogenation reactor to carry out hydrogenation reaction; the diluent is purified by rectification operation and is recycled after pressurization.
Optionally, the cyclopentadiene II is an unreacted raw material and is recycled as a circulating raw material.
Optionally, the temperature of the top of the recovery tower is 0-60 ℃ and the operating pressure is 0-300 kPaA;
The temperature of the top of the product tower is 0-60 ℃, and the operating pressure is 0-300 kPaA;
the temperature of the top of the dilution tower is 0-60 ℃ and the operating pressure is 0-300 kPaA.
Alternatively, the top temperature of the recovery column is independently selected from any value or range of values between any two points of 0 ℃, 20 ℃, 40 ℃, 42 ℃, 60 ℃.
Alternatively, the operating pressure of the recovery column is independently selected from any of 0kPaA, 10kPaA, 50kPaA, 100kPaA, 120kPaA, 150kPaA, 200kPaA, 250kPaA, 300kPaA, or a range of values between any two of the foregoing.
Alternatively, the product column overhead temperature is independently selected from any value or range of values between any two points above, from 0 ℃, 20 ℃, 40 ℃, 45 ℃, 60 ℃.
Alternatively, the product column operating pressure is independently selected from any of 0kPaA, 10kPaA, 50kPaA, 105kPaA, 150kPaA, 200kPaA, 250kPaA, 300kPaA, or a range of values between any two of the foregoing.
Alternatively, the top temperature of the dilution column is independently selected from any value or range of values between any two points of 0 ℃, 20 ℃, 40 ℃, 47 ℃, 60 ℃.
Alternatively, the operating pressure of the dilution column is independently selected from any of 0kPaA, 10kPaA, 50kPaA, 105kPaA, 150kPaA, 200kPaA, 250kPaA, 300kPaA, or a range of values between any two of the foregoing.
In another aspect of the present application, there is provided a production apparatus for a low-carbon annular hydrocarbon, the production apparatus comprising a reaction unit and a separation unit connected by a pipeline;
the reaction unit comprises a preheating module, a cracking reactor and a hydrogenation reactor;
the preheating module is respectively communicated with the cracking reactor and the hydrogenation reactor through pipelines;
the separation unit comprises a gas-liquid separation module, a recovery tower, a product tower and a dilution tower which are connected in sequence;
the gas-liquid separation module is provided with a liquid phase inlet and a gas phase outlet I, the hydrogenation reactor is connected with the liquid phase inlet pipeline, and the gas phase outlet I is connected with the preheating module through a pipeline;
The side wall of the recovery tower is provided with a cyclopentadiene II outlet, and the cyclopentadiene II outlet is connected with the preheating module through a pipeline;
a cyclopentene outlet is arranged at the top of the product tower;
the top of the dilution tower is provided with a cyclopentane outlet, the bottom of the dilution tower is provided with a diluent outlet, and the diluent outlet is connected with the hydrogenation reactor through a pipeline;
The recovery tower, the product tower and the dilution tower are all rectifying towers.
Optionally, the preheating module comprises a raw material preheater I and a raw material preheater II which are connected through pipelines;
the raw material preheater I is provided with a raw material inlet I, a cracking reaction product inlet I and a cracking reaction product outlet I;
The outlet of the cyclopentadiene II is communicated with the raw material inlet I through a pipeline;
The gas phase outlet I is communicated with the raw material inlet I through a pipeline;
the cracking reactor is provided with a raw material inlet II and a cracking reaction product outlet II;
the raw material preheater II is connected with a raw material inlet II of the cracking reactor through a pipeline;
The cracking reaction product inlet I of the raw material preheater I is connected with the cracking reaction product outlet II through a pipeline;
The hydrogenation reactor is provided with a hydrogenation raw material inlet, and the cracking reaction product outlet I is connected with the hydrogenation raw material inlet through a pipeline.
Optionally, the gas-liquid separation module is sequentially connected with a condenser, a condensation tank, a cryocooler and a cryocooler;
The condenser is communicated with the hydrogenation reactor;
The bottom of the condensation tank is provided with a condensate outlet I, and the bottom of the cryogenic tank is provided with a condensate outlet II; the condensate outlet I and the condensate outlet II are respectively communicated with the recovery tower;
the top of the cryogenic tank is provided with a gas phase outlet I;
and a pressurizing device I is arranged on a pipeline connected with the gas phase outlet I and the raw material inlet I.
Optionally, the diluent outlet is connected with the hydrogenation raw material inlet through a pipeline;
A pipeline connecting the diluent outlet and the hydrogenation raw material inlet is provided with a supercharging device II;
A condensate inlet is arranged on the side wall of the recovery tower, and the condensate outlet I and the condensate outlet II are respectively communicated with the condensate inlet;
the bottom of the recovery tower is communicated with the tower side wall of the product tower;
The bottom of the product tower is communicated with the tower side wall of the dilution tower.
Optionally, the reflux ratio of the recovery tower is 10-120, and the theoretical plate number is 10-80;
The reflux ratio of the product tower is 10-100, and the theoretical plate number is 20-120;
the reflux ratio of the dilution tower is 10-120, and the theoretical plate number is 10-100.
Optionally, the reflux ratio of the recovery tower is independently selected from any value of 10, 20, 40, 60, 80, 100, 120 or a range of values between any two points.
Alternatively, the theoretical plate number of the recovery tower is independently selected from any value of 10, 20, 40, 50, 60, 80 or a range value between any two points.
Alternatively, the reflux ratio of the product column is independently selected from any of 10, 20, 40, 60, 80, 100 or a range between any two of the above.
Alternatively, the theoretical plate number of the product column is independently selected from any value of 20, 40, 60, 80, 100, 120 or a range value between any two points.
Optionally, the reflux ratio of the dilution tower is independently selected from any of 10, 20, 40, 60, 80, 100, 120 or a range between any two points.
Alternatively, the theoretical plate number of the dilution tower is independently selected from any value of 10, 20, 40, 60, 80, 100 or a range value between any two points.
As a specific embodiment, the production method and the production device include:
The production device comprises a raw material heat exchanger, a raw material preheater, a cracker, a reactor, a condenser, a condensing tank, a cryocooler, a circulating hydrogen compressor, a recovery tower, a product tower 11, a diluent tower 12 and a diluent pump. The production method using the device comprises the following steps:
s01, mixing fresh cyclopentadiene with circulating cyclopentadiene and hydrogen required by reaction, and heating a pyrolysis product in a raw material heat exchanger to obtain a superheated gas-phase mixture;
S02, heating the gas-phase raw material to a cracking temperature in a raw material preheater, and carrying out a cracking reaction in the cracker to crack a small amount of dicyclopentadiene impurities into cyclopentadiene, so that the purity of the raw material is improved;
s03, cooling the cracking product to hydrogenation reaction temperature by a cold raw material through a raw material heat exchanger, mixing the cracking product with a circulating diluent, and then entering a reactor to perform partial hydrogenation reaction;
S04, condensing the reaction product into vapor-liquid two phases through a condenser, and then performing vapor-liquid separation in a condensing tank;
S05, the gas phase of the condensing tank is further condensed in the cryocooler and then subjected to secondary gas-liquid separation in the cryocooler to obtain high-purity unreacted hydrogen, and the unreacted hydrogen is pressurized by the circulating hydrogen compressor and then mixed with the supplemented fresh hydrogen to return to the inlet of the raw material heat exchanger;
s06, mixing liquid phases of the condensing tank and the cryogenic tank, sending the mixed liquid phases to a recovery tower, separating non-condensable gas and unreacted liquid-phase cyclopentadiene raw materials at the top of the tower, and returning the liquid-phase raw materials to an inlet of the raw material heat exchanger 1 for recycling;
S07, delivering the fraction obtained at the bottom of the recovery tower to a product tower, rectifying to obtain a cyclopentene product at the top of the tower, obtaining a mixture of cyclopentane and a diluent at the bottom of the tower, and delivering the mixture to the diluent tower for separation;
S08, rectifying the diluent tower to obtain cyclopentane byproducts at the tower top, obtaining purified diluent at the tower bottom, pressurizing the diluent tower by a diluent pump, and recycling the diluent tower;
Wherein the mole ratio of the diluent to cyclopentadiene at the inlet of the reactor is 1.5-5:1.
As a specific embodiment, the process flow of the method comprises:
Is divided into a reaction unit and a separation unit. The reaction unit is composed of a circulating flow strand, preheating equipment and a reactor, takes industrial cyclopentadiene as a raw material, reduces vaporization temperature by pre-mixing reaction hydrogen after being mixed with the circulating flow strand, effectively avoids high-temperature vaporization and coking of the raw material, enables polymerization impurities to be cracked in a cracker after being preheated to the cracking temperature, and then carries out partial hydrogenation reaction in the reactor after being cooled to the reaction temperature by heat exchange with the raw material. The reaction product is sent to a separation unit, and the separation unit consists of a flash evaporation device and a rectification device. The reaction product is subjected to fractional condensation, unreacted hydrogen is recovered, and the condensate is sent to a sequential rectifying tower to separate impurities, unreacted raw materials, circulating diluent, cyclopentene products and cyclopentane byproducts.
The application has the beneficial effects that:
The method can be used for producing cyclopentene by partial hydrogenation of cyclopentadiene, has continuous process and simple flow, saves high-grade cold energy consumption by fractional condensation, controls hydrogenation reaction temperature rise by adopting a method of circulating inert diluents, and is suitable for industrialized large-scale continuous operation.
Drawings
FIG. 1 is a schematic diagram of a process for producing a low carbon ring hydrocarbon in an embodiment of the application.
Wherein:
1. A raw material heat exchanger; 2. a raw material preheater; 3. a cracker; 4. a reactor; 5. a condenser; 6. a condensing tank; 7. a chiller; 8. a cryogenic tank; 9. a recycle hydrogen compressor; 10. a recovery tower; 11. a product tower; 12. a diluent column; 13. a diluent pump.
Detailed Description
The present application is described in detail below with reference to examples, but the present application is not limited to these examples.
Unless otherwise indicated, the starting materials in the examples of the present application were purchased commercially.
Example 1
As shown in fig. 1, a production apparatus for low-carbon annular hydrocarbon comprises the following components:
A raw material heat exchanger 1, a raw material preheater 2, a cracker 3, a reactor 4, a condenser 5, a condensing tank 6, a cryocooler 7, a cryocooler 8, a recycle hydrogen compressor 9, a recovery column 10, a product column 11, a diluent column 12, and a diluent pump 13.
The raw material heat exchanger 1, the raw material preheater 2 and the cracker 3 are sequentially connected, and an outlet at the top of the cracker 3 is connected with the raw material heat exchanger 1 for heat exchange; the outlet of the raw material heat exchanger 1 is connected with the inlet of the side wall of the reactor 4;
The bottom outlet of the reactor 4, the condenser 5, the condensing tank 6, the cryocooler 7 and the cryocooler 8 are sequentially connected, condensate outlets are respectively arranged at the bottoms of the condensing tank 6 and the cryocooler 8 and are respectively connected with the side wall of the recovery tower 10, and the bottom of the recovery tower is communicated with the side wall of the product tower; the bottom of the product tower is communicated with the tower side wall of the dilution tower. The top of the cryogenic tank 8 is provided with a hydrogen outlet which is communicated with the raw material heat exchanger 1 through a circulating hydrogen compressor 9.
The side wall of the recovery tower 10 is arranged at the outlet of cyclopentadiene II, and a noncondensable gas outlet is arranged at the top of the tower; the top of the product tower is provided with a cyclopentene outlet; the top of the dilution tower is provided with a cyclopentane outlet, the bottom of the dilution tower is provided with a diluent outlet, and the diluent outlet is connected with the side wall inlet of the reactor 4 through a diluent pump 13.
The outlet of cyclopentadiene II is communicated with the raw material heat exchanger 1.
Example 2
With the production apparatus described in example 1, fresh cyclopentadiene was mixed with recycled cyclopentadiene and hydrogen required for the reaction, and then heated to 132℃via cleavage products in the feed heat exchanger 1 to become a superheated gas phase mixture, in which the molar ratio of hydrogen to cyclopentadiene components was 1:1. The gas phase mixture is then fed into a feed preheater 2, heated to 350 c, and fed into a cracker 3 where a cracking reaction takes place to crack small amounts of dicyclopentadiene impurities into cyclopentadiene. The cracking product is cooled to 112 ℃ by cold raw materials through a raw material heat exchanger 1 to obtain hydrogenation raw materials, the hydrogenation raw materials and circulating diluent cyclohexane are mixed and then enter a reactor 4, and the mol ratio of the cyclohexane to cyclopentadiene in the raw materials is 2.9:1. The material in the reactor 4 is subjected to partial hydrogenation reaction under the pressure of 0.14MPaA to generate cyclopentene. The reaction product is condensed to 42 ℃ through a condenser 5, gas-liquid separation is carried out in a condensing tank 6 under the pressure of 0.12MPaA after vapor phase is formed, gas phase is further condensed to-30 ℃ in a cryocooler 7, secondary gas-liquid separation is carried out in a cryocooler 8 under the pressure of 0.11MPaA, high-purity unreacted hydrogen is obtained, and the high-purity unreacted hydrogen is mixed with supplementary fresh hydrogen after being pressurized by a circulating hydrogen compressor 9 and returned to the inlet of a raw material heat exchanger 1. The liquid phase of the condensing tank 6 and the cryogenic tank 8 are mixed and then sent to a recovery tower 10 for separation, the recovery tower 10 adopts fractional condensation rectification, the tower top pressure is 120kPaA, the theoretical plate number is 50, the reflux ratio is 100, the tower top temperature is 42 ℃, noncondensable gas and unreacted liquid phase cyclopentadiene raw materials are separated at the tower top, the liquid phase raw materials are returned to the inlet of the raw material heat exchanger 1 for recycling, the fraction obtained at the tower bottom of the recovery tower 10 is a mixture of cyclopentene, cyclopentane and cyclohexane, and the mixture is sent to a product tower 11 for separation. The product tower 11 adopts full condensation rectification, the tower top pressure is 105kPaA, the theoretical plate number is 80, the reflux ratio is 60, the tower top temperature is 45 ℃, the cyclopentene product with the purity higher than 99 percent by weight is obtained at the tower top through rectification, the mixture of cyclopentane and cyclohexane is obtained at the tower bottom, and the mixture is sent to the diluent tower 12 for separation. The diluent tower 12 adopts full condensation rectification, the tower top pressure is 105kPaA, the theoretical plate number is 60, the reflux ratio is 100, the tower top temperature is 47 ℃, cyclopentane byproducts are obtained at the tower top through rectification, cyclohexane with the purity of 99.2 percent by weight is obtained at the tower bottom, and the cyclohexane is pressurized by the diluent pump 13 and then returned to the inlet of the reactor 4 for recycling.
While the application has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the application, and it is intended that the application is not limited to the specific embodiments disclosed.
Claims (10)
1. A process for producing a low-carbon hydrocarbon compound, characterized in that,
The low-carbon ring-shaped hydrocarbon comprises cyclopentene and cyclopentane;
The production method comprises a reaction stage and a separation stage;
The reaction stage comprises: preheating a raw material I containing cyclopentadiene I and hydrogen I, introducing the raw material I into a cracking reactor, performing cracking reaction to obtain a cracking reaction product, performing heat exchange on the cracking reaction product and the raw material I to obtain a hydrogenation raw material, mixing the hydrogenation raw material with a diluent, introducing the mixture into the hydrogenation reactor to perform hydrogenation reaction to obtain a hydrogenation reaction product;
The separation stage comprises: and (3) carrying out gas-liquid separation and three-stage rectification treatment on the hydrogenation reaction product to sequentially obtain hydrogen II, cyclopentadiene II, cyclopentene and cyclopentane.
2. The method according to claim 1, wherein,
The raw material I also comprises hydrogen II and cyclopentadiene II;
In the raw material I, the molar ratio of cyclopentadiene to hydrogen is 0.1-5, wherein the molar quantity of cyclopentadiene is calculated by the total molar quantity of cyclopentadiene I and cyclopentadiene II, and the molar quantity of hydrogen is calculated by the total molar quantity of hydrogen I and hydrogen II;
preferably, the preheating comprises a first stage preheating and a second stage preheating;
the first stage of preheating is that the raw material I exchanges heat with the cracking reaction product to obtain a heat exchanged raw material II, wherein the raw material II is a superheated gas phase mixture;
the temperature of the overheated gas-phase mixture is 100-200 ℃;
The second stage of preheating is to heat the raw material II;
Preferably, the raw material I also comprises dicyclopentadiene;
The cracking reaction product comprises cyclopentadiene III obtained by cracking dicyclopentadiene.
3. The method of claim 2, wherein,
The reaction temperature of the cracking reaction is 200-500 ℃;
the reaction temperature of the hydrogenation reaction is 50-200 ℃, and the reaction pressure is 0.1-3 MPaA;
preferably, the molar ratio of the diluent to the cyclopentadiene is 1.5-5:1, wherein the molar amount of the cyclopentadiene is calculated by the total molar amount of cyclopentadiene I, cyclopentadiene II and cyclopentadiene III in the hydrogenation raw material;
preferably, the diluent is an inert diluent;
the inert diluent is at least one selected from cyclohexane, benzene and heptane.
4. The method according to claim 1, wherein,
The gas-liquid separation comprises: sequentially carrying out gas-liquid separation in a first stage and gas-liquid separation in a second stage on the hydrogenation reaction product to obtain hydrogen II and condensate after separation, wherein the hydrogen II is recycled;
preferably, the condensation temperature of the gas-liquid separation in the first stage is 0-60 ℃, and the separation pressure is 0-0.3 MpaA;
the condensation temperature of the gas-liquid separation in the second stage is-60 to-10 ℃, and the separation pressure is 0-0.3 MpaA.
5. The method according to claim 4, wherein,
The three-stage rectification treatment comprises the following steps:
introducing the condensate into a recovery tower for rectification separation I, obtaining cyclopentadiene II in a liquid phase from the side wall of the tower, and obtaining a distillate from the bottom of the tower;
Introducing the distillate into a product tower for rectification separation II, obtaining cyclopentene at the top of the tower, and obtaining a mixture containing cyclopentane and a diluent at the bottom of the tower;
introducing the mixture containing cyclopentane and the diluent into a dilution tower for rectification separation III, obtaining cyclopentane at the top of the tower and obtaining the diluent at the bottom of the tower;
The diluent is mixed with the hydrogenation raw material and is introduced into a hydrogenation reactor to carry out hydrogenation reaction;
The cyclopentadiene II is recycled.
6. The method according to claim 5, wherein,
The temperature of the top of the recovery tower is 0-60 ℃ and the operating pressure is 0-300 kPaA;
The temperature of the top of the product tower is 0-60 ℃, and the operating pressure is 0-300 kPaA;
the temperature of the top of the dilution tower is 0-60 ℃ and the operating pressure is 0-300 kPaA.
7. A device for producing low-carbon annular hydrocarbon is characterized in that,
The production device comprises a reaction unit and a separation unit which are connected through a pipeline;
the reaction unit comprises a preheating module, a cracking reactor and a hydrogenation reactor;
the preheating module is respectively communicated with the cracking reactor and the hydrogenation reactor through pipelines;
the separation unit comprises a gas-liquid separation module, a recovery tower, a product tower and a dilution tower which are connected in sequence;
the gas-liquid separation module is provided with a liquid phase inlet and a gas phase outlet I, the hydrogenation reactor is connected with the liquid phase inlet pipeline, and the gas phase outlet I is connected with the preheating module through a pipeline;
The side wall of the recovery tower is provided with a cyclopentadiene II outlet, and the cyclopentadiene II outlet is connected with the preheating module through a pipeline;
a cyclopentene outlet is arranged at the top of the product tower;
the top of the dilution tower is provided with a cyclopentane outlet, the bottom of the dilution tower is provided with a diluent outlet, and the diluent outlet is connected with the hydrogenation reactor through a pipeline;
The recovery tower, the product tower and the dilution tower are all rectifying towers.
8. The apparatus for producing of claim 7, wherein,
The preheating module comprises a raw material preheater I and a raw material preheater II which are connected through pipelines;
the raw material preheater I is provided with a raw material inlet I, a cracking reaction product inlet I and a cracking reaction product outlet I;
The outlet of the cyclopentadiene II is communicated with the raw material inlet I through a pipeline;
The gas phase outlet I is communicated with the raw material inlet I through a pipeline;
the cracking reactor is provided with a raw material inlet II and a cracking reaction product outlet II;
the raw material preheater II is connected with a raw material inlet II of the cracking reactor through a pipeline;
The cracking reaction product inlet I of the raw material preheater I is connected with the cracking reaction product outlet II through a pipeline;
The hydrogenation reactor is provided with a hydrogenation raw material inlet, and the cracking reaction product outlet I is connected with the hydrogenation raw material inlet through a pipeline.
9. The apparatus for producing of claim 8, wherein,
The gas-liquid separation module is sequentially connected with a condenser, a condensing tank, a cryocooler and a cryocooler;
The condenser is communicated with the hydrogenation reactor;
The bottom of the condensation tank is provided with a condensate outlet I, and the bottom of the cryogenic tank is provided with a condensate outlet II; the condensate outlet I and the condensate outlet II are respectively communicated with the recovery tower;
the top of the cryogenic tank is provided with a gas phase outlet I;
and a pressurizing device I is arranged on a pipeline connected with the gas phase outlet I and the raw material inlet I.
10. The apparatus for producing of claim 8, wherein,
The diluent outlet is connected with the hydrogenation raw material inlet through a pipeline;
A pipeline connecting the diluent outlet and the hydrogenation raw material inlet is provided with a supercharging device II;
A condensate inlet is arranged on the side wall of the recovery tower, and the condensate outlet I and the condensate outlet II are respectively communicated with the condensate inlet;
the bottom of the recovery tower is communicated with the tower side wall of the product tower;
the bottom of the product tower is communicated with the tower side wall of the dilution tower;
Preferably, the reflux ratio of the recovery tower is 10-120, and the theoretical plate number is 10-80;
The reflux ratio of the product tower is 10-100, and the theoretical plate number is 20-120;
the reflux ratio of the dilution tower is 10-120, and the theoretical plate number is 10-100.
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