CN118063278A - Production method and production device of unsaturated cyclic hydrocarbon - Google Patents
Production method and production device of unsaturated cyclic hydrocarbon Download PDFInfo
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- CN118063278A CN118063278A CN202211476219.XA CN202211476219A CN118063278A CN 118063278 A CN118063278 A CN 118063278A CN 202211476219 A CN202211476219 A CN 202211476219A CN 118063278 A CN118063278 A CN 118063278A
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 125000000753 cycloalkyl group Chemical group 0.000 title claims abstract description 13
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims abstract description 111
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000009833 condensation Methods 0.000 claims abstract description 58
- 230000005494 condensation Effects 0.000 claims abstract description 58
- 238000006356 dehydrogenation reaction Methods 0.000 claims abstract description 51
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims abstract description 50
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- 238000012719 thermal polymerization Methods 0.000 claims abstract description 18
- 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 abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 52
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 33
- 239000007791 liquid phase Substances 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 15
- 239000012071 phase Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 13
- 239000007795 chemical reaction product Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 3
- 238000007670 refining Methods 0.000 abstract description 4
- 238000010924 continuous production Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract 2
- 238000000926 separation method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 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
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- XCIXKGXIYUWCLL-UHFFFAOYSA-N cyclopentanol Chemical compound OC1CCCC1 XCIXKGXIYUWCLL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 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
- 238000005191 phase separation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920003050 poly-cycloolefin Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C13/00—Cyclic hydrocarbons containing rings other than, or in addition to, six-membered aromatic rings
- C07C13/02—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof
- C07C13/08—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring
- C07C13/12—Monocyclic hydrocarbons or acyclic hydrocarbon derivatives thereof with a five-membered ring with a cyclopentene ring
-
- 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
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3332—Catalytic processes with metal oxides or metal sulfides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/005—Processes comprising at least two steps in series
-
- 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
- C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
- C07C7/177—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by selective oligomerisation or polymerisation of at least one compound of the mixture
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (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 unsaturated cyclic hydrocarbon, wherein the production method comprises the following steps: (1) The raw material containing cyclopentane is contacted with a catalyst to carry out catalytic dehydrogenation reaction, and dehydrogenation products containing hydrogen, cyclopentene, cyclopentadiene and cyclopentane I are obtained; (2) And the dehydrogenation product is subjected to fractional condensation, fractional condensation rectification, thermal polymerization reaction and complete condensation rectification to sequentially obtain hydrogen, cyclopentane I, cyclopentene and dicyclopentadiene. The method can be used for preparing the cyclopentene by dehydrogenating the cyclopentane, has continuous process and simple flow, saves high-grade cold energy consumption by fractional condensation, reduces the refining difficulty of the product by combining cyclopentadiene thermal polymerization, and obtains the high-purity cyclopentene product, thereby being suitable for industrialized large-scale continuous operation.
Description
Technical Field
The application relates to a production method and a production device of unsaturated cyclic 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 mainly comprises cyclopentadiene partial catalytic hydrogenation, but the corresponding industrial process technology has a certain technical barrier. With the increase of the domestic cyclopentane yield, the price is continuously lowered, and the research of new cyclopentene synthesis routes is necessary.
Disclosure of Invention
The application provides a method for preparing cyclopentene by dehydrogenating cyclopentane, which has the advantages of continuous process, simple flow, high-grade cold energy consumption saving by fractional condensation, reduction of product refining difficulty by combining cyclopentadiene thermal polymerization, and acquisition of high-purity cyclopentene product, and is suitable for industrial large-scale continuous operation.
In one aspect of the present application, there is provided a process for producing an unsaturated cyclic hydrocarbon,
The production method comprises the following steps:
(1) The raw material containing cyclopentane is contacted with a catalyst to carry out catalytic dehydrogenation reaction, and dehydrogenation products containing hydrogen, cyclopentene, cyclopentadiene and cyclopentane I are obtained;
(2) And the dehydrogenation product is subjected to fractional condensation, fractional condensation rectification, thermal polymerization reaction and complete condensation rectification to sequentially obtain hydrogen, cyclopentane I, cyclopentene and dicyclopentadiene.
In the present application, the catalyst mainly refers to a dehydrogenation catalyst, including but not limited to a fixed bed catalyst such as a metal catalyst, a supported catalyst, a molecular sieve catalyst, etc., and can be selected by those skilled in the art according to practical situations.
Optionally, step (1) further comprises:
the dehydrogenation product exchanges heat with the raw material;
the temperature of the dehydrogenation product after heat exchange is 0-100 ℃.
Alternatively, the temperature of the dehydrogenation product after heat exchange is independently selected from any value or range of values between any two of 0 ℃, 20 ℃, 40 ℃, 60 ℃, 77 ℃, 80 ℃, 100 ℃.
Alternatively, the reaction temperature of the thermal polymerization reaction is 40-150 ℃ and the reaction pressure is 500-1000 kPaA.
Alternatively, the reaction temperature of the thermal polymerization reaction is independently selected from any value of 40 ℃, 60 ℃, 80 ℃, 100 ℃, 120 ℃, 150 ℃ or a range of values between any two points.
Alternatively, the reaction pressure of the thermal polymerization reaction is independently selected from any value of 500kPaA, 600kPaA, 700kPaA, 800kPaA, 900kPaA, 1000kPaA or a range of values between any two of the foregoing.
Optionally, the step (2) includes:
(a) After fractional condensation of the dehydrogenation product, obtaining the hydrogen and a condensed liquid phase;
(b) The condensed liquid phase is subjected to fractional condensation and rectification through an alkane tower to obtain the cyclopentane I and a mixture containing cyclopentene and cyclopentadiene;
(c) The mixture containing cyclopentene and cyclopentadiene is subjected to thermal polymerization reaction and product tower complete condensation rectification to obtain the cyclopentene and dicyclopentadiene;
Wherein in the step (1), the raw material further comprises the cyclopentane I.
Optionally, the fractional condensation comprises a first-stage condensation and a second-stage condensation which are sequentially carried out;
after primary condensation, the dehydrogenation product is subjected to gas phase I and condensed liquid phase I;
the gas phase I is subjected to secondary condensation to obtain hydrogen and a condensed liquid phase II;
Wherein the condensation temperature of the primary condensation is 0-60 ℃ and the condensation pressure is 0.1-0.5 MPaA.
The condensation temperature of the secondary condensation is-60 to-10 ℃, and the condensation pressure is 0.1 to 0.5MPaA.
Alternatively, the condensation temperature of the primary condensation is independently selected from any value or range of values between any two points of 0 ℃, 10 ℃, 20 ℃, 30 ℃, 42 ℃,50 ℃, 60 ℃.
Alternatively, the condensing pressure of the primary condensate is independently selected from any of 0.1MPaA, 0.2MPaA, 0.3MPaA, 0.4MPaA, 0.5MPaA, or a range of values between any two of the foregoing.
Optionally, the condensing temperature of the secondary condensate is independently selected from any of-60 ℃, -50 ℃, -40 ℃, -30 ℃, -20 ℃, -10 ℃ or a range of values between any two of the above.
Alternatively, the condensing pressure of the secondary condensate is independently selected from any of 0.1MPaA, 0.2MPaA, 0.3MPaA, 0.4MPaA, 0.5MPaA, or a range of values between any two of the foregoing.
Optionally, the temperature of the top of the alkane tower is 0-60 ℃ and the operating pressure is 0-300 kPaA;
The tower top temperature of the product tower is 0-60 ℃ and the operating pressure is 0-300 kPaA.
Alternatively, the top temperature of the alkane column is independently selected from any value or range of values between any two points of 0 ℃,10 ℃, 20 ℃, 30 ℃, 42 ℃, 50 ℃,60 ℃.
Alternatively, the operating pressure of the alkane column is independently selected from any of 0kPaA, 100kPaA, 115kPaA, 200kPaA, 300kPaA, or a range of values between any two of the foregoing.
Alternatively, the product column top temperature is independently selected from any value or range of values between any two points of 0 ℃,10 ℃, 20 ℃, 30 ℃,44 ℃, 50 ℃,60 ℃.
Alternatively, the operating pressure of the product column is independently selected from any of 0kPaA, 100kPaA, 120kPaA, 200kPaA, 300kPaA, or a range of values between any two of the foregoing.
In the present application kPaA refers to absolute pressure.
In another aspect of the application, there is provided a production device of unsaturated cyclic hydrocarbon, the production device comprising a dehydrogenation reaction unit, a fractional condensation unit, an alkane tower, a thermal polymerization reactor and a product tower which are sequentially communicated;
the alkane tower and the product tower are both rectifying towers;
The fractional condensation unit is arranged at the hydrogen outlet;
The bottom of the alkane tower is provided with a cyclopentane I outlet;
the top of the product tower is provided with a cyclopentene outlet, and the bottom of the product tower is provided with a dicyclopentadiene outlet.
Optionally, the dehydrogenation reaction unit comprises a heat exchanger, a preheater and a dehydrogenation reactor which are sequentially communicated;
The dehydrogenation reaction product outlet I of the dehydrogenation reactor is communicated with the dehydrogenation reaction product inlet of the heat exchanger; and a dehydrogenation reaction product outlet II of the heat exchanger is communicated with the fractional condensation unit.
Optionally, the fractional condensation unit comprises a condenser, a condensation tank, a cryocooler and a cryocooler which are sequentially communicated;
The condenser is communicated with the dehydrogenation reaction unit;
The condensing tank is provided with a condensed liquid phase I outlet;
the cryogenic tank is provided with a condensed liquid phase II outlet;
the condensed liquid phase I outlet and the condensed liquid phase II outlet are communicated with the alkane tower;
The cryogenic tank is provided with the hydrogen outlet.
Optionally, the top of the alkane tower is provided with a gas phase outlet and a mixture outlet containing cyclopentene and cyclopentadiene;
the mixture outlet containing cyclopentene and cyclopentadiene is communicated with the thermal polymerization reactor through a pipeline;
a heater is further arranged on a pipeline which is communicated with the thermal polymerization reactor and is used for the mixture outlet containing cyclopentene and cyclopentadiene;
the cyclopentane I outlet is communicated with the heat exchanger.
Optionally, the reflux ratio of the alkane tower is 30-140, and the theoretical plate number is 30-100;
the reflux ratio of the product tower is 0.1-10, and the theoretical plate number is 1-60.
Optionally, the reflux ratio of the alkane tower is independently selected from any value of 30, 60, 90, 110, 120, 140 or a range of values between any two points.
Alternatively, the theoretical plate number of the alkane tower is independently selected from any value of 30, 40, 60, 80, 90 and 100 or a range value between any two points.
Optionally, the reflux ratio of the product column is independently selected from any of 0.1, 1, 3, 5, 8, 10 or a range between any two points.
Alternatively, the theoretical plate number of the product column is independently selected from any value of 1, 10, 20, 30, 40, 60 or a range of values between any two points.
As a specific embodiment, the method for producing an unsaturated cyclic hydrocarbon comprises:
The production device comprises a raw material heat exchanger, a raw material preheater, a reactor, a condenser, a condensing tank, a deep cooler, a deep cooling tank, an alkane tower, a heater, a polymerizer and a product tower, and the specific method is as follows:
S01, mixing fresh cyclopentane with a circulating raw material, heating to a reaction temperature by a raw material heat exchanger and a raw material preheater, and then carrying out catalytic dehydrogenation reaction in a reactor to obtain a dehydrogenation product containing hydrogen, cyclopentene, cyclopentadiene and unreacted cyclopentane;
S02, condensing the dehydrogenation product to low temperature by circulating water in a condenser after heat exchange between a raw material heat exchanger and the raw material to form vapor-liquid two phases, performing vapor-liquid separation in a condensing tank, performing cryogenic separation on the obtained vapor phase by a cryogenic cooler, and separating again in the cryogenic tank to obtain crude hydrogen gas as the obtained vapor phase;
S03, sending the liquid phases of the condensing tank and the cryogenic tank to an alkane tower, carrying out fractional condensation and rectification to obtain unreacted cyclopentane raw materials at the bottom of the tower, and sending the unreacted cyclopentane raw materials back to the inlet of a raw material heat exchanger to be mixed with fresh raw materials for recycling;
S04, discharging a gas phase obtained at the top of an alkane tower as waste gas, wherein the obtained liquid phase fraction is a cyclopentene/cyclopentadiene mixture, and sending the mixture to a polymerizer after heating the mixture to a polymerization temperature by a heater to enable cyclopentadiene components to undergo polymerization reaction to generate dicyclopentadiene;
S05, delivering the polymerized flow to a product tower for full condensation rectification, obtaining cyclopentene with purity of more than 98.5 wt% at the top of the tower, and obtaining dicyclopentadiene heavy impurities at the bottom of the tower.
As a specific embodiment, the process flow of the method for producing unsaturated cyclic hydrocarbon comprises: a reaction unit and a separation unit. The reaction unit is composed of a circulating flow strand, a preheating device and a reactor, takes cyclopentane as a raw material, is mixed with the circulating flow strand, is heated to a reaction temperature by a heat exchanger and a preheater, and then is subjected to dehydrogenation reaction in the reactor to obtain a reaction product containing cyclopentene and cyclopentadiene. The reaction product is sent to a separation unit, and the separation unit consists of a flash evaporation device, a rectification device and a polymerizer. The reaction product is subjected to fractional condensation to obtain cracked hydrogen, and the condensate is sent to an alkane tower to recycle unreacted cyclopentane. And (3) polymerizing the crude product after the cyclopentane removal by a polymerizer, and refining the cyclopentene product in a product tower to obtain the cyclopentene product and dicyclopentadiene byproducts.
The application has the beneficial effects that:
The unsaturated cyclic hydrocarbon production process provided by the application has the advantages of continuous process and simple flow, saves high-grade cold energy consumption through fractional condensation, reduces the product refining difficulty by combining cyclopentadiene thermal polymerization, and obtains high-purity cyclopentene products, thereby being suitable for industrial large-scale continuous operation.
Drawings
FIG. 1 is a schematic view of an apparatus for producing unsaturated cyclic hydrocarbons according to an embodiment of the application.
Wherein:
1. A raw material heat exchanger; 2. a raw material preheater; 3. a dehydrogenation reactor; 4. a condenser; 5. a condensing tank; 6. a chiller; 7. a cryogenic tank; 8. an alkane column; 9. a heater; 10. a polymerizer; 11. and (5) a product tower.
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, all starting materials in the examples of the present application were purchased commercially.
Example 1
As shown in fig. 1, an unsaturated cyclic hydrocarbon production apparatus comprises the following components:
a raw material heat exchanger 1, a raw material preheater 2, a dehydrogenation reactor 3, a condenser 4, a condensing tank 5, a cryocooler 6, a cryocooler 7, an alkane tower 8, a heater 9, a polymerizer 10 and a product tower 11.
The raw material heat exchanger 1, the raw material preheater 2 and the dehydrogenation reactor 3 are sequentially connected, a dehydrogenation reaction product outlet I of the dehydrogenation reactor 3 is communicated with a dehydrogenation reaction product inlet of the raw material heat exchanger 1, and a dehydrogenation reaction product outlet II of the raw material heat exchanger 1 is connected with an inlet of the condenser 4.
The outlet of the condenser 4 is connected with a condensing tank 5, and the top gas phase I outlet of the condensing tank 5 is connected with a cryogenic tank 7 through a cryogenic device 6; the bottom of the condensation tank 5 is provided with a condensed liquid phase I outlet, the bottom of the cryogenic tank 7 is provided with a condensed liquid phase II outlet, and the condensed liquid phase I outlet and the condensed liquid phase II outlet are both communicated with the alkane tower 8; the top of the cryogenic tank 7 is provided with a hydrogen outlet.
The alkane tower 8, the heater 9, the polymerizer 10 and the product tower 11 are connected in sequence, a gas phase II outlet is arranged at the top of the alkane tower 8, a cyclopentane I outlet is arranged at the bottom of the alkane tower, and the cyclopentane I outlet is communicated with the raw material heat exchanger 1; the top of the product tower 11 is provided with a cyclopentene outlet, and the bottom of the product tower is provided with a dicyclopentadiene outlet.
Example 2
By adopting the production device described in the example, the material I containing fresh cyclopentane and the recycled unreacted cyclopentane raw material is heated to 200 ℃ through the raw material heat exchanger 1, then is sent into the dehydrogenation reactor 3 filled with the platinum-loaded ZSM-5 molecular sieve dehydrogenation catalyst after being heated to 390 ℃ through the raw material preheater 2, and is subjected to catalytic dehydrogenation reaction at 390 ℃ and 130kPaA pressure to obtain a dehydrogenation product containing hydrogen, cyclopentene, cyclopentadiene and unreacted cyclopentane. The dehydrogenation product is condensed to 42 ℃ by circulating water in a condenser 4 after heat exchange between a raw material heat exchanger 1 and a material I to 77 ℃ to form vapor-liquid two phases, gas-liquid separation is carried out in a condensing tank 5 under the pressure of 115kPaA, the obtained gas phase is subjected to deep cooling to-30 ℃ for phase separation by a deep cooler 6, and the obtained gas phase is separated again in a deep cooling tank 7 in 110kPaA, so that the obtained gas phase is crude hydrogen. The liquid phase obtained at the bottoms of the condensing tank 5 and the cryogenic tank 7 is sent to an alkane tower 8 for separation, the alkane tower 8 adopts fractional condensation rectification, the tower top temperature is 42 ℃, the operating pressure is 115kPaA, 90 theoretical plates are arranged, the reflux ratio is 110, unreacted cyclopentane raw material with the purity of 99.8%wt is obtained at the tower bottom, and the unreacted cyclopentane raw material is sent back to the inlet of the raw material heat exchanger 1 for mixed recycling with fresh cyclopentane. The gas phase obtained at the top of the alkane tower 8 is discharged as waste gas, the obtained liquid phase fraction is a cyclopentene/cyclopentadiene mixture, the cyclopentene/cyclopentadiene mixture is sent to a polymerizer 10 after being heated to 120 ℃ by a heater 9, cyclopentadiene components are polymerized to generate dicyclopentadiene under the pressure of 800kPaA, the polymerized flow is sent to a product tower 11 for full condensation rectification, the temperature at the top of the product tower 11 is 44 ℃, the operation pressure is 120kPaA, 30 theoretical plates are arranged, the reflux ratio is 1, cyclopentene with the purity of 99.2 percent weight is obtained at the top of the tower, and dicyclopentadiene heavy impurities are obtained at the bottom of the tower.
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 unsaturated cyclic hydrocarbon, which is characterized in that,
(1) The raw material containing cyclopentane is contacted with a catalyst to carry out catalytic dehydrogenation reaction, and dehydrogenation products containing hydrogen, cyclopentene, cyclopentadiene and cyclopentane I are obtained;
(2) And the dehydrogenation product is subjected to fractional condensation, fractional condensation rectification, thermal polymerization reaction and complete condensation rectification to sequentially obtain hydrogen, cyclopentane I, cyclopentene and dicyclopentadiene.
2. The method according to claim 1, wherein,
Step (1) further comprises:
the dehydrogenation product exchanges heat with the raw material;
The temperature of the dehydrogenation product after heat exchange is 0-100 ℃;
Preferably, the reaction temperature of the thermal polymerization reaction is 40-150 ℃ and the reaction pressure is 500-1000 kPaA.
3. The method according to claim 1, wherein,
The step (2) comprises the following steps:
(a) After fractional condensation of the dehydrogenation product, obtaining the hydrogen and a condensed liquid phase;
(b) The condensed liquid phase is subjected to fractional condensation and rectification through an alkane tower to obtain the cyclopentane I and a mixture containing cyclopentene and cyclopentadiene;
(c) The mixture containing cyclopentene and cyclopentadiene is subjected to thermal polymerization reaction and product tower complete condensation rectification to obtain the cyclopentene and dicyclopentadiene;
Wherein in the step (1), the raw material further comprises the cyclopentane I.
4. The method according to claim 1, wherein,
The fractional condensation comprises primary condensation and secondary condensation which are sequentially carried out;
after primary condensation, the dehydrogenation product is subjected to gas phase I and condensed liquid phase I;
the gas phase I is subjected to secondary condensation to obtain hydrogen and a condensed liquid phase II;
wherein the condensation temperature of the primary condensation is 0-60 ℃ and the condensation pressure is 0.1-0.5 MPaA;
The condensation temperature of the secondary condensation is-60 to-10 ℃, and the condensation pressure is 0.1 to 0.5MPaA.
5. The method according to claim 3, wherein,
The temperature of the top of the alkane tower is 0-60 ℃ and the operating pressure is 0-300 kPaA;
The tower top temperature of the product tower is 0-60 ℃ and the operating pressure is 0-300 kPaA.
6. A device for producing unsaturated cyclic hydrocarbon is characterized in that,
The production device comprises a dehydrogenation reaction unit, a fractional condensation unit, an alkane tower, a thermal polymerization reactor and a product tower which are sequentially communicated;
the alkane tower and the product tower are both rectifying towers;
The fractional condensation unit is arranged at the hydrogen outlet;
The bottom of the alkane tower is provided with a cyclopentane I outlet;
the top of the product tower is provided with a cyclopentene outlet, and the bottom of the product tower is provided with a dicyclopentadiene outlet.
7. The apparatus for producing of claim 6, wherein,
The dehydrogenation reaction unit comprises a heat exchanger, a preheater and a dehydrogenation reactor which are sequentially communicated;
The dehydrogenation reaction product outlet I of the dehydrogenation reactor is communicated with the dehydrogenation reaction product inlet of the heat exchanger; and a dehydrogenation reaction product outlet II of the heat exchanger is communicated with the fractional condensation unit.
8. The apparatus for producing of claim 6, wherein,
The fractional condensation unit comprises a condenser, a condensation tank, a cryocooler and a cryocooler which are sequentially communicated;
The condenser is communicated with the dehydrogenation reaction unit;
The condensing tank is provided with a condensed liquid phase I outlet;
the cryogenic tank is provided with a condensed liquid phase II outlet;
the condensed liquid phase I outlet and the condensed liquid phase II outlet are communicated with the alkane tower;
The cryogenic tank is provided with the hydrogen outlet.
9. The apparatus for producing of claim 6, wherein,
The top of the alkane tower is provided with a gas phase outlet and a mixture outlet containing cyclopentene and cyclopentadiene;
the mixture outlet containing cyclopentene and cyclopentadiene is communicated with the thermal polymerization reactor through a pipeline;
a heater is further arranged on a pipeline which is communicated with the thermal polymerization reactor and is used for the mixture outlet containing cyclopentene and cyclopentadiene;
the cyclopentane I outlet is communicated with the heat exchanger.
10. The apparatus for producing of claim 6, wherein,
The reflux ratio of the alkane tower is 30-140, and the theoretical plate number is 30-100;
the reflux ratio of the product tower is 0.1-10, and the theoretical plate number is 1-60.
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| CN202211476219.XA CN118063278A (en) | 2022-11-23 | 2022-11-23 | Production method and production device of unsaturated cyclic hydrocarbon |
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