CN111748366A - Device and method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation - Google Patents
Device and method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation Download PDFInfo
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- CN111748366A CN111748366A CN202010669963.6A CN202010669963A CN111748366A CN 111748366 A CN111748366 A CN 111748366A CN 202010669963 A CN202010669963 A CN 202010669963A CN 111748366 A CN111748366 A CN 111748366A
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 192
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 96
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 96
- 239000003502 gasoline Substances 0.000 title claims abstract description 74
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 67
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 40
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 39
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 34
- 238000000926 separation method Methods 0.000 claims abstract description 106
- 239000001257 hydrogen Substances 0.000 claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000004064 recycling Methods 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 295
- 239000012528 membrane Substances 0.000 claims description 114
- 239000002994 raw material Substances 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 41
- 238000011084 recovery Methods 0.000 claims description 38
- 230000006837 decompression Effects 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000012071 phase Substances 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000007791 liquid phase Substances 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 14
- 239000002131 composite material Substances 0.000 claims description 12
- 239000002808 molecular sieve Substances 0.000 claims description 11
- 230000035939 shock Effects 0.000 claims description 11
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 11
- 239000011229 interlayer Substances 0.000 claims description 10
- 238000010791 quenching Methods 0.000 claims description 9
- 230000000171 quenching effect Effects 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- 238000012856 packing Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 238000000746 purification Methods 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 238000009434 installation Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- 230000009286 beneficial effect Effects 0.000 abstract description 9
- 239000000446 fuel Substances 0.000 abstract description 7
- 230000000295 complement effect Effects 0.000 abstract description 5
- 239000000295 fuel oil Substances 0.000 abstract description 5
- 238000002156 mixing Methods 0.000 abstract description 5
- 239000005431 greenhouse gas Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 93
- 239000003921 oil Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000835 fiber Substances 0.000 description 12
- 239000012510 hollow fiber Substances 0.000 description 12
- 239000012466 permeate Substances 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 230000000717 retained effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A device and a method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation relate to the technical field of gasoline production, and comprise a carbon dioxide feeding pipe, a hydrogen feeding pipe, a feeding and product heat exchanger, a heater I, a hydrogenation reactor, a cooler, a deep cooler, a high-pressure separation tank I, a pressure reducing valve I, a product separation tank, a pressure reducing valve IV, a light component removal tower, a product delivery pump, a heater II, a recycle compressor I, a recycle compressor II, a reboiler, a condenser, a pressure reducing valve III and a switch valve; the high-quality clean gasoline fuel can be directly obtained by a one-step method, can be directly used as finished fuel oil, can also be used as a gasoline blending component, and is complementary with other gasoline products; the carbon dioxide, a greenhouse gas, is utilized as a carbon resource, which is beneficial to realizing the recycling of the carbon resource and reducing the dependence on fossil energy.
Description
The technical field is as follows:
the invention relates to the technical field of gasoline production, in particular to a device and a method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation.
Background art:
the destruction effect of the carbon dioxide emission problem caused by the large consumption of fossil energy on the ecological environment is increasingly prominent, so that technologies and research works related to carbon dioxide emission reduction, such as carbon dioxide capture, sequestration, conversion and utilization, and the like, are highly regarded by the world.
From two basic points of effective protection of the global environment and storage and effective utilization of carbon resources, research and development of effective utilization and immobilization of carbon dioxide are important research subjects in green chemistry.
Carbon dioxide is used as a cheap and abundant 'carbon source' compound in the nature, hydrogen is prepared by electrolyzing water by means of renewable energy sources (water energy, solar energy, wind energy and the like), so that the carbon dioxide is converted into a chemical with a high added value, the environmental problem can be solved, excessive dependence on fossil fuels can be eliminated, and economic benefits are obtained. Furthermore, storing energy in chemicals and fuels also provides an important strategy for the storage of renewable energy sources.
Among many products, hydrocarbon compounds such as gasoline are important transportation fuels, are widely applied worldwide, have high economic value, and are considered as target products with great potential for carbon dioxide hydrogenation.
The patent application with the application number of 201911032747.4 and the publication number of CN110669543A relates to a device and a method for directly preparing gasoline by carbon dioxide hydrogenation. The device and the method adopt an indium oxide/molecular sieve (In 2O 3/HZSM-5) bifunctional composite catalyst, a reactor type tubular synthesis reactor with an external circulating heat exchange mechanism is selected, the outlet of the reactor is cooled In multiple stages, a molecular sieve adsorber is dehydrated, gas-liquid separation is carried out, part of gas-phase components In the gas-liquid separation is recycled, and part of the gas-phase components is used as purge gas and discharged out of a torch system.
In the above patent, the reactor type is not suitable for the adiabatic fixed bed layered packing method using an iron-based/molecular sieve (Na-Fe 3O 4/HZSM-5) multifunctional composite catalyst; the molecular sieve adsorber for dehydrating the mixed gas at the outlet of the reactor is also not suitable for dehydrating the mixed gas containing non-trace moisture; meanwhile, a large amount of unreacted raw material gas components in the purge gas are directly discharged, and the total conversion rate of the reaction is also reduced.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and overcome the defect that a device for directly preparing gasoline fraction hydrocarbon by hydrogenating carbon dioxide by adopting an iron-based/molecular sieve (Na-Fe 3O 4/HZSM-5) multifunctional composite catalyst does not exist, and provides a device and a method for directly preparing gasoline fraction hydrocarbon by hydrogenating carbon dioxide, which are suitable for the iron-based/molecular sieve (Na-Fe 3O 4/HZSM-5) multifunctional composite catalyst.
The invention is realized by the following technical scheme:
a device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation is characterized by comprising a carbon dioxide feeding pipe, a hydrogen feeding pipe, a feeding and product heat exchanger, a heater I, a hydrogenation reactor, a cooler, a deep cooler, a high-pressure separation tank I, a pressure reducing valve I, a product separation tank, a pressure reducing valve IV, a light component removal tower, a product conveying pump, a heater II, a circulating compressor I, a circulating compressor II, a reboiler, a condenser, a pressure reducing valve III and a switch valve;
the pipe body of the carbon dioxide feeding pipe is communicated with a switch valve, an outlet pipeline of the switch valve is communicated with the pipe body of the hydrogen feeding pipe, the hydrogen feeding pipe at the rear side of a mounting point of the switch valve is communicated with a cold side inlet pipeline of the feeding and product heat exchanger, a hot side outlet pipeline of the feeding and product heat exchanger is communicated with a cold side inlet of a heater I, a hot side outlet pipeline of the heater I is communicated with a top inlet of a hydrogenation reactor, a bottom outlet pipeline of the hydrogenation reactor is communicated with a hot side inlet of the feeding and product heat exchanger, a cold side outlet pipeline of the feeding and product heat exchanger is communicated with a hot side inlet of a cooler, a cold side outlet pipeline of the cooler is communicated with a hot side inlet of a cryogenic device, a cold side outlet pipeline of the cryogenic device is communicated with an inlet of a high-pressure separation tank I, and a bottom liquid phase outlet pipeline of the;
a gas phase outlet pipeline at the top of the high-pressure separation tank I is communicated with a cold side inlet of a heater II, a hot side outlet of the heater II is divided into two paths, one path is communicated with an inlet of a circulating compressor I, the other path is communicated with a gas recovery device, and an outlet pipeline of the circulating compressor I is communicated with a hydrogen feeding pipe; a recovery pipeline of the gas recovery device is communicated with an inlet of a circulating compressor II, and a discharge pipeline of the gas recovery device is communicated with a tail gas main pipe through a pressure reducing valve II;
a gas phase outlet pipeline at the top of the product separation tank is communicated with a tail gas main pipe through a pressure reducing valve III, and an oil phase outlet pipeline of the product separation tank is communicated with an inlet of the light component removal tower through a pressure reducing valve IV;
the top gas phase pipeline of the lightness-removing tower is communicated with a hot side inlet of a condenser, a cold side gas phase outlet pipeline of the condenser is communicated with a tail gas main pipe, and a cold side liquid phase outlet pipeline of the condenser is communicated with a top reflux opening of the lightness-removing tower; the bottom liquid phase outlet pipeline of the light component removing tower is divided into two paths, wherein one path is communicated with a cold side inlet of a reboiler, the other path is communicated with a product conveying pump inlet, and a hot side outlet pipeline of the reboiler is communicated with a reboiler interface on the bottom side wall of the light component removing tower.
In another aspect of the invention, the gas recovery device is a membrane separator or a pressure swing adsorption device, a membrane permeation gas outlet pipeline of the membrane separator is communicated with an inlet of the circulation compressor II, and membrane separation tail gas of the membrane separator is communicated with a tail gas main pipe after being decompressed by a decompression valve II.
In another aspect of the invention, the hydrogenation reactor adopts an adiabatic fixed bed reactor, and the catalyst is filled in a layered manner.
In another aspect of the invention, the high-pressure separation device further comprises a high-pressure separation tank II, the deep cooler is arranged at a gas phase outlet of the high-pressure separation tank II, a hot side outlet pipeline of the deep cooler is communicated with an inlet of the high-pressure separation tank I, a cold side outlet pipeline of the cooler is communicated with an inlet of the high-pressure separation tank II, and a bottom liquid phase outlet pipeline of the high-pressure separation tank II is communicated with an inlet of the product separation tank through a pressure reducing valve V.
The method for directly preparing the gasoline fraction hydrocarbon by carbon dioxide hydrogenation is characterized by comprising the following operation steps of:
step 3, introducing fresh raw material hydrogen at the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
nCO2＋（n～6n）H2＝ n1CO＋n2CH4＋(n3C2～ n5C4)＋(n6C5～n12C11)＋n13H2o, the reaction catalyst is an iron-based/molecular sieve (Na-Fe 3O 4/HZSM-5) multifunctional composite catalyst;
step 7, separating the low-temperature mixed gas/liquid through a high-pressure separation tank I to obtain gas and liquid, wherein the pressure of the high-pressure separation tank I is 1.0-6.0 Mpa; after the gas is subjected to heat exchange and temperature rise by a heater II, part of the gas is directly recycled, the gas is pressurized by a circulating compressor I and then is combined with fresh raw material gas, the temperature of the circulating gas is 20-60 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is separated by a gas recovery device to obtain a reactant component which can be recycled;
and step 10, conveying the liquid oil from the pressure reducing valve III to a light component removal tower, discharging light components dissolved in the crude gasoline product and a small amount of water and the like out of a flare system from the top of the light component removal tower, pressurizing other gasoline product components from the bottom of the light component removal tower through a pump to be used as a gasoline product, wherein the temperature of the light component removal tower is 0-160 ℃, and the pressure is 0.1-0.6 Mpa.
In another aspect of the invention, the hydrogenation reactor adopts an interlayer quenching mode, the quenching gas can adopt one of carbon dioxide or hydrogen, or a mixed gas of carbon dioxide and hydrogen in a certain ratio, and different types of the quenching gas or the ratio thereof are adjusted and controlled by an adjusting valve I arranged on a raw material carbon dioxide pipeline and an adjusting valve II arranged on a raw material hydrogen pipeline.
In another aspect of the invention, the gas recovery device is a membrane separator, the membrane separator separates recyclable membrane permeation gas, the temperature is 20-60 ℃, the pressure is 0.4-2.5 Mpa, the gas is pressurized by the recycle compressor II and then is connected to the inlet of the recycle compressor I to be used as a part of recycle gas, the recycle gas and the direct recycle part in the step 7 are recycled together, and the membrane separation tail gas of the membrane separator is decompressed by the decompression valve II to be used as a tail gas discharge flare system.
In another aspect of the invention, the ratio of the directly recycled gas volume in the step 7 to the gas volume entering the membrane separator is 5-50.
In another aspect of the invention, the gas recovery device is a pressure swing adsorption device, the pressure swing adsorption device separates recyclable gas, the temperature is 20-60 ℃, the pressure is 1.0-6.0 Mpa, the gas is pressurized by a circulation compressor II and then is connected to an inlet of the circulation compressor I to be used as a part of the circulation gas, the circulation gas and the direct circulation part in the step 7 are recycled together, and the tail gas discharged from the pressure swing adsorption device is discharged out of a flare system after being decompressed by a decompression valve II.
In another aspect of the present invention, the light component removal column in step 10 uses steam as a heat source of a reboiler, uses chilled water as a cold source of a condenser, and realizes control by adjusting the amount of bottom steam, the amount of top chilled water and the amount of top exhaust gas.
The invention has the beneficial effects that: the device and the method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation have the advantages of simple reactor type, short flow, low equipment investment and low energy consumption; the high-quality clean gasoline fuel can be directly obtained by a one-step method, the gasoline does not contain pollutants such as sulfur, nitrogen and the like, the gasoline component meets the national VI standard, and can be directly used as finished fuel oil or gasoline blending component and is complementary with other gasoline products; the carbon dioxide is used as a carbon resource, which is beneficial to realizing the recycling of the carbon resource, reducing the dependence on fossil energy and reducing the environmental burden.
Description of the drawings:
fig. 1 is a schematic view of a connection structure in embodiment 1 of the present invention.
Fig. 2 is a schematic view of a connection structure in embodiment 2 of the present invention.
Fig. 3 is a schematic view of a connection structure in embodiment 3 of the present invention.
In the drawings: 1. the device comprises a feeding and product heat exchanger, 2, heaters I, 3, a hydrogenation reactor, 4, a cooler, 5, a deep cooler, 6, high-pressure separation tanks I, 7, a product separation tank, 8, heaters II, 9, recycle compressors I, 10, a membrane separator, 11, recycle compressors II, 12, a light component removal tower, 13, a reboiler, 14, a condenser, 15, a product delivery pump, 16, regulating valves I, 17, regulating valves II, 18, pressure reducing valves I, 19, pressure reducing valves II, 20, pressure reducing valves III, 21, pressure reducing valves IV, 22, high-pressure separation tanks II, 23, pressure reducing valves V, 24, a pressure swing adsorption device, 25, a switch valve, 26, a carbon dioxide feeding strong magnetic ring, 27, a carbon dioxide feeding pipe, 28 and a hydrogen feeding pipe.
The specific implementation mode is as follows:
the following describes the embodiments of the present invention with reference to the drawings and examples:
in the description of the present invention, it is to be understood that the description indicating the orientation or positional relationship is based on the orientation or positional relationship shown in the drawings only for the convenience of describing the present invention and simplifying the description, and does not indicate or imply that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the scope of the present invention.
In the description of the present invention, it is to be noted that, unless otherwise explicitly specified or limited, the terms "disposed," "connected," and "connected" are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
A device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation comprises a carbon dioxide feeding pipe 27, a hydrogen feeding pipe 28, a feeding and product heat exchanger 1, a heater I2, a hydrogenation reactor 3, a cooler 4, a deep cooler 5, a high-pressure separation tank I6, a pressure reducing valve I18, a product separation tank 7, a pressure reducing valve IV21, a light component removal tower 12, a product conveying pump 15, a heater II8, a circulating compressor I9, a circulating compressor II11, a reboiler 13, a condenser 14, a pressure reducing valve III20, a switch valve 25 and a carbon dioxide feeding strong magnetic ring 26; a carbon dioxide feeding strong magnetic ring 26 is communicated with the front part of a carbon dioxide feeding pipe, the pipe body of the carbon dioxide feeding pipe is communicated with a switch valve 25, an outlet pipeline of the switch valve 25 is communicated with the pipe body of the hydrogen feeding pipe, the hydrogen feeding pipe behind the installation point of the switch valve 25 is communicated with a cold side inlet pipeline of a feeding and product heat exchanger 1, a hot side outlet pipeline of the feeding and product heat exchanger 1 is communicated with a cold side inlet of a heater I2, a hot side outlet pipeline of a heater I2 is communicated with a top inlet of a hydrogenation reactor 3, a bottom outlet pipeline of the hydrogenation reactor 3 is communicated with a hot side inlet of the feeding and product heat exchanger 1, a cold side outlet pipeline of the feeding and product heat exchanger 1 is communicated with a hot side inlet of a cooler 4, a cold side outlet pipeline of the cooler 4 is communicated with a hot side inlet of a chiller 5, and a cold side outlet pipeline of the chiller, the liquid phase outlet pipeline at the bottom of the high-pressure separation tank I6 is decompressed by a decompression valve I18 and then is communicated with the inlet of the product separation tank 7; a gas phase outlet pipeline at the top of the high-pressure separation tank I6 is communicated with a cold side inlet of a heater II8, a hot side outlet of the heater II8 is divided into two paths, one path is communicated with an inlet of a circulating compressor I9, the other path is communicated with a gas recovery device, and an outlet pipeline of the circulating compressor I9 is communicated with a hydrogen feeding pipe; a recovery pipeline of the gas recovery device is communicated with an inlet of a circulating compressor II11, and a discharge pipeline of the gas recovery device is communicated with a tail gas main pipe through a pressure reducing valve II 19; a gas phase outlet pipeline at the top of the product separation tank 7 is communicated with a tail gas main pipe through a pressure reducing valve III20, an oil phase outlet pipeline of the product separation tank 7 is communicated with an inlet of the light component removal tower 12 through a pressure reducing valve IV21, and a water phase outlet pipeline at the bottom of the product separation tank 7 continuously discharges wastewater; a gas phase pipeline at the top of the light component removal tower 12 is communicated with a hot side inlet of a condenser 14, a cold side gas phase outlet pipeline of the condenser 14 is communicated with a tail gas main pipe, and a cold side liquid phase outlet pipeline of the condenser 14 is communicated with a reflux port at the top of the light component removal tower; the bottom liquid phase outlet pipeline of the light component removing tower 12 has two paths, wherein one path is communicated with a cold side inlet of the reboiler 13, the other path is communicated with a product conveying pump inlet, a product conveying pump outlet pipeline sends qualified gasoline products out, and a hot side outlet pipeline of the reboiler 13 is communicated with a reboiler interface on the bottom side wall of the light component removing tower 12. The gas recovery device is a membrane separator 10, a membrane permeation gas outlet pipeline of the membrane separator 10 is communicated with an inlet of a circulating compressor II11, and membrane separation tail gas of the membrane separator 10 is communicated with a tail gas main pipe after being decompressed by a decompression valve II 19. The hydrogenation reactor 3 adopts an adiabatic fixed bed reactor, and the catalyst adopts a layered filling mode.
The membrane method gas separation technology is a high-tech technology which is competitively developed in the world nowadays, and the basic principle of the technology is that when a mixture of two or more gases passes through a polymer membrane, the solubility and the diffusion coefficient of each gas in the membrane are different, so that the relative permeation rates of different gases in the membrane are different. Under the action of driving force, namely pressure difference on two sides of the membrane, gas with relatively high permeation rate, such as water vapor, hydrogen, helium, hydrogen sulfide and the like, permeates the membrane preferentially to be enriched; the gas with relatively slow permeation rate, such as methane, nitrogen, carbon monoxide, hydrocarbon, etc., is enriched on the stagnation side of the membrane, so as to achieve the purpose of separating the mixed gas. The diffusion rate of the membrane is controlled by the partial pressure gradient, molecular size and stream composition characteristics, and membrane fiber characteristics. The hydrogen separation membrane used in the patent scheme is based on a high-performance polymeric material, and the membrane separator has the characteristics of high equipment packing density, high membrane selective separation performance, high permeation flux, high chemical tolerance, good temperature resistance (can be used at 90 ℃ for a long time), long service life, high pressure resistance and the like, and can be used at high temperature and pressure. The membrane module is similar to a shell-and-tube heat exchanger and is filled with tens of thousands of fine hollow fiber filaments. Compared with separation membranes of other shapes (such as flat plates, tubular plates and the like), the hollow fibers have the highest packing density (the area of the packed separation membranes in a unit volume) and can provide the largest separation area in the smallest volume, so that the separation system is compact and efficient. Meanwhile, the hollow fiber membrane yarn has the best pressure resistance and can bear larger pressure difference. The raw material gas enters the shell side of the membrane separator through a side opening of the membrane separator and is distributed in a ring between the fiber membrane tows and the wall of the container. The raw material gas flows through each membrane wire in a radial shape and flows along the outer side of the fiber. When the proper pressure difference between the inner side and the outer side of the membrane wire is maintained, the gas is driven by the partial pressure difference to selectively and preferentially permeate through the hollow fiber wall to diffuse, flow through the fiber holes, and be enriched at the low-pressure side in the membrane wire to be taken as permeate gas (product gas) to be led out of the membrane separation system. The gas (hydrocarbon) with slower permeation rate is retained in the non-permeation side, and the pressure is almost the same as that of the raw material gas, and the gas is sent out of the battery limit after decompression and cooling. The inlet gas of the membrane separation system is subjected to oil, water condensate droplets and fine particle powder removal by a coalescing filter, then enters a heater for heating, and then enters a membrane separator. The membrane separator is filled with hollow fiber membrane wire components. Under the action of the pressure difference between the inside and the outside of the hollow fiber yarn, hydrogen permeates the fiber membrane yarn at a higher speed, and a hydrogen-rich product is obtained at the fiber core side, namely permeating gas. The slower diffusion rate component is retained on the membrane feed side and is referred to as the non-permeate gas or membrane tail gas.
When the device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation is used, the specific working process is as follows:
step 3, introducing fresh raw material hydrogen at the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa through a hydrogen inlet pipe;
nCO2＋（n~6n）H2＝ n1CO＋n2CH4＋(n3C2~ n5C4)＋(n6C5~n12C11)＋n13H2o, the reaction catalyst is an iron-based/molecular sieve (Na-Fe 3O 4/HZSM-5) multifunctional composite catalyst;
step 7, separating the low-temperature mixed gas/liquid by a high-pressure separation tank I6 to obtain gas and liquid, wherein the pressure of the high-pressure separation tank I6 is 1.0-6.0 Mpa; wherein, after the heat exchange and temperature rise of the gas are carried out by a heater II8, part of the gas is directly recycled, the gas is pressurized by a recycle compressor I9 and then is combined with fresh raw material gas, the temperature of the recycle gas is 20-60 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is separated by a gas recovery device to obtain reactant components which can be recycled;
and step 10, conveying the liquid oil from the pressure reducing valve III21 to a light component removal tower 12, discharging light components dissolved in the crude gasoline product and a small amount of water and the like out of a flare system from the top of the light component removal tower 12, pressurizing other gasoline product components from the bottom of the light component removal tower 12 through a pump to serve as a gasoline product, meeting national VI standards, and controlling the temperature of the light component removal tower 12 to be 0-160 ℃ and the pressure to be 0.1-0.6 Mpa.
The hydrogenation reactor 3 adopts an interlayer cold shock mode, cold shock gas can adopt one of carbon dioxide or hydrogen or mixed gas of carbon dioxide and hydrogen in a certain ratio, and different types or ratios of cold shock gas realize regulation and control through a regulating valve I16 arranged on a raw material carbon dioxide pipeline and a regulating valve II17 arranged on a raw material hydrogen pipeline.
The ratio of the directly recycled gas amount in the step 7 to the gas amount in the membrane separator 10 is 5-50.
In the light component removal tower 12 in the step 10, steam is used as a heat source of a reboiler 13, chilled water is used as a cold source of a condenser 14, and control is realized by adjusting the amount of steam at the bottom of the tower, the amount of chilled water at the top of the tower and the amount of tail gas discharged from the top of the tower.
The invention has the beneficial effects that:
1. the invention provides a device and a method suitable for directly preparing gasoline fraction hydrocarbon by adopting a multifunctional composite catalyst to carry out a carbon dioxide hydrogenation one-step method, and the device and the method have the advantages of simple reactor type, short flow, less equipment investment and low energy consumption;
2. the invention can directly obtain high-quality clean gasoline fuel by one-step method, the gasoline does not contain pollutants such as sulfur, nitrogen and the like, the gasoline component meets the national VI standard, can be directly used as finished fuel oil, can also be used as a gasoline blending component, and is complementary with other gasoline products;
3. the invention utilizes the greenhouse gas of carbon dioxide as carbon resource, is beneficial to realizing the recycling of the carbon resource, reduces the dependence on fossil energy and simultaneously lightens the environmental burden.
Example 2
Example 2 differs from example 1 in that the membrane separator 10 in example 1 is replaced with a pressure swing adsorption unit 24, and the remaining embodiment is the same as example 1.
Example 3
The difference between the embodiment 3 and the embodiment 1 is that a high-pressure separation tank II22 and a pressure reducing valve V23 are added, and the specific steps are as follows:
a device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation comprises a carbon dioxide feeding pipe, a hydrogen feeding pipe, a feeding and product heat exchanger 1, a heater I2, a hydrogenation reactor 3, a cooler 4, a deep cooler 5, a high-pressure separation tank I6, a pressure reducing valve I18, a product separation tank 7, a pressure reducing valve IV21, a light component removal tower 12, a product conveying pump 15, a heater II8, a circulating compressor I9, a circulating compressor II11, a reboiler 13, a condenser 14, a pressure reducing valve III20, a switch valve 25 and a carbon dioxide feeding strong magnetic ring 26; a carbon dioxide feeding strong magnetic ring 26 is communicated with the front part of a carbon dioxide feeding pipe, the pipe body of the carbon dioxide feeding pipe is communicated with a switch valve 25, an outlet pipeline of the switch valve 25 is communicated with the pipe body of the hydrogen feeding pipe, the hydrogen feeding pipe behind the installation point of the switch valve 25 is communicated with a cold side inlet pipeline of a feeding and product heat exchanger 1, a hot side outlet pipeline of the feeding and product heat exchanger 1 is communicated with a cold side inlet of a heater I2, a hot side outlet pipeline of a heater I2 is communicated with a top inlet of a hydrogenation reactor 3, a bottom outlet pipeline of the hydrogenation reactor 3 is communicated with a hot side inlet of the feeding and product heat exchanger 1, a cold side outlet pipeline of the feeding and product heat exchanger 1 is communicated with a hot side inlet of a cooler 4, a cold side outlet pipeline of the cooler 4 is communicated with a hot side inlet of a chiller 5, and a cold side outlet pipeline of the chiller, the liquid phase outlet pipeline at the bottom of the high-pressure separation tank I6 is decompressed by a decompression valve I18 and then is communicated with the inlet of the product separation tank 7; a gas phase outlet pipeline at the top of the high-pressure separation tank I6 is communicated with a cold side inlet of a heater II8, a hot side outlet of the heater II8 is divided into two paths, one path is communicated with an inlet of a circulating compressor I9, the other path is communicated with a gas recovery device, and an outlet pipeline of the circulating compressor I9 is communicated with a hydrogen feeding pipe; a recovery pipeline of the gas recovery device is communicated with an inlet of a circulating compressor II11, and a discharge pipeline of the gas recovery device is communicated with a tail gas main pipe through a pressure reducing valve II 19; a gas phase outlet pipeline at the top of the product separation tank 7 is communicated with a tail gas main pipe through a pressure reducing valve III20, an oil phase outlet pipeline of the product separation tank 7 is communicated with an inlet of the light component removal tower 12 through a pressure reducing valve IV21, and a water phase outlet pipeline at the bottom of the product separation tank 7 continuously discharges wastewater; a gas phase pipeline at the top of the light component removal tower 12 is communicated with a hot side inlet of a condenser 14, a cold side gas phase outlet pipeline of the condenser 14 is communicated with a tail gas main pipe, and a cold side liquid phase outlet pipeline of the condenser 14 is communicated with a reflux port at the top of the light component removal tower; the bottom liquid phase outlet pipeline of the light component removing tower 12 has two paths, wherein one path is communicated with a cold side inlet of the reboiler 13, the other path is communicated with a product conveying pump inlet, a product conveying pump outlet pipeline sends qualified gasoline products out, and a hot side outlet pipeline of the reboiler 13 is communicated with a reboiler interface on the bottom side wall of the light component removing tower 12. The gas recovery device is a membrane separator 10, a membrane permeation gas outlet pipeline of the membrane separator 10 is communicated with an inlet of a circulating compressor II11, and membrane separation tail gas of the membrane separator 10 is communicated with a tail gas main pipe after being decompressed by a decompression valve II 19. The hydrogenation reactor 3 adopts an adiabatic fixed bed reactor, and the catalyst adopts a layered filling mode. Still include high-pressure knockout drum II22, chiller 5 sets up in high-pressure knockout drum II22 gaseous phase export, and chiller 5 cold side outlet pipe is being linked together the import of high-pressure knockout drum I6, and the import of high-pressure knockout drum II22 is being linked together to the cold side outlet pipe of cooler 4, and the bottom liquid phase outlet pipeline of high-pressure knockout drum II22 passes through relief pressure valve V23 and product knockout drum 7's import intercommunication.
The membrane method gas separation technology is a high-tech technology which is competitively developed in the world nowadays, and the basic principle of the technology is that when a mixture of two or more gases passes through a polymer membrane, the solubility and the diffusion coefficient of each gas in the membrane are different, so that the relative permeation rates of different gases in the membrane are different. Under the action of driving force, namely pressure difference on two sides of the membrane, gas with relatively high permeation rate, such as water vapor, hydrogen, helium, hydrogen sulfide and the like, permeates the membrane preferentially to be enriched; the gas with relatively slow permeation rate, such as methane, nitrogen, carbon monoxide, hydrocarbon, etc., is enriched on the stagnation side of the membrane, so as to achieve the purpose of separating the mixed gas. The diffusion rate of the membrane is controlled by the partial pressure gradient, molecular size and stream composition characteristics, and membrane fiber characteristics. The hydrogen separation membrane used in the patent scheme is based on a high-performance polymeric material, and the membrane separator has the characteristics of high equipment packing density, high membrane selective separation performance, high permeation flux, high chemical tolerance, good temperature resistance (can be used at 90 ℃ for a long time), long service life, high pressure resistance and the like, and can be used at high temperature and pressure. The membrane module is similar to a shell-and-tube heat exchanger and is filled with tens of thousands of fine hollow fiber filaments. Compared with separation membranes of other shapes (such as flat plates, tubular plates and the like), the hollow fibers have the highest packing density (the area of the packed separation membranes in a unit volume) and can provide the largest separation area in the smallest volume, so that the separation system is compact and efficient. Meanwhile, the hollow fiber membrane yarn has the best pressure resistance and can bear larger pressure difference. The raw material gas enters the shell side of the membrane separator through a side opening of the membrane separator and is distributed in a ring between the fiber membrane tows and the wall of the container. The raw material gas flows through each membrane wire in a radial shape and flows along the outer side of the fiber. When the proper pressure difference between the inner side and the outer side of the membrane wire is maintained, the gas is driven by the partial pressure difference to selectively and preferentially permeate through the hollow fiber wall to diffuse, flow through the fiber holes, and be enriched at the low-pressure side in the membrane wire to be taken as permeate gas (product gas) to be led out of the membrane separation system. The gas (hydrocarbon) with slower permeation rate is retained in the non-permeation side, and the pressure is almost the same as that of the raw material gas, and the gas is sent out of the battery limit after decompression and cooling. The inlet gas of the membrane separation system is subjected to oil, water condensate droplets and fine particle powder removal by a coalescing filter, then enters a heater for heating, and then enters a membrane separator. The membrane separator is filled with hollow fiber membrane wire components. Under the action of the pressure difference between the inside and the outside of the hollow fiber yarn, hydrogen permeates the fiber membrane yarn at a higher speed, and a hydrogen-rich product is obtained at the fiber core side, namely permeating gas. The slower diffusion rate component is retained on the membrane feed side and is referred to as the non-permeate gas or membrane tail gas.
When the device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation is used, the specific working process is as follows:
step 3, introducing fresh raw material hydrogen at the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa through a hydrogen inlet pipe;
nCO2＋（n~6n）H2＝ n1CO＋n2CH4＋(n3C2~ n5C4)＋(n6C5~n12C11)＋n13H2o, the reaction catalyst is an iron-based/molecular sieve (Na-Fe 3O 4/HZSM-5) multifunctional composite catalyst;
step 7, separating the mixture by a cooler 4 and then a high-pressure separation tank II22, a deep cooler 5 and a high-pressure separation tank I6 to obtain gas and liquid; wherein, after the heat exchange and temperature rise of the gas are carried out by a heater II8, part of the gas is directly recycled, the gas is pressurized by a recycle compressor I9 and then is combined with fresh raw material gas, the temperature of the recycle gas is 20-60 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is separated by a gas recovery device to obtain reactant components which can be recycled;
and step 10, conveying the liquid oil from the pressure reducing valve IV21 to the light component removal tower 12, discharging light components dissolved in the crude gasoline product and a small amount of water and the like out of a flare system from the top of the light component removal tower 12, pressurizing other gasoline product components from the bottom of the light component removal tower 12 through a pump to be used as a gasoline product, meeting national VI standards, and controlling the temperature of the light component removal tower 12 to be 0-160 ℃ and the pressure to be 0.1-0.6 Mpa.
The hydrogenation reactor 3 adopts an interlayer cold shock mode, cold shock gas can adopt one of carbon dioxide or hydrogen or mixed gas of carbon dioxide and hydrogen in a certain ratio, and different types or ratios of cold shock gas realize regulation and control through a regulating valve I16 arranged on a raw material carbon dioxide pipeline and a regulating valve II17 arranged on a raw material hydrogen pipeline.
The ratio of the directly recycled gas amount in the step 7 to the gas amount in the membrane separator 10 is 5-50.
In the light component removal tower 12 in the step 10, steam is used as a heat source of a reboiler 13, chilled water is used as a cold source of a condenser 14, and control is realized by adjusting the amount of steam at the bottom of the tower, the amount of chilled water at the top of the tower and the amount of tail gas discharged from the top of the tower.
The invention has the beneficial effects that:
1. the invention provides a device and a method suitable for directly preparing gasoline fraction hydrocarbon by adopting a multifunctional composite catalyst to carry out a carbon dioxide hydrogenation one-step method, and the device and the method have the advantages of simple reactor type, short flow, less equipment investment and low energy consumption;
2. the invention can directly obtain high-quality clean gasoline fuel by one-step method, the gasoline does not contain pollutants such as sulfur, nitrogen and the like, the gasoline component meets the national VI standard, can be directly used as finished fuel oil, can also be used as a gasoline blending component, and is complementary with other gasoline products;
3. the invention utilizes the greenhouse gas of carbon dioxide as carbon resource, is beneficial to realizing the recycling of the carbon resource, reduces the dependence on fossil energy and simultaneously lightens the environmental burden.
Example 4
A method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation adopts the device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation in the embodiment 1 or the embodiment 2, and comprises the following operation steps:
step 3, introducing fresh raw material hydrogen at the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa through a hydrogen inlet pipe;
nCO2＋（n~6n）H2＝ n1CO＋n2CH4＋(n3C2~ n5C4)＋(n6C5~n12C11)＋n13H2o, reactionThe catalyst is an iron-based/molecular sieve (Na-Fe 3O 4/HZSM-5) multifunctional composite catalyst;
step 7, separating the low-temperature mixed gas/liquid by a high-pressure separation tank I6 to obtain gas and liquid, wherein the pressure of the high-pressure separation tank I6 is 1.0-6.0 Mpa; wherein, after the heat exchange and temperature rise of the gas are carried out by a heater II8, part of the gas is directly recycled, the gas is pressurized by a recycle compressor I9 and then is combined with fresh raw material gas, the temperature of the recycle gas is 20-60 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is separated by a gas recovery device to obtain reactant components which can be recycled;
and step 10, conveying the liquid oil from the pressure reducing valve IV21 to a light component removal tower 12, discharging light components dissolved in the crude gasoline product and a small amount of water and the like out of a flare system from the top of the light component removal tower 12, pressurizing other gasoline product components from the bottom of the light component removal tower 12 through a pump to be used as a gasoline product, wherein the temperature of the light component removal tower 12 is 0-160 ℃, and the pressure is 0.1-0.6 Mpa.
The hydrogenation reactor 3 adopts an interlayer cold shock mode, cold shock gas can adopt one of carbon dioxide or hydrogen or mixed gas of carbon dioxide and hydrogen in a certain ratio, and different types or ratios of cold shock gas realize regulation and control through a regulating valve I16 arranged on a raw material carbon dioxide pipeline and a regulating valve II17 arranged on a raw material hydrogen pipeline. In the light component removal tower 12 in the step 10, steam is used as a heat source of a reboiler 13, chilled water is used as a cold source of a condenser 14, and control is realized by adjusting the amount of steam at the bottom of the tower, the amount of chilled water at the top of the tower and the amount of tail gas discharged from the top of the tower.
The invention has the beneficial effects that:
1. the method for directly preparing the gasoline fraction hydrocarbon by the carbon dioxide hydrogenation is suitable for directly preparing the gasoline fraction hydrocarbon by a one-step method of the carbon dioxide hydrogenation by adopting a multifunctional composite catalyst, and has the advantages of simple reactor type, short flow, less equipment investment and low energy consumption;
2. the invention can directly obtain high-quality clean gasoline fuel by one-step method, the gasoline does not contain pollutants such as sulfur, nitrogen and the like, the gasoline component meets the national VI standard, can be directly used as finished fuel oil, can also be used as a gasoline blending component, and is complementary with other gasoline products;
3. the invention utilizes the greenhouse gas of carbon dioxide as carbon resource, is beneficial to realizing the recycling of the carbon resource, reduces the dependence on fossil energy and simultaneously lightens the environmental burden.
In summary, the above-mentioned embodiments are only preferred embodiments of the present invention, and all equivalent changes and modifications made in the claims of the present invention should be covered by the claims of the present invention.
Claims (10)
1. A device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation is characterized by comprising a carbon dioxide feeding pipe (27), a hydrogen feeding pipe (28), a feeding and product heat exchanger (1), a heater I (2), a hydrogenation reactor (3), a cooler (4), a deep cooler (5), a high-pressure separation tank I (6), a pressure reducing valve I (18), a product separation tank (7), a pressure reducing valve IV (21), a light component removal tower (12), a product conveying pump (15), a heater II (8), a circulating compressor I (9), a circulating compressor II (11), a reboiler (13), a condenser (14), a pressure reducing valve III (20) and a switch valve (25);
the pipe body of the carbon dioxide feeding pipe is communicated with a switch valve (25), an outlet pipeline of the switch valve (25) is communicated with the pipe body of the hydrogen feeding pipe, the hydrogen feeding pipe at the rear side of the installation point of the switch valve (25) is communicated with a cold side inlet pipeline of the feeding and product heat exchanger (1), a hot side outlet pipeline of the feeding and product heat exchanger (1) is communicated with a cold side inlet of a heater I (2), a hot side outlet pipeline of the heater I (2) is communicated with a top inlet of a hydrogenation reactor (3), a bottom outlet pipeline of the hydrogenation reactor (3) is communicated with a hot side inlet of the feeding and product heat exchanger (1), a cold side outlet pipeline of the feeding and product heat exchanger (1) is communicated with a hot side inlet of a cooler (4), a cold side outlet pipeline of the cooler (4) is communicated with an inlet of a chiller (5), and a cold side outlet pipeline of the chiller (5) is communicated with an inlet of a high-pressure separation tank I, the liquid phase outlet pipeline at the bottom of the high-pressure separation tank I (6) is decompressed by a decompression valve I (18) and then is communicated with the inlet of the product separation tank (7);
a gas phase outlet pipeline at the top of the high-pressure separation tank I (6) is communicated with a cold side inlet of a heater II (8), a hot side outlet of the heater II (8) is divided into two paths, one path is communicated with an inlet of a circulating compressor I (9), the other path is communicated with a gas recovery device, and an outlet pipeline of the circulating compressor I (9) is communicated with a hydrogen feeding pipe; a recovery pipeline of the gas recovery device is communicated with an inlet of a circulating compressor II (11), and a discharge pipeline of the gas recovery device is communicated with a tail gas main pipe through a pressure reducing valve II (19);
a gas phase outlet pipeline at the top of the product separation tank (7) is communicated with a tail gas main pipe through a pressure reducing valve III (20), and an oil phase outlet pipeline of the product separation tank (7) is communicated with an inlet of a light component removal tower (12) through a pressure reducing valve IV (21);
a gas phase pipeline at the top of the light component removal tower (12) is communicated with a hot side inlet of a condenser (14), a cold side gas phase outlet pipeline of the condenser (14) is communicated with a tail gas main pipe, and a cold side liquid phase outlet pipeline of the condenser (14) is communicated with a reflux opening at the top of the light component removal tower; the liquid phase outlet pipeline at the bottom of the light component removing tower (12) has two paths, wherein one path is communicated with the cold side inlet of the reboiler (13), the other path is communicated with the product delivery pump inlet, and the hot side outlet pipeline of the reboiler (13) is communicated with the reboiler interface on the bottom side wall of the light component removing tower (12).
2. The device for directly preparing gasoline fraction hydrocarbon by hydrogenation of carbon dioxide according to claim 1, wherein the gas recovery device is a membrane separator (10) or a pressure swing adsorption device (24), a membrane permeation gas outlet pipeline of the membrane separator (10) is communicated with an inlet of a circulation compressor II (11), and membrane separation tail gas of the membrane separator (10) is reduced in pressure by a pressure reducing valve II (19) and then is communicated with a tail gas main pipe.
3. The apparatus for directly preparing gasoline fraction hydrocarbon by hydrogenation of carbon dioxide according to any one of claims 1 or 2, wherein the hydrogenation reactor (3) adopts an adiabatic fixed bed reactor, and the catalyst adopts a layered packing mode.
4. The device for directly preparing gasoline fraction hydrocarbons by hydrogenating carbon dioxide according to any one of claims 1 or 2, further comprising a high-pressure separation tank II (22), wherein the chiller (5) is arranged at a gas phase outlet of the high-pressure separation tank II (22), a cold side outlet pipeline of the chiller (5) is communicated with an inlet of the high-pressure separation tank I (6), a cold side outlet pipeline of the cooler (4) is communicated with an inlet of the high-pressure separation tank II (22), and a bottom liquid phase outlet pipeline of the high-pressure separation tank II (22) is communicated with an inlet of the product separation tank (7) through a pressure reducing valve V (23).
5. A method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation, which is characterized in that the device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation according to claim 1 comprises the following operation steps:
step 1, introducing fresh raw material carbon dioxide with the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
step 2, the raw material carbon dioxide is sequentially subjected to heat exchange and temperature rise through the feeding and product heat exchanger (1), the heater I (2) is further heated and temperature rise, the temperature of heated gas is 250-450 ℃, and the heat exchange load of the feeding and product heat exchanger (1) is gradually increased in the heating process of the heated gas;
step 3, introducing fresh raw material hydrogen at the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
step 4, the raw material hydrogen and the raw material carbon dioxide are sequentially subjected to heat exchange and temperature rise through the feeding and product heat exchanger (1), the heater I (2) is further heated and temperature rise, and the temperature of the heated mixed heating gas is 250-450 ℃;
step 5, introducing mixed heating gas into a fixed bed layer of the hydrogenation reactor (3) for reaction by adopting an interlayer cold shock mode in the hydrogenation reactor (3) to obtain reaction mixed gas, wherein the reaction temperature is 250-500 ℃, the pressure is 1.0-6.0 Mpa, and the general formula of the total reaction equation is as follows:
nCO2＋（n~6n）H2＝ n1CO＋n2CH4＋(n3C2~ n5C4)＋(n6C5~n12C11)＋n13H2o, reaction catalyst is iron-based/molecular sieve(Na-Fe 3O 4/HZSM-5) multifunctional composite catalyst;
step 6, exchanging heat, cooling and condensing the reaction mixed gas from the bottom of the hydrogenation reactor (3) through a feed and product heat exchanger (1), a cooler (4) and a deep cooler (5) in sequence to obtain cooled and partially condensed low-temperature mixed gas/liquid, wherein the temperature of the low-temperature mixed gas/liquid is-30-10 ℃;
step 7, separating the low-temperature mixed gas/liquid by a high-pressure separation tank I (6) to obtain gas and liquid, wherein the pressure of the high-pressure separation tank I (6) is 1.0-6.0 Mpa; wherein, after the heat exchange and temperature rise of the gas by a heater II (8), part of the gas is directly recycled, the gas is pressurized by a recycle compressor I (9) and then is combined with fresh raw material gas, the temperature of the recycle gas is 20-60 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is separated by a gas recovery device to obtain reactant components which can be recycled;
step 8, separating recyclable gas by a gas recovery device, wherein the temperature is 20-60 ℃, the pressure is 0.4-6.0 Mpa, the recyclable gas is pressurized by a circulating compressor II (11), then is connected to an inlet of a circulating compressor I (9) and is used as a part of circulating gas, and the circulating gas and the direct circulating part in the step 7 are recycled together, and tail gas discharged by the gas recovery device is discharged out of a torch system after being decompressed by a decompression valve II (19);
step 9, decompressing the liquid obtained in the step 7 through the high-pressure separation tank I (6) through a decompression valve I (18), entering a product separation tank (7), decompressing the product separation tank at 0.5-2.5 Mpa, decompressing the separated small amount of light hydrocarbon gas through a decompression valve III (20) to be used as a tail gas discharge torch system; the separated liquid oil is decompressed by a decompression valve IV (21) and sent to a downstream lightness-removing tower (12) for further rectification and purification; liquid water separated out by the product separating tank (7) is discharged continuously;
and step 10, conveying the liquid oil from the pressure reducing valve IV (21) to a light component removal tower (12), discharging light components dissolved in the crude gasoline product and a small amount of water and the like out of a flare system from the top of the light component removal tower (12), pressurizing other gasoline product components from the bottom of the light component removal tower (12) through a pump to obtain a gasoline product, wherein the temperature of the light component removal tower (12) is 0-160 ℃, and the pressure is 0.1-0.6 Mpa.
6. The method for directly preparing gasoline fraction hydrocarbons by carbon dioxide hydrogenation according to claim 5, wherein the hydrogenation reactor (3) adopts an interlayer quenching mode, the quenching gas can adopt one of carbon dioxide or hydrogen, or a mixed gas of carbon dioxide and hydrogen with a certain ratio, and the adjustment control of different types of the quenching gas or the ratio thereof is realized by an adjusting valve I (16) arranged on a raw material carbon dioxide pipeline and an adjusting valve II (17) arranged on a raw material hydrogen pipeline.
7. The method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation according to claim 5 or 6, characterized in that the gas recovery device is a membrane separator (10), membrane permeation gas capable of being recycled is separated by the membrane separator (10), the temperature is 20-60 ℃, the pressure is 0.4-2.5 Mpa, the membrane permeation gas is pressurized by a recycle compressor II (11), and then the membrane permeation gas is connected to an inlet of the recycle compressor I (9) to be used as a part of recycle gas and recycled together with the direct recycle part in the step 7, and membrane separation tail gas of the membrane separator (10) is depressurized by a pressure reducing valve II (19) to be used as a tail gas discharge flare system.
8. The method for directly preparing gasoline fraction hydrocarbons by carbon dioxide hydrogenation according to claim 7, wherein the ratio of the direct recycling gas amount in the step 7 to the gas amount entering the membrane separator (10) is 5-50.
9. The method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation according to claim 5 or 6, characterized in that the gas recovery device is a pressure swing adsorption device (24), the pressure swing adsorption device (24) separates recyclable gas at a temperature of 20-60 ℃ and a pressure of 1.0-6.0 MPa, the recyclable gas is pressurized by a recycle compressor II (11), then the recyclable gas is connected to an inlet of the recycle compressor I (9) and used as a part of recycle gas, and the recyclable gas and the direct recycle part in the step 7 are recycled together, and the tail gas discharged from the pressure swing adsorption device (24) is decompressed by a decompression valve II (19) and then discharged to a flare system.
10. The method for directly preparing gasoline fraction hydrocarbons by carbon dioxide hydrogenation according to claim 5 or 6, wherein the light component removal tower (12) in the step 10 uses steam as a heat source of the reboiler (13), uses chilled water as a cold source of the condenser (14), and is controlled by adjusting the amount of bottom steam, the amount of top chilled water and the amount of top exhaust gas.
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| CN113061456A (en) * | 2021-03-08 | 2021-07-02 | 众一伍德工程有限公司 | Fluidized bed process for preparing gasoline from carbon dioxide and hydrogen |
| CN114479902A (en) * | 2020-11-13 | 2022-05-13 | 中国科学院大连化学物理研究所 | Device and method for preparing gasoline by catalytic hydrogenation of carbon dioxide |
| CN114671730A (en) * | 2022-03-07 | 2022-06-28 | 中石化广州工程有限公司 | Method for preparing alpha-olefin by carbon dioxide hydrogenation |
| CN114874803A (en) * | 2022-05-18 | 2022-08-09 | 王承东 | Method and device for preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation powered by solar energy |
| WO2022177536A1 (en) * | 2021-02-22 | 2022-08-25 | Turkiye Petrol Rafinerileri Anonim Sirketi Tupras | A method and a system for producing fuel and high value-added chemicals from carbon dioxide-rich process gases |
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| CN212246906U (en) * | 2020-07-13 | 2020-12-29 | 珠海市福沺能源科技有限公司 | Device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation |
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