CN113004931A - Single-tube test device and method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation - Google Patents
Single-tube test device and method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation Download PDFInfo
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- CN113004931A CN113004931A CN202110335761.2A CN202110335761A CN113004931A CN 113004931 A CN113004931 A CN 113004931A CN 202110335761 A CN202110335761 A CN 202110335761A CN 113004931 A CN113004931 A CN 113004931A
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- 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
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- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
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Abstract
A single tube test device and a method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation relate to the technical field of gasoline production chemical process, and comprise a gas-gas heat exchanger, a heater, a single tube reactor, a cooling condenser, a gas-liquid separator I, an oil-water separator, a circulating compressor, a heat-conducting oil circulating pump, a heat-conducting oil cooler, a gas-liquid separator II, an expansion tank, a raw material hydrogen regulating valve and a raw material carbon dioxide regulating valve, the reactor is suitable for a layered filling reactor adopting two multifunctional composite catalysts, namely an iron-based catalyst and a molecular sieve catalyst, and the reactor type is suitable for reaction conditions with different reaction thermodynamic properties and optimal reaction temperatures of reaction media in which the two catalysts are positioned.
Description
The technical field is as follows:
the invention relates to the technical field of gasoline production chemical processes, in particular to a single-tube test device and a single-tube test method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation.
Background art:
in recent years, with the rapid development of industry, fossil energy has been increasingly depleted, and global environmental problems caused by the depletion of a large amount of carbon dioxide due to the use of fossil energy in large quantities have been receiving wide attention from countries around the world. The carbon dioxide is converted into the synthesis gas or other hydrocarbons by a chemical conversion method, so that the resource utilization of the carbon dioxide can be realized, and the greenhouse effect caused by the carbon dioxide can be reduced "
Although the greenhouse effect of carbon dioxide causes global warming and climate change, it is widely used as an industrial raw material. The conversion of carbon dioxide into liquid fuels and high value-added chemicals by chemical conversion is a recent research hotspot at home and abroad. The process not only can realize the resource utilization of the carbon dioxide, but also can reduce the greenhouse effect caused by the carbon dioxide.
However, carbon dioxide is very stable, and its activation and selective conversion are very challenging problems. Because the adsorption and reaction rate on the surface of the catalyst is slow, and the chain growth capability is poor, the hydrogenation products of the catalyst are concentrated in low-carbon compounds such as methane, methanol, formic acid and the like. If the process can be used for selectively producing high-carbon hydrocarbons such as oil products, olefins or aromatic hydrocarbons with higher carbon chains and higher added values, important and profound influences are generated on the traditional coal and natural gas chemical industry routes.
At present, a single-tube test device and a single-tube test method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation cannot be inquired from published data, and particularly the single-tube test device and the single-tube test method are suitable for a layered filling reactor by adopting two multifunctional composite catalysts, namely an iron-based catalyst and a molecular sieve catalyst, wherein the reaction thermodynamic properties of reaction media of the two catalysts are different from the optimal reaction temperature conditions.
The invention content is as follows:
the invention aims to overcome the defects in the prior art and provides a single-tube test device and a single-tube test method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation, which aim at overcoming the defects of a single-tube test device and a single-tube test method for preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation by using two multifunctional composite catalysts, namely an iron-based catalyst and a molecular sieve catalyst, which are filled in a reactor in a layered manner.
The invention is realized by the following technical scheme:
a single-tube test device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation is characterized by comprising a gas-gas heat exchanger, a heater, a single-tube reactor, a cooling condenser, a gas-liquid separator I, an oil-water separator, a circulating compressor, a heat-conducting oil circulating pump, a heat-conducting oil cooler, a gas-liquid separator II, an expansion tank, a raw material hydrogen regulating valve, a raw material carbon dioxide regulating valve, a pressure reducing valve I, a regulating valve I, a pressure reducing valve II, a regulating valve III, a start-up heater, an iron-based row tube section, an iron-based heat insulation section, a molecular sieve heat insulation section, a row tube section shell, a;
the outlet pipeline of the raw material carbon dioxide regulating valve is communicated with the raw material hydrogen pipeline at the outlet of the raw material hydrogen regulating valve, the mixed raw material carbon dioxide and raw material hydrogen pipeline is communicated with the cold side inlet pipeline of the gas-gas heat exchanger, the hot side outlet pipeline of the gas-gas heat exchanger is communicated with the cold side inlet of the heater, the hot side outlet pipeline of the heater is communicated with the top inlet of the single-tube reactor, the bottom outlet pipeline of the single-tube reactor is communicated with the hot side inlet of the gas-gas heat exchanger, the cold side outlet pipeline of the gas-gas heat exchanger is communicated with the hot side inlet of the cooling condenser, the cold side outlet pipeline of the cooling condenser is communicated with the inlet of the gas-liquid separator I, and the bottom liquid phase outlet pipeline of the;
a gas phase outlet at the top of the gas-liquid separator I is divided into two paths, wherein one path is communicated with an inlet of a circulating compressor, and an outlet pipeline of the circulating compressor is communicated with a mixed gas pipeline of the raw material carbon dioxide and the hydrogen; the other path of the tail gas is communicated with an inlet pipeline of a pressure reducing valve I, and an outlet of the pressure reducing valve I is communicated with a tail gas main pipe through a decompressed gas pipeline;
a gas phase outlet pipeline at the top of the oil-water separator is communicated with an inlet of the pressure reducing valve II;
the bottom pipe orifice of the expansion tank is communicated with the top pipe orifice of the gas-liquid separator II through a pipeline; the bottom outlet pipeline of the gas-liquid separator II is communicated with the inlet of the heat conducting oil pump; the outlet of the heat conducting oil pump is divided into two paths, wherein one path is communicated with the inlet of the regulating valve II, and the outlet pipeline of the regulating valve II is communicated with the cold side inlet of the start-up heater; the other path is communicated with a hot side inlet pipeline of the heat conduction oil cooler, and a heat conduction oil outlet pipeline cooled by the heat conduction oil cooler is communicated with an outlet pipeline of the regulating valve II; the hot side outlet of the start-up heater is communicated with a heat conduction oil inlet below the shell of the tube array section of the single-tube reactor; and a heat conduction oil outlet pipeline above the shell of the tube section of the single-tube reactor is communicated with an inlet of the gas-liquid separator II.
In another aspect of the invention, the single-tube reactor is respectively composed of an iron-based pipe section, an iron-based heat-insulating section and a molecular sieve heat-insulating section from top to bottom, and electric tracing bands are wound on the outer walls of the iron-based pipe section, the iron-based heat-insulating section and the molecular sieve heat-insulating section.
In another aspect of the invention, the heater and the start-up heater use electrical or steam heating.
In another aspect of the invention, the deep cooling device further comprises a deep cooling device and a gas-liquid separator III, wherein a top gas-phase outlet pipeline of the gas-liquid separator I is connected with a hot-side inlet of the deep cooling device, a cold-side outlet of the deep cooling device is communicated with an inlet of the gas-liquid separator III, and a bottom liquid-phase outlet pipeline of the gas-liquid separator III is communicated with an inlet of the oil-water separator after being regulated and controlled by a regulating valve III; and a gas phase outlet at the top of the gas-liquid separator III is divided into two paths, wherein one path is communicated with an inlet of the circulating compressor, and the other path is communicated with an inlet pipeline of the pressure reducing valve I.
In another aspect of the invention, the system further comprises a chiller and a gas-liquid separator III, wherein the circulating compressor is arranged on a top gas-phase outlet pipeline of the gas-liquid separator I, an outlet pipeline of the circulating compressor is communicated with a hot-side inlet of the chiller, a cold-side outlet of the chiller is communicated with an inlet of the gas-liquid separator III, and a bottom liquid-phase outlet pipeline of the gas-liquid separator III is communicated with an inlet of the oil-water separator after being regulated and controlled by a regulating valve III; and a gas phase outlet at the top of the gas-liquid separator III is divided into two paths, wherein one path is communicated with a mixed gas pipeline of the raw material carbon dioxide and the hydrogen, and the other path is communicated with an inlet pipeline of the pressure reducing valve I.
A single-tube test method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation is characterized by comprising the following steps:
the heat conduction oil is sent to an expansion tank, when the heat conduction oil circulating system is filled with the heat conduction oil, and meanwhile, the liquid level of the heat conduction oil in the expansion tank is in a proper position, a heat conduction oil circulating pump is started;
starting a start-up heater and electric tracing bands on the outer walls of the equipment of the iron-based tubular section, the iron-based heat insulation section and the molecular sieve heat insulation section of the single-tube reactor, heating the heat conduction oil circulation system, and raising the temperature to the required set temperature;
introducing fresh raw material carbon dioxide with the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
introducing fresh raw material hydrogen at the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
the method comprises the following steps that raw material hydrogen and raw material carbon dioxide are sequentially subjected to heat exchange and temperature rise through a gas-gas heat exchanger, a heater is used for further heating and temperature rise, the temperature of heated mixed heating gas is 250-450 ℃, and the heat exchange load of the gas-gas heat exchanger is gradually increased in the heating process of the heating gas;
introducing mixed heating gas into the single-tube reactor, and sequentially passing through a fixed bed catalyst bed layer of an iron-based tubular section, an iron-based heat insulation section and a molecular sieve heat insulation section from top to bottom to perform chemical reaction 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 general reaction equation is as follows: nCO2+(n～6n)H2＝n1CO+n2CH4+(n3C2～n5C4)+(n6C5～n12C11)+n13H2O, the reaction catalyst is an iron-based/molecular sieve (Na-Fe3O4/HZSM-5) multifunctional composite catalyst;
turning off an operating heater in the heat conduction oil circulating system, cutting into a heat conduction oil cooler to control the temperature of the heat conduction oil circulating system and further control the temperature of an iron-based catalyst bed layer in a tube section reaction tube of the single-tube reactor;
the reaction mixed gas is subjected to heat exchange, temperature reduction and condensation sequentially through a gas-gas heat exchanger and a cooling condenser from the bottom of the single-tube reactor to obtain low-temperature mixed gas/liquid after temperature reduction and partial condensation, wherein the temperature of the low-temperature mixed gas/liquid is-30-10 ℃;
separating the low-temperature mixed gas/liquid by a gas-liquid separator I to obtain gas and liquid, wherein the pressure of the gas-liquid separator I is 1.0-6.0 Mpa; one part of the gas is directly recycled, the gas is pressurized by a recycle compressor and then is combined with fresh raw material gas, the temperature of the recycle gas is 0-60 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is decompressed by a decompression valve I and then is discharged as one part of tail gas.
In another aspect of the invention, the liquid separated by the gas-liquid separator I is regulated by the regulating valve I to control the flow rate of the liquid, the liquid enters the oil-water separator, the pressure of the oil-water separator is 0.5-3.0 MPa, and a small amount of separated gas is discharged as tail gas after being decompressed by the pressure reducing valve II; the separated liquid crude gasoline and waste water are continuously delivered.
In another aspect of the invention, the gas separated by the gas-liquid separator I enters a deep cooler for further cooling and condensation, the outlet temperature of the deep cooler is-40 to 5 ℃, the low-temperature mixed gas/liquid at the outlet of the deep cooler is separated by a gas-liquid separator III to obtain gas and liquid, and the pressure of the gas-liquid separator IIII 5 is 1.0 to 6.0 MPa; one part of the gas is directly recycled, the gas is pressurized by a recycle compressor and then is combined with fresh raw material gas, the temperature of the recycle gas is-20-50 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is decompressed by a decompression valve I and then is discharged as one part of tail gas.
In another aspect of the invention, a recycle compressor is provided on the conduit between the top gas phase outlet of the gas liquid separator I and the hot side inlet of the chiller.
The invention has the beneficial effects that:
(1) the scheme provides a single-tube test device and a single-tube test method for preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation, wherein the single-tube test device and the single-tube test method are suitable for a reactor filled with two multifunctional composite catalysts, namely an iron-based catalyst and a molecular sieve catalyst, in a layered mode, and the reactor type is suitable for reaction conditions with different reaction thermodynamic properties and optimal reaction temperatures of reaction media in which the two catalysts are positioned;
(2) according to the scheme, most of the iron-based catalyst bed layers with larger reaction heat release are filled above the single-tube reactor in an isothermal tubular fixed bed mode, and a small number of iron-based catalyst bed layers and all molecular sieve catalyst bed layers are sequentially filled at an outlet below the isothermal tubular fixed bed reactor, so that the balance and control between the heat release amount and the heat transfer amount in the iron-based catalyst bed layers are ensured, and the requirement of the condition that the reaction temperature value of the molecular sieve catalyst bed layer with less reaction heat release is higher than the reaction temperature value of the outlet of the isothermal tubular reactor bed is met;
(3) the central reaction bed temperature of the isothermal single-tube reactor is mainly controlled by adjusting the temperature and circulation quantity of heat-conducting oil in the sleeve, corresponding heat calculation can be carried out according to factors such as the specific heat of the heat-conducting oil, the temperature of the heat-conducting oil entering and exiting the sleeve, the flow velocity in the tube, the temperature of a reaction medium entering and exiting the reaction tube in the catalyst bed, the heat transfer area, the material of the reactor and the like, the calculation result can be popularized and applied to the design work of the reactor with a high-pressure steam and a steam pocket on the shell side of an industrial scale, and the difficulty in design and operation of a single-tube test device caused by the fact that the single-tube scale is small and the shell side adopts.
Description of the drawings:
fig. 1 is a schematic structural diagram of embodiment 1 of the present invention.
Fig. 2 is a schematic structural diagram of embodiment 2 of the present invention.
Fig. 3 is a schematic structural diagram of embodiment 3 of the present invention.
FIG. 4 is a schematic view of a single-tube reactor according to the present invention.
In the drawings: 1. the system comprises a gas-gas heat exchanger, 2, a heater, 3, a single-tube reactor, 4, a cooling condenser, 5, gas-liquid separators I, 6, an oil-water separator, 7, a circulating compressor, 8, a heat-conducting oil circulating pump, 9, a heat-conducting oil cooler, 10, gas-liquid separators II, 11, an expansion tank, 12, a raw material hydrogen regulating valve, 13, a raw material carbon dioxide regulating valve, 14, a pressure reducing valve I, 15, regulating valves I, 16, a pressure reducing valve II, 17, regulating valves II, 18, a deep cooler, 19, gas-liquid separators III, 20, regulating valves III, 21, a start-up heater, 22, an iron-based section, 23, an insulating iron-based section, 24, a molecular sieve insulating section, 25, a column section shell, 26, a column section reaction tube, 27, an electric tracing band, 28, heat-conducting oil, 29, raw material carbon dioxide, 30, raw material hydrogen, 31, tail.
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 single-tube test device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation comprises a gas-gas heat exchanger 1, a heater 2, a single-tube reactor 3, a cooling condenser 4, a gas-liquid separator I5, an oil-water separator 6, a circulating compressor 7, a heat-conducting oil circulating pump 8, a heat-conducting oil cooler 9, a gas-liquid separator II 10, an expansion tank 11, a raw material hydrogen regulating valve 12, a raw material carbon dioxide regulating valve 13, a pressure reducing valve I14, a regulating valve I15, a pressure reducing valve II 16, a regulating valve II 17, a start-up heater 21, an iron-based tube section 22, an iron-based heat-insulating section 23, a molecular sieve heat-insulating section 24, a tube section shell 25, a tube section reaction tube;
the inlet pipeline of the raw material carbon dioxide regulating valve 13 is communicated with raw material carbon dioxide, the inlet pipeline of the raw material hydrogen regulating valve 12 is communicated with raw material hydrogen, the outlet pipeline of the raw material carbon dioxide regulating valve 13 is communicated with the raw material hydrogen pipeline of the outlet of the raw material hydrogen regulating valve 12, the mixed raw material carbon dioxide and raw material hydrogen pipeline is communicated with the cold side inlet pipeline of the gas-gas heat exchanger 1, the hot side outlet pipeline of the gas-gas heat exchanger 1 is communicated with the cold side inlet of the heater 2, the hot side outlet pipeline of the heater 2 is communicated with the top inlet of the single-tube reactor 3, the bottom outlet pipeline of the single-tube reactor 3 is communicated with the hot side inlet of the gas-gas heat exchanger 1, the cold side outlet pipeline of the gas-gas heat exchanger 1 is communicated with the hot side inlet of the cooling condenser 4, the cold side outlet pipeline of the cooling condenser 4 is, is communicated with the inlet of the oil-water separator 6;
a gas phase outlet at the top of the gas-liquid separator I5 is divided into two paths, wherein one path is communicated with an inlet of a circulating compressor 7, and an outlet pipeline of the circulating compressor 7 is communicated with a mixed gas pipeline of the raw material carbon dioxide and the hydrogen; the other path of the tail gas is communicated with an inlet pipeline of a pressure reducing valve I14, and an outlet of the pressure reducing valve I14 is communicated with a tail gas main pipe through a decompressed gas pipeline;
a top gas phase outlet pipeline of the oil-water separator 6 is communicated with an inlet of a pressure reducing valve II 16, an outlet of the pressure reducing valve II 16 is continuously discharged out of tail gas after pressure reduction, an oil phase outlet pipeline of the oil-water separator 6 is continuously discharged out of crude gasoline products, and a bottom water phase outlet pipeline of the oil-water separation tank 6 is continuously discharged out of waste water;
the intermittently supplemented heat conduction oil is communicated with a heat conduction oil inlet at the top of the expansion tank 11 through a pipeline, and a bottom pipe orifice of the expansion tank 11 is communicated with a top pipe orifice of the gas-liquid separator II 10 through a pipeline, so that the intermittently supplemented heat conduction oil is used for supplementing the heat conduction oil of the circulating heat conduction oil system and is also used for discharging gas phase components generated in the circulating heat conduction oil system; the bottom outlet pipeline of the gas-liquid separator II 10 is communicated with the inlet of the heat conducting oil pump 8; the outlet of the heat-conducting oil pump 8 is divided into two paths, wherein one path is communicated with the inlet of the regulating valve II 17, and the outlet pipeline of the regulating valve II 17 is communicated with the cold-side inlet of the start-up heater 21; the other path is communicated with a hot side inlet pipeline of the heat conduction oil cooler 9, and a heat conduction oil outlet pipeline cooled by the heat conduction oil cooler 9 is communicated with an outlet pipeline of the regulating valve II 17; the hot side outlet of the start-up heater 21 is communicated with a heat conduction oil inlet below the shell 25 of the tube section of the single-tube reactor 3; a heat-conducting oil outlet pipeline above the shell 25 of the tube section of the single-tube reactor 3 is communicated with an inlet of the gas-liquid separator II 10;
the single-tube reactor 3 is respectively composed of an iron-based tubular section 22, an iron-based heat-insulating section 23 and a molecular sieve heat-insulating section 24 from top to bottom, and electric tracing bands 27 are wound on the outer walls of the iron-based tubular section 22, the iron-based heat-insulating section 23 and the molecular sieve heat-insulating section 24 and are used for maintaining the outer walls of the tubular section shell 25, the iron-based heat-insulating section 23 and the molecular sieve heat-insulating section 24 at constant temperature so as to compensate heat dissipation to the surrounding environment.
The heater 2 and the start-up heater 21 may be electrically heated or steam heated.
When the single-tube test device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation is used, the single-tube test device specifically comprises the following operation steps:
step (1), heat conduction oil is sent to an expansion tank 11, when a heat conduction oil circulating system is filled with the heat conduction oil, and meanwhile, the liquid level of the heat conduction oil in the expansion tank 11 is in a proper position, a heat conduction oil circulating pump 8 is started;
step (2), starting a start-up heater 21 and electric tracing bands on the outer walls of the iron-based tubular sections 22, the iron-based heat-insulating sections 23 and the molecular sieve heat-insulating sections 24 of the single-tube reactor 3, heating a heat-conducting oil circulating system, and raising the temperature to a required set temperature;
introducing fresh raw material carbon dioxide with the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
introducing fresh raw material hydrogen at the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
step (5), the raw material hydrogen and the raw material carbon dioxide are subjected to heat exchange and temperature rise through the gas-gas heat exchanger 1 in sequence, the heater 2 is further heated and temperature rise, the temperature of the heated mixed heating gas is 250-450 ℃, and the heat exchange load of the gas-gas heat exchanger 1 is gradually increased in the heating process of the heating gas;
step (6), mixingIntroducing the combined heating gas into the single-tube reactor 3, and sequentially passing through a fixed bed catalyst bed layer of an iron-based tubular section 22, an iron-based heat insulation section 23 and a molecular sieve heat insulation section 24 from top to bottom to perform chemical reaction 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 general reaction equation is as follows: nCO2+(n～6n)H2＝n1CO+n2CH4+(n3C2～n5C4)+(n6C5～n12C11)+n13H2O, the reaction catalyst is an iron-based/molecular sieve (Na-Fe3O4/HZSM-5) multifunctional composite catalyst;
step (7), turning off a start-up heater 21 in the heat conduction oil circulation system, and cutting into a heat conduction oil cooler 9 to control the temperature of the heat conduction oil circulation system and further control the temperature of an iron-based catalyst bed layer in a tube section reaction tube 26 of the single-tube reactor 3;
step (8), the reaction mixed gas is subjected to heat exchange, temperature reduction and condensation through a gas-gas heat exchanger 1 and a cooling condenser 4 from the bottom of the single-tube reactor 3 in sequence to obtain low-temperature mixed gas/liquid after temperature reduction and partial condensation, and the temperature of the low-temperature mixed gas/liquid is-30-10 ℃;
step (9), separating the low-temperature mixed gas/liquid by a gas-liquid separator I5 to obtain gas and liquid, wherein the pressure of the gas-liquid separator I5 is 1.0-6.0 Mpa; one part of the gas is directly recycled, is pressurized by a recycle compressor 7 and then is combined with fresh raw material gas, the temperature of the recycle gas is 0-60 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is depressurized by a pressure reducing valve I14 and then is discharged as one part of tail gas;
step (10), the liquid separated by the gas-liquid separator I5 in the step (9) is regulated and controlled in flow rate by a regulating valve I15, the liquid enters an oil-water separator 6, the pressure of the oil-water separator is 0.5-3.0 MPa, and a small amount of separated gas is reduced in pressure by a pressure reducing valve II 16 and then is discharged as tail gas; the separated liquid crude gasoline and waste water are continuously delivered.
(1) The scheme provides a single-tube test device and a single-tube test method for preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation, wherein the single-tube test device and the single-tube test method are suitable for a reactor filled with two multifunctional composite catalysts, namely an iron-based catalyst and a molecular sieve catalyst, in a layered mode, and the reactor type is suitable for reaction conditions with different reaction thermodynamic properties and optimal reaction temperatures of reaction media in which the two catalysts are positioned;
(2) according to the scheme, most of the iron-based catalyst bed layers with larger reaction heat release are filled above the single-tube reactor in an isothermal tubular fixed bed mode, and a small number of iron-based catalyst bed layers and all molecular sieve catalyst bed layers are sequentially filled at an outlet below the isothermal tubular fixed bed reactor, so that the balance and control between the heat release amount and the heat transfer amount in the iron-based catalyst bed layers are ensured, and the requirement of the condition that the reaction temperature value of the molecular sieve catalyst bed layer with less reaction heat release is higher than the reaction temperature value of the outlet of the isothermal tubular reactor bed is met;
(3) the central reaction bed temperature of the isothermal single-tube reactor is mainly controlled by adjusting the temperature and circulation quantity of heat-conducting oil in the sleeve, corresponding heat calculation can be carried out according to factors such as the specific heat of the heat-conducting oil, the temperature of the heat-conducting oil entering and exiting the sleeve, the flow velocity in the tube, the temperature of a reaction medium entering and exiting the reaction tube in the catalyst bed, the heat transfer area, the material of the reactor and the like, the calculation result can be popularized and applied to the design work of the reactor with a high-pressure steam and a steam pocket on the shell side of an industrial scale, and the difficulty in design and operation of a single-tube test device caused by the fact that the single-tube scale is small and the shell side adopts.
Example 2
In the embodiment, a top gas-phase outlet pipeline of a gas-liquid separator I5 in embodiment 1 is communicated with a hot-side inlet of a chiller 18, a cold-side outlet of the chiller 18 is communicated with an inlet of a gas-liquid separator III 19, and a bottom liquid-phase outlet pipeline of the gas-liquid separator III 19 is communicated with an inlet of an oil-water separator 6 after being regulated and controlled by a regulating valve III 20; the top gas-phase outlet of the gas-liquid separator III 19 is divided into two paths, wherein one path is communicated with the inlet of the circulating compressor 7, and the other path is communicated with the inlet pipeline of the pressure reducing valve I14.
Example 3
In the embodiment, the circulating compressor 7 in the embodiment 2 is arranged on the top gas-phase outlet pipeline of the gas-liquid separator I5, and the outlet pipeline of the circulating compressor 7 is communicated with the hot-side inlet of the chiller 18.
Example 4
A single-tube test method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation comprises the following steps:
step (1), heat conduction oil is sent to an expansion tank 11, when a heat conduction oil circulating system is filled with the heat conduction oil, and meanwhile, the liquid level of the heat conduction oil in the expansion tank 11 is in a proper position, a heat conduction oil circulating pump 8 is started;
step (2), starting a start-up heater 21 and electric tracing bands on the outer walls of the iron-based tubular sections 22, the iron-based heat-insulating sections 23 and the molecular sieve heat-insulating sections 24 of the single-tube reactor 3, heating a heat-conducting oil circulating system, and raising the temperature to a required set temperature;
introducing fresh raw material carbon dioxide with the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
introducing fresh raw material hydrogen at the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
step (5), the raw material hydrogen and the raw material carbon dioxide are subjected to heat exchange and temperature rise through the gas-gas heat exchanger 1 in sequence, the heater 2 is further heated and temperature rise, the temperature of the heated mixed heating gas is 250-450 ℃, and the heat exchange load of the gas-gas heat exchanger 1 is gradually increased in the heating process of the heating gas;
and (6) introducing mixed heating gas into the single-tube reactor 3, and sequentially passing through a fixed bed catalyst bed layer of an iron-based tubular section 22, an iron-based heat insulation section 23 and a molecular sieve heat insulation section 24 from top to bottom to perform chemical reaction 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, the reaction catalyst is an iron-based/molecular sieve (Na-Fe3O4/HZSM-5) multifunctional composite catalyst;
step (7), turning off a start-up heater 21 in the heat conduction oil circulation system, and cutting into a heat conduction oil cooler 9 to control the temperature of the heat conduction oil circulation system and further control the temperature of an iron-based catalyst bed layer in a tube section reaction tube 26 of the single-tube reactor 3;
step (8), the reaction mixed gas is subjected to heat exchange, temperature reduction and condensation through a gas-gas heat exchanger 1 and a cooling condenser 4 from the bottom of the single-tube reactor 3 in sequence to obtain low-temperature mixed gas/liquid after temperature reduction and partial condensation, and the temperature of the low-temperature mixed gas/liquid is-30-10 ℃;
step (9), separating the low-temperature mixed gas/liquid by a gas-liquid separator I5 to obtain gas and liquid, wherein the pressure of the gas-liquid separator I5 is 1.0-6.0 Mpa; one part of the gas is directly recycled, the gas is pressurized by a recycle compressor 7 and then is combined with fresh raw material gas, the temperature of the recycle gas is 0-60 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is decompressed by a decompression valve I14 and then is discharged as one part of tail gas.
The liquid separated by the gas-liquid separator I5 in the step (9) is regulated and controlled in flow rate by a regulating valve I15, the liquid enters an oil-water separator 6, the pressure of the oil-water separator is 0.5-3.0 Mpa, and a small amount of separated gas is reduced in pressure by a pressure reducing valve II 16 and then is discharged as tail gas; the separated liquid crude gasoline and waste water are continuously delivered.
The gas separated by the gas-liquid separator I in the step (9) can also enter a deep cooler 18 for further cooling and condensation, the outlet temperature of the deep cooler 18 is minus 40-5 ℃, the low-temperature mixed gas/liquid at the outlet of the deep cooler 18 is separated by a gas-liquid separator III 19 to obtain gas and liquid, and the pressure of the gas-liquid separator IIII 5 is 1.0-6.0 Mpa; one part of the gas is directly recycled, the gas is pressurized by a recycle compressor 7 and then is combined with fresh raw material gas, the temperature of the recycle gas is-20-50 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is depressurized by a pressure reducing valve I14 and then is discharged as one part of tail gas.
The recycle compressor 7 may also be provided on the conduit between the top gas phase outlet of the gas-liquid separator I5 and the hot side inlet of the chiller 18.
The single-tube test method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation has the beneficial effects that:
(1) the scheme provides a single-tube test device and a single-tube test method for preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation, wherein the single-tube test device and the single-tube test method are suitable for a reactor filled with two multifunctional composite catalysts, namely an iron-based catalyst and a molecular sieve catalyst, in a layered mode, and the reactor type is suitable for reaction conditions with different reaction thermodynamic properties and optimal reaction temperatures of reaction media in which the two catalysts are positioned;
(2) according to the scheme, most of the iron-based catalyst bed layers with larger reaction heat release are filled above the single-tube reactor in an isothermal tubular fixed bed mode, and a small number of iron-based catalyst bed layers and all molecular sieve catalyst bed layers are sequentially filled at an outlet below the isothermal tubular fixed bed reactor, so that the balance and control between the heat release amount and the heat transfer amount in the iron-based catalyst bed layers are ensured, and the requirement of the condition that the reaction temperature value of the molecular sieve catalyst bed layer with less reaction heat release is higher than the reaction temperature value of the outlet of the isothermal tubular reactor bed is met;
(3) the central reaction bed temperature of the isothermal single-tube reactor is mainly controlled by adjusting the temperature and circulation quantity of heat-conducting oil in the sleeve, corresponding heat calculation can be carried out according to factors such as the specific heat of the heat-conducting oil, the temperature of the heat-conducting oil entering and exiting the sleeve, the flow velocity in the tube, the temperature of a reaction medium entering and exiting the reaction tube in the catalyst bed, the heat transfer area, the material of the reactor and the like, the calculation result can be popularized and applied to the design work of the reactor with a high-pressure steam and a steam pocket on the shell side of an industrial scale, and the difficulty in design and operation of a single-tube test device caused by the fact that the single-tube scale is small and the shell side adopts.
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 (9)
1. A single-tube test device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation is characterized in that, the device comprises a gas-gas heat exchanger (1), a heater (2), a single-tube reactor (3), a cooling condenser (4), a gas-liquid separator I (5), an oil-water separator (6), a circulating compressor (7), a heat-conducting oil circulating pump (8), a heat-conducting oil cooler (9), a gas-liquid separator II (10), an expansion tank (11), a raw material hydrogen regulating valve (12), a raw material carbon dioxide regulating valve (13), a pressure reducing valve I (14), a regulating valve I (15), a pressure reducing valve II (16), a regulating valve II (17), a regulating valve III (20), a start-up heater (21), an iron-based row tube section (22), an iron-based heat insulating section (23), a molecular sieve heat insulating section (24), a row tube section shell (25), a row tube section reaction;
an outlet pipeline of a raw material carbon dioxide regulating valve (13) is communicated with a raw material hydrogen pipeline at the outlet of a raw material hydrogen regulating valve (12), the mixed raw material carbon dioxide and raw material hydrogen pipeline is communicated with a cold side inlet pipeline of a gas-gas heat exchanger (1), a hot side outlet pipeline of the gas-gas heat exchanger (1) is communicated with a cold side inlet of a heater (2), a hot side outlet pipeline of the heater (2) is communicated with a top inlet of a single-tube reactor (3), a bottom outlet pipeline of the single-tube reactor (3) is communicated with a hot side inlet of the gas-gas heat exchanger (1), a cold side outlet pipeline of the gas-gas heat exchanger (1) is communicated with a hot side inlet of a cooling condenser (4), a cold side outlet pipeline of the cooling condenser (4) is communicated with an inlet of a gas-liquid separator I (5), and a bottom liquid phase outlet pipeline of the gas-liquid separator, is communicated with the inlet of the oil-water separator (6);
a gas phase outlet at the top of the gas-liquid separator I (5) is divided into two paths, wherein one path is communicated with an inlet of a circulating compressor (7), and an outlet pipeline of the circulating compressor (7) is communicated with a mixed gas pipeline of the raw material carbon dioxide and hydrogen; the other path of the tail gas is communicated with an inlet pipeline of a pressure reducing valve I (14), and an outlet of the pressure reducing valve I (14) is communicated with a tail gas main pipe through a decompressed gas pipeline;
a top gas phase outlet pipeline of the oil-water separator (6) is communicated with an inlet of the pressure reducing valve II (16);
the bottom orifice of the expansion tank (11) is communicated with the top orifice of the gas-liquid separator II (10) through a pipeline; the bottom outlet pipeline of the gas-liquid separator II (10) is communicated with the inlet of the heat conducting oil pump 8; the outlet of the heat-conducting oil pump 8 is divided into two paths, wherein one path is communicated with the inlet of the regulating valve II (17), and the outlet pipeline of the regulating valve II (17) is communicated with the cold side inlet of the start-up heater (21); the other path of the heat conduction oil cooler is communicated with a hot side inlet pipeline of the heat conduction oil cooler (9), and a heat conduction oil outlet pipeline cooled by the heat conduction oil cooler (9) is communicated with an outlet pipeline of the regulating valve II (17); the hot side outlet of the start-up heater (21) is communicated with a heat conduction oil inlet below a shell (25) of the tube section of the single-tube reactor (3); a heat conducting oil outlet pipeline above the tube section shell (25) of the single-tube reactor (3) is communicated with an inlet of the gas-liquid separator II (10).
2. The single-pipe test device for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation according to claim 1, characterized in that the single-pipe reactor (3) is composed of an iron-based row pipe section (22), an iron-based heat-insulating section (23) and a molecular sieve heat-insulating section (24) from top to bottom, and electric tracing bands (27) are wound on the outer walls of the iron-based row pipe section (22), the iron-based heat-insulating section (23) and the molecular sieve heat-insulating section (24).
3. The single-tube test device for directly preparing gasoline fraction hydrocarbon by hydrogenating carbon dioxide according to claim 1, wherein the heater (2) and the start-up heater (21) adopt an electric heating mode or a steam heating mode.
4. The single-pipe test device for directly preparing gasoline fraction hydrocarbon by hydrogenating carbon dioxide according to claim 1, further comprising a chiller 18 and a gas-liquid separator III 19, wherein a top gas-phase outlet pipeline of the gas-liquid separator I (5) is connected with a hot-side inlet of the chiller 18, a cold-side outlet of the chiller 18 is communicated with an inlet of the gas-liquid separator III 19, and a bottom liquid-phase outlet pipeline of the gas-liquid separator III 19 is communicated with an inlet of the oil-water separator (6) after being adjusted and controlled by an adjusting valve III (20); the top gas phase outlet of the gas-liquid separator III 19 is divided into two paths, wherein one path is communicated with the inlet of the circulating compressor (7), and the other path is communicated with the inlet pipeline of the pressure reducing valve I (14).
5. The single-pipe test device for directly preparing gasoline fraction hydrocarbon by hydrogenating carbon dioxide according to claim 1 is characterized by further comprising a chiller 18 and a gas-liquid separator III 19, wherein the recycle compressor (7) is arranged on a top gas-phase outlet pipeline of the gas-liquid separator I (5), an outlet pipeline of the recycle compressor (7) is communicated with a hot-side inlet of the chiller 18, a cold-side outlet of the chiller 18 is communicated with an inlet of the gas-liquid separator III 19, and a bottom liquid-phase outlet pipeline of the gas-liquid separator III 19 is communicated with an inlet of the oil-water separator (6) after being adjusted and controlled by an adjusting valve III (20); the top gas phase outlet of the gas-liquid separator III 19 is divided into two paths, wherein one path is communicated with a mixed gas pipeline of the raw material carbon dioxide and hydrogen, and the other path is communicated with an inlet pipeline of a pressure reducing valve I (14).
6. A single-tube test method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation is characterized by comprising the following steps:
the heat conduction oil is sent to an expansion tank (11), when the heat conduction oil circulating system is filled with the heat conduction oil, and meanwhile, the liquid level of the heat conduction oil in the expansion tank (11) is in a proper position, a heat conduction oil circulating pump (8) is started;
starting a start-up heater (21) and electric tracing bands on the outer walls of the iron-based tubular sections (22), the iron-based heat insulation sections (23) and the molecular sieve heat insulation sections (24) of the single-tube reactor (3), heating a heat conduction oil circulating system, and raising the temperature to a required set temperature;
introducing fresh raw material carbon dioxide with the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
introducing fresh raw material hydrogen at the temperature of 10-50 ℃ and the pressure of 1.5-7.0 Mpa;
the raw material hydrogen and the raw material carbon dioxide are sequentially subjected to heat exchange and temperature rise through the gas-gas heat exchanger (1), the heater (2) is further heated and temperature rise, the temperature of the heated mixed heating gas is 250-450 ℃, and the heat exchange load of the gas-gas heat exchanger (1) is gradually increased in the heating process of the heating gas;
introducing mixed heating gas into the single-tube reactor (3), and sequentially passing through a fixed bed catalyst bed layer of an iron-based tubular section (22), an iron-based heat insulation section (23) and a molecular sieve heat insulation section (24) from top to bottom to perform chemical reaction 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，The reaction catalyst is an iron-based/molecular sieve (Na-Fe3O4/HZSM-5) multifunctional composite catalyst;
the method comprises the following steps of closing an internal working heater (21) of a heat conduction oil circulation system, cutting into a heat conduction oil cooler (9) to control the temperature of the heat conduction oil circulation system and further control the temperature of an iron-based catalyst bed layer in a tube array section reaction tube (26) of a single-tube reactor (3);
the reaction mixed gas is subjected to heat exchange, temperature reduction and condensation sequentially through a gas-gas heat exchanger (1) and a cooling condenser (4) from the bottom of the single-tube reactor (3) to obtain low-temperature mixed gas/liquid after temperature reduction and partial condensation, wherein the temperature of the low-temperature mixed gas/liquid is-30-10 ℃;
separating the low-temperature mixed gas/liquid by a gas-liquid separator I (5) to obtain gas and liquid, wherein the pressure of the gas-liquid separator I (5) is 1.0-6.0 Mpa; one part of the gas is directly recycled, the gas is pressurized by a recycle compressor (7) and then is combined with fresh raw material gas, the temperature of the recycle gas is 0-60 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is decompressed by a decompression valve I (14) and then is discharged as one part of tail gas.
7. The single-tube test method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation according to claim 6, characterized in that liquid separated by a gas-liquid separator I (5) is adjusted by an adjusting valve I (15) to control the flow rate, the liquid enters an oil-water separator (6), the pressure of the oil-water separator is 0.5-3.0 Mpa, and a small amount of separated gas is discharged as tail gas after being decompressed by a decompression valve II (16); the separated liquid crude gasoline and waste water are continuously delivered.
8. The single-tube test method for directly preparing gasoline fraction hydrocarbon by carbon dioxide hydrogenation according to claim 6, characterized in that the gas separated by the gas-liquid separator I enters a deep cooler 18 for further cooling and condensation, the outlet temperature of the deep cooler 18 is-40 to 5 ℃, the low-temperature mixed gas/liquid at the outlet of the deep cooler 18 is separated by a gas-liquid separator III 19 to obtain gas and liquid, and the pressure of the gas-liquid separator IIII 5 is 1.0 to 6.0 MPa; one part of the gas is directly recycled, the gas is pressurized by a recycle compressor (7) and then is combined with fresh raw material gas, the temperature of the recycle gas is-20-50 ℃, the pressure is 1.5-7.0 Mpa, and the other part of the gas is decompressed by a decompression valve I (14) and then is discharged as one part of tail gas.
9. The single-pipe test method for directly preparing gasoline fraction hydrocarbons by hydrogenating carbon dioxide according to claim 6 is characterized in that a recycle compressor (7) is arranged on a pipeline between a top gas-phase outlet of the gas-liquid separator I (5) and a hot-side inlet of the chiller 18.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
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