CN114053745B - Method and device for on-line separation and analysis of Fischer-Tropsch reaction products - Google Patents
Method and device for on-line separation and analysis of Fischer-Tropsch reaction products Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/06—Flash distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/42—Regulation; Control
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- 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
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/34—Apparatus, reactors
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Abstract
The invention relates to the technical field of material separation, in particular to a method and a device for on-line separation and analysis of a Fischer-Tropsch reaction product, wherein the device for on-line separation and analysis of the Fischer-Tropsch reaction product comprises the following components: a flash separation tank in communication with the Fischer-Tropsch reactor for separating the Fischer-Tropsch reaction product into a liquid phase and a gas phase; the gas phase outlet pipeline is arranged at the top of the flash separation tank and is used for leading the gas phase out of the flash separation tank; a second valve disposed on the vapor phase outlet line for regulating the pressure of the flash separation tank; an analysis unit disposed downstream of the second valve for measuring composition in the gas phase; and the liquid phase collecting unit is arranged at the bottom of the flash separation tank and is used for collecting the liquid phase. The device prevents water from entering the gas phase, protects the analysis unit from being influenced by the water, ensures the accuracy of subsequent data analysis and protects the service life of the analysis unit.
Description
Technical Field
The invention relates to the technical field of material separation, in particular to a method and a device for separating and analyzing Fischer-Tropsch reaction products on line.
Background
The Fischer-Tropsch synthesis reaction is a process for converting raw materials such as coal, natural gas, biomass and the like into liquid fuel and high-added-value chemicals through synthesis gas, wherein the raw materials are simple, but the reaction products are complex, the carbon number distribution of organic oxygen-containing compounds such as chain alkane, alkene, alcohol and the like is wider, and the highest carbon number of the products even reaches C 70 -C 120 。
At present, the Fischer-Tropsch reaction product is generally collected by adopting two-stage or even multi-stage cooling to generate wax, oil, water and tail gas, and the following problems are easy to occur: (1) The actual separation effect of each stage is difficult to control by stage-by-stage cooling, and the emulsification and mutual entrainment of water and oil are serious; (2) The products are collected in a grading way, and then the sample treatment of the offline analysis is needed to be separated and mixed again (for example, water and oil in a cold trap and a hot trap are separated and mixed respectively, and then more analysis errors (weighing, volatilization loss and the like) are superposed; (3) The low carbon number and volatile components generate flash evaporation losses with different degrees in the lofting process; (4) Poor separation effect, which causes heavy components to be easily entrained to a subsequent flow path, and then the heavy components are condensed to cause pipeline blockage; (5) After the liquid phase product is collected, the steps of standing, separating, off-line chromatographic analysis and the like are required, so that the manual operation is more, and the error is more; (6) Flash evaporation causes poor visual field near the sampling port, and is difficult to accurately capture the moment when the liquid phase sample is just emptied, thereby causing gas phase components (containing CO and H 2 ) Escape, system pressure fluctuation, air entering the system and other problems, and has great influence on the circulation process; (7) The multi-stage separation results in a higher overall layout, taking up device space.
In the prior art, experimental study of Fischer-Tropsch reaction product distribution (Natural gas chemical industry, C1 chemistry and chemical industry, volume 41 in 2016, pages 15-19), reaction products enter a gas-liquid separator device (similar to a hot trap in a traditional Fischer-Tropsch device) through a reactor outlet, gas phase products after the reaction products are directly decompressed through a back pressure valve and then go to online chromatographic analysis, liquid phase products at the bottom of the separator are collected at fixed time and then are analyzed offline, and a cold trap device in the traditional operation is eliminated; in order to match with high-temperature on-line analysis of Fischer-Tropsch synthesis gas phase products, a high-temperature heating (300 ℃) and tight heat preservation are implemented on a chromatography sample inlet pipeline and components in the process, a high-temperature-resistant back pressure valve is replaced, and an Agilent original chromatographic valve box device is replaced by a self-made independent heating valve box capable of realizing high-temperature heating and heat preservation; in order to ensure that the gas phase components exiting the separator can maintain a gaseous state and enter the gas chromatograph, the device is introduced with high-purity nitrogen as diluent gas (selectively used) after the gas-liquid separator so as to reduce the actual partial pressure of each component. The first-stage cooling collection scheme is designed aiming at Fischer-Tropsch reaction products, but the scheme needs to be provided with a self-made independent heating valve box capable of realizing high-temperature heating and heat preservation, a high-temperature-resistant back pressure valve is replaced, and measures such as high-temperature heating (300 ℃) and tight heat preservation of a chromatogram removing sample inlet pipeline and a component, and high-purity nitrogen gas as diluent gas are introduced after a gas-liquid separator are ensured. The device and the chromatograph are integrally modified more, the implementation is not easy, and the service life of the chromatographic column can be seriously influenced by long-term chromatographic feeding of a large amount of water contained in the product.
Therefore, it is important to develop a method for efficiently and accurately analyzing the Fischer-Tropsch reaction products on line in real time.
Disclosure of Invention
The invention aims to overcome the defects of poor separation effect and high moisture content in gas phase of Fischer-Tropsch reaction products in the prior art, and provides a method and a device for separating and analyzing the Fischer-Tropsch reaction products on line.
The general composition of the fischer-tropsch reaction product is: (1) h 2 、CO、CO 2 、CH 4 Waiting for permanent gas; (2) organic substances such as alkanes, alkenes, and oxygenates; (3) and (3) water. Wherein the boiling point is more than that of the water phase (C 5 ～C 8 Etc.). Gas chromatography can analyze permanent gases and low carbon number organics on line in real time, but cannot feed water in large amounts for a long time (damage to the chromatographic column, unstable and inaccurate analysis results), so it is necessary to collect and analyze water as liquid phase as much as possible. The Fischer-Tropsch reaction products have various components, are comprehensively influenced by various factors such as catalyst performance, reaction conditions, separation system temperature and pressure, and the like, have large variation intervals of composition and partial pressure of each component, and further cause serious emulsification of water and oil of the products and mutual entrainment. The invention intercepts water through the hydrophobic membrane to separate the water from other organic gases, thereby reducing the content of water in the gas phase.
The invention provides an apparatus for on-line separation and analysis of Fischer-Tropsch reaction products, the apparatus comprising:
a flash separation tank in communication with the Fischer-Tropsch reactor for separating the Fischer-Tropsch reaction product into a liquid phase and a gas phase; the flash separation tank is internally further provided with a U-shaped separation unit, and the U-shaped separation unit sequentially comprises the following components from inside to outside: a hydrophobic membrane for intercepting moisture in the Fischer-Tropsch reaction product, a supporting net for fixing the hydrophobic membrane and a liquid blocking grid for foam breaking and flow guiding;
a first valve disposed on a connecting line of the Fischer-Tropsch reactor and the flash separation tank;
the gas phase outlet pipeline is arranged at the top of the flash separation tank and is used for leading the gas phase out of the flash separation tank;
a second valve disposed on the vapor phase outlet line for regulating the pressure of the flash separation tank;
an analysis unit disposed downstream of the second valve for measuring composition in the gas phase;
and the liquid phase collecting unit is arranged at the bottom of the flash separation tank and is used for collecting the liquid phase.
The invention also provides a method for the on-line separation and analysis of a Fischer-Tropsch reaction product, which comprises the on-line separation and analysis of a Fischer-Tropsch reaction product in the device,
the method comprises the following steps: flash separation, water interception, foam breaking and diversion are carried out on the Fischer-Tropsch reaction product at the same time, so that a gas phase and a liquid phase are obtained;
and respectively carrying out composition analysis on the gas phase and the liquid phase.
Through the technical scheme, the U-shaped separation unit is used for preventing water from entering the gas phase, so that the water quantity entering the gas phase is greatly reduced, the analysis unit is protected from being influenced by the water, the high-temperature gas phase can directly enter the analysis unit for real-time analysis, the accuracy of subsequent data analysis is ensured, the service life of the analysis unit is prolonged, and a series of problems such as sample loss, environmental pollution, system pressure fluctuation and the like are avoided.
Drawings
FIG. 1 is a schematic diagram of an apparatus for on-line separation and analysis of Fischer-Tropsch reaction products, provided in accordance with a preferred embodiment of the present invention;
fig. 2 is a schematic structural view of a U-shaped separation unit according to a preferred embodiment of the present invention;
FIG. 3 is a top view of a U-shaped separation unit provided in accordance with a preferred embodiment of the present invention;
FIG. 4 is water and C 5 -C 9 Component temperature versus saturated vapor pressure.
Description of the reference numerals
1. Fischer-Tropsch reactor 2, first valve
3. Flash separation tank 4, gas phase outlet line
5. Analysis unit 6, second valve
7. Pressure interlocking unit 8, U-shaped separating unit
801. Hydrophobic membrane 802, support net
803. Liquid-blocking grille
9. Temperature control unit 10, U-shaped catheter
11. Liquid phase receiver 12, fourth valve
13. Gas collection unit 14, third valve
15. Liquid phase collection tank 16 and temperature control unit
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
FIG. 1 is a schematic diagram of an apparatus for on-line separation and analysis of Fischer-Tropsch reaction products, provided in accordance with a preferred embodiment of the present invention; fig. 2 is a schematic structural view of a U-shaped separation unit according to a preferred embodiment of the present invention; fig. 3 is a top view of a U-shaped separation unit provided in accordance with a preferred embodiment of the present invention.
According to a preferred embodiment of the invention, the apparatus for the on-line separation and analysis of Fischer-Tropsch reaction products according to the invention has the structure shown in FIG. 1, in particular:
a flash separation tank 3 in communication with the Fischer-Tropsch reactor 1 for separating the Fischer-Tropsch reaction product into a liquid phase and a gas phase; the flash separation tank 3 is further internally provided with a U-shaped separation unit 8, and the U-shaped separation unit 8 sequentially comprises from inside to outside: a hydrophobic membrane 801 for trapping moisture in the Fischer-Tropsch reaction product, a support net 802 for fixing the hydrophobic membrane, and a liquid blocking grid 803 for foam breaking and flow guiding;
a first valve 2 arranged on a connecting pipeline of the Fischer-Tropsch reactor 1 and the flash separation tank 3;
a gas phase outlet line 4 arranged at the top of the flash separation tank 3 for leading the gas phase out of the flash separation tank 3;
a second valve 6 provided on the gas phase outlet line 4 for regulating the pressure of the flash separation tank 3;
an analysis unit 5 arranged downstream of the second valve 6 for measuring the composition in the gas phase;
and the liquid phase collecting unit is arranged at the bottom of the flash separation tank 3 and is used for collecting the liquid phase.
The separation principle of the U-shaped separation unit 8 in the invention is as follows: after the Fischer-Tropsch reaction product flows into the flash separation tank 3, part of liquid phase (oil phase and water phase) carried by the gas phase passes through the liquid blocking grid 803 upwards to be broken, so that larger liquid is trapped and guided to drop to the bottom of the flash separation tank 3. Avoiding the problems of blockage caused by heavy components being entrained in the subsequent process and easy coagulation, damage to chromatographic columns caused by a large amount of water entering the subsequent analysis unit, and the like. The gas phase passing through the liquid blocking grating 803 is selectively trapped under the action of the hydrophobic membrane 801, water is gradually guided and dropped to the bottom of the flash separation tank under the action of gravity, and the gas phase passing through the hydrophobic membrane 801 passes through the second valve 6 and reaches the analysis unit 5 for online real-time analysis under the heat tracing and insulation. Through setting up U type separation unit 8 in flash distillation knockout drum 3, can carry out effective separation with liquid phase and the gaseous phase in the Fischer-Tropsch reaction product, prevent that water from getting into the gaseous phase, reduced the smuggleing of water, improved online separation effect, improved the accuracy of follow-up composition analysis simultaneously, can also prevent that water from getting into analysis unit 5, make high temperature gaseous phase can directly get into analysis unit 5 real-time analysis constitution to improve the life-span of analysis unit 5 and the accuracy of analysis, also improved analysis effect and efficiency.
Preferably, the analysis unit 5 is a gas chromatograph.
FIG. 4 is water and C 5 -C 9 As can be seen from FIG. 4, the composition temperature and the saturated vapor pressure of (C) 5 -C 9 Organic gas at low temperature<The saturated vapor pressure at 100 ℃ is relatively close, and the water pressure can be higher than the saturated vapor pressure by adjusting the pressure and the temperature of the flash separation tank. In a preferred embodiment of the present invention, in order to enhance the separation effect of the gas phase and the liquid phase, a first valve 2 is disposed on a pipeline connecting the fischer-tropsch reactor 1 and the flash separation tank 3, and the fischer-tropsch reactor 1 and the flash separation tank 3 can be separated into two independent systems by disposing the first valve 2, so that the pressure and the temperature of the flash separation tank 3 can be flexibly controlled according to the test requirements, and the water content in the gas phase under the condition of meeting the separation requirements (<5 wt%) reduces the pressure of the separation system as much as possible, reduces the gap between the flash separation tank 3 and normal temperature and normal pressure, reduces the phenomena of entrainment, emulsification and the like, can also avoid analysis errors and environmental pollution caused by sampling flash evaporation due to larger pressure difference, reduces the lofting difficulty, reduces lofting loss and improves the accuracy of data.
Preferably, the first valve 2 is a back pressure valve.
In a preferred embodiment of the present invention, in order to facilitate the collection of the liquid phase, it is preferred that the flash separation tank 3 comprises a first cylindrical section and a first conical section arranged below the first cylindrical section, the conical angle of the first conical section (the two end points of the cone apex and a diameter form an isosceles triangle, the apex angle of the isosceles triangle being the cone angle) being further preferably 50-80 ° (for example, any value in the range which may be 50 °, 60 °, 75 °, 80 ° or any two of the above values), most preferably 60 °.
In the invention, in order to further improve the gas-liquid separation effect, it is preferable that the first cylinder section is divided into a cooling section and a heat preservation section, the cooling section is from 1/3 of the upper part of the first cylinder section to the top part of the first cylinder section, and the heat preservation section is from 1/3 of the upper part of the first cylinder section to the bottom part of the first cylinder section. Further, a cooling unit is provided on the cooling section, by which the temperature at the flash separation tank can be controlled within 0-120 ℃, said cooling unit preferably being a circulating water cooling device. The heat preservation section is provided with a heat preservation unit, and the Fischer-Tropsch reaction product can be preserved by arranging the heat preservation unit, so that the temperature of the Fischer-Tropsch reaction product is controlled at 30-180 ℃.
In the present invention, in order to accurately measure the temperatures of the cooling section and the heat-preserving section, it is preferable that temperature sensors are provided on the cooling section and the heat-preserving section, respectively, and more preferable that the temperature sensors are provided at 1/5 and 4/5 of the first straight section (from top to bottom), respectively.
In the present invention, in order to increase the area of the U-shaped separation unit, to extend the gas transmission path and to enhance the gas-liquid separation effect, the aspect ratio of the flash separation tank 3 is preferably 7-9:1, and preferably 8:1.
In a preferred embodiment of the present invention, the hydrophobic membrane 801 can trap moisture in the gas phase and prevent the moisture from entering the gas phase outlet pipeline 4, so as to reduce the moisture content in the gas phase, preferably, the hydrophobic membrane 801 can be made of a membrane material of a temperature and pressure resistant material, and is flexibly selected according to the moisture content in the gas phase and the water removal rate to be achieved, for example, can be inorganic SiO 2 The nanometer fiber film and the base material are Gao Wenshu-resistant water film of modified epoxy resin, etc.
In the present invention, in order to reduce the gas phase transmission resistance and increase the area of the hydrophobic membrane, it is preferable that the hydrophobic membrane 801 includes a second straight cylindrical section and a second tapered section provided below the second straight cylindrical section, and the taper angle of the second tapered section is preferably 50 to 80 ° (for example, may be 50 °, 60 °, 75 °, 80 °, or any value in a range of any two of the above values), and is most preferably 60 °.
According to the invention, by adjusting the intervals of the hydrophobic membrane, the liquid blocking grating and the flash evaporation separation tank, the gas phase can be uniformly distributed, and the diversion of the liquid phase is facilitated. Preferably, the ratio of the inner diameter of the second straight barrel section to the inner diameter of the first straight barrel section is 0.3-0.6:1, for example, can be 0.4:1.
In the present invention, preferably, the ratio of the length of the second straight section to the length of the first straight section is 0.6-0.8:1, for example, may be 0.7:1.
In the invention, the support net 802 can support and fix the hydrophobic membrane 801 so as not to deform and damage; more preferably, the support mesh may be a stainless steel mesh or a ceramic mesh material, and still more preferably, the support mesh 802 may be a single-layer structure or a multi-layer structure, and most preferably, a double-layer structure.
Preferably, when the support net 802 is a multi-layer structure, the spacing between the multi-layer support net can be flexibly adjusted according to the thickness of the hydrophobic film and the spacing between the hydrophobic film and the liquid-blocking grille.
In order to further improve the gas-liquid separation effect, it is preferable that a foam breaking unit, preferably a fibrous barb, is disposed on a side of the support net 802 adjacent to the liquid-blocking grille 803; the length of the fibrous barbs is preferably 0.3-0.8cm (for example, the fibrous barbs can be 0.3cm, 0.5cm, 0.6cm, 0.8cm or any value in a range formed by any two of the above values), and most preferably 0.5cm, and the fibrous barbs can not only break foam, but also play a role in guiding flow.
In the invention, the liquid-blocking grating 803 has foam breaking and flow guiding functions and can be hydrophobic membrane dispersion resistance, so that the gas-liquid separation effect is improved, and the liquid-blocking grating 803 is preferably made of stainless steel mesh or ceramic and other materials.
In order to further improve the foam breaking, flow guiding and air speed reducing effects of the liquid blocking grating 803, it is preferable that the inner side and/or the outer side of the liquid blocking grating 803 is provided with flow guiding grooves, preferably a plurality of spiral flow guiding grooves forming a downward included angle, and more preferably, the downward included angle formed by the plurality of spiral flow guiding grooves is 30 °.
According to the invention, the gas phase contacts the liquid-blocking grille in a more uniform plug flow mode by adjusting the distance between the liquid-blocking grille and the inner wall of the flash tank, so that the gas phase transmission resistance is reduced. Preferably, the ratio of the inner diameter of the liquid-blocking grating 803 to the inner diameter of the first barrel section is 0.4-0.8:1, most preferably 0.6:1.
In a preferred embodiment of the invention, the gas phase outlet line 4 is further provided with:
a pressure interlocking unit 7 connected with the second valve 6 and used for starting to adjust the opening degree of the second valve 6;
and the controller is connected with the pressure interlocking device 7 and the analysis unit 5 and is used for controlling the pressure interlocking device 7 based on the measurement result of the analysis unit 5.
In the present invention, the pressure interlocking unit 7 may be an existing pressure interlocking structure, including but not limited to a pneumatic adjusting valve, a stepping motor, etc., which are known to those skilled in the art.
In a preferred embodiment of the present invention, the liquid phase collection unit comprises: a liquid phase collection tank 15, which is communicated with the flash separation tank 3, and is used for collecting the liquid phase flowing out from the bottom of the flash separation tank 3. All liquid phases are collected in the same tank body, so that all phase products are mixed more uniformly, and the losses and errors caused by respectively mixing cold trap water and hot trap oil (wax) and separating water phase from oil phase by off-line of a cold trap and a hot trap sample are reduced.
In the present invention, preferably, a temperature control unit 16 is disposed in the liquid phase collecting tank 15, and is used for maintaining the temperature of the liquid phase, so that the liquid phase in the liquid phase collecting tank 15 can maintain the lowest temperature that can flow, where the temperature control unit 16 may be set according to practical situations, and may be, for example, a heating device or a refrigerating device.
In the present invention, the height-to-diameter ratio of the liquid phase collection tank 15 is preferably 1:1 to 3, and most preferably 1:2. By controlling the height-to-diameter ratio of the liquid phase collection tank 15, on one hand, the bottom area of the liquid phase collection tank 15 can be increased, which is beneficial to heating the heavy components deposited at the bottom of the liquid phase collection tank 15; on the other hand, the overall height of the device can be reduced, and the height of the flash separation tank can be increased as much as possible under the condition that the overall height of the device is unchanged, so that the flash separation effect is improved.
In a preferred embodiment of the present invention, in order to avoid the problems of uneven components, environmental damage, system pressure fluctuation, etc. caused by easy flash evaporation of light components, easy coagulation and easy blockage of heavy components in the lofting process, the liquid phase collecting unit further comprises:
the liquid phase receiver 11 is communicated with the liquid phase collecting tank 15 through a U-shaped conduit 10. Since the pressure of the liquid phase collection tank 15 is greater than that of the liquid phase receiver 11, the liquid phase in the liquid phase collection tank 15 can enter the liquid phase receiver 11 by siphoning after the two are connected by the U-shaped conduit 10.
Preferably, a third valve 14 is arranged on a pipeline connecting the flash separation tank 3 and the liquid phase collection tank 15, and a fourth valve 12 is arranged on the U-shaped conduit 10. During the test, the third valve 14 is normally open; when the liquid phase needs to be analyzed in real time, the third valve 14 is closed, the fourth valve 12 is opened, the pressure of the liquid phase collecting tank 15 is higher than that of the liquid phase receiver 11, the liquid phase automatically flows into the liquid phase receiver through the U-shaped conduit 10, and the purpose of rapid and accurate analysis can be achieved by analyzing the components of the liquid in the liquid phase receiver 11.
Preferably, a blind hole is formed in the bottom of the liquid phase collection tank 15, and one end of the U-shaped conduit 10 is disposed in the blind hole; thereby ensuring that the liquid phase in the liquid phase collection tank 15 is completely sucked into the liquid phase receiver 11 under the siphon action. Preferably, the diameter of the blind hole is 1cm, and the depth is 0.5cm.
Preferably, a gas collecting unit 13 is disposed at the top of the liquid phase receiver 11, and the gas collecting unit 13 may collect the gas generated by the flash evaporation. More preferably, the gas collecting unit 13 is a gas pump, which can collect gas and generate negative pressure for the liquid phase receiver 11, so as to increase the pressure difference between the liquid phase collecting tank 15 and the liquid phase receiver 11.
In a specific embodiment of the present invention, in order to facilitate the observation of whether the liquid extraction is completed, the liquid phase receiver 11 is a glass bottle, and the end of the U-shaped conduit 10 disposed in the liquid phase receiver 11 is connected to a transparent quartz glass tube.
The invention also provides a method for the on-line separation and analysis of a Fischer-Tropsch reaction product, which method comprises the on-line separation and analysis of a Fischer-Tropsch reaction product in said apparatus,
the method comprises the following steps: the Fischer-Tropsch reaction product flows out of the reactor and enters a flash separation tank 3 through a first valve 2, and flash separation, water interception, foam breaking and flow guiding are carried out when the Fischer-Tropsch reaction product passes through a U-shaped separation unit 8, so that a gas phase and a liquid phase are obtained;
the gas phase flows out through the gas phase outlet pipeline 4, enters the analysis unit 5 through the second valve 6, and is subjected to composition analysis in the analysis unit 5;
the liquid phase flows out from the bottom of the flash separation tank 3 and enters a liquid phase collecting unit for composition analysis.
Preferably, the flash separation, water interception, foam breaking and diversion temperatures are from 0 to 180 ℃, and the pressures are from 0.1 to 5MPa, more preferably from 0.1 to 2MPa.
In a preferred embodiment of the invention, the method further comprises: measuring the water content in the gas phase, and increasing the pressure of the flash separation, water interception, foam breaking and diversion when the water content in the gas phase is higher than a predetermined value; the predetermined value is 5wt%;
preferably, the temperature of the gas phase is 20-100 ℃.
In a preferred embodiment of the present invention, when it is desired to analyze the composition of the liquid phase, the third valve 14 is first closed and the fourth valve 12 is opened, and at this time, the pressure in the liquid phase collection tank 15 is higher than that in the liquid phase receiver 11, and the liquid phase automatically flows into the liquid phase receiver 11 through the U-shaped conduit 10. Preferably, the temperature of the liquid phase is 20-60 ℃.
The present invention will be described in detail by examples.
Example 1
The apparatus for on-line separation and analysis of Fischer-Tropsch reaction products used in this example is shown in FIG. 1, and the structure of the U-shaped separation unit is shown in FIGS. 2 and 3.
The Fischer-Tropsch reaction product flows out of the reactor, flows into a flash separation tank through a backpressure valve, and after flowing into the flash separation tank, the gas phase sequentially passes through a liquid blocking grid, a hydrophobic membrane supporting net and a hydrophobic membrane to be subjected to flash separation, water interception, foam breaking and flow guiding at the same time, and the gas phase and the liquid phase are separated;
the gas phase passes through a hydrophobic membrane and then passes through a second valve, and is sent to gas chromatography for real-time analysis at 60 ℃ with heat preservation; the analysis unit on the gas phase outlet pipeline analyzes the water content of the gas phase at any time, and if the water content is higher than 5wt%, the opening of the second valve is pneumatically regulated through the pressure interlocking unit, so that the pressure of the flash separation tank is increased by 0.1MPa;
the liquid phase (water-oil mixture) enters the liquid phase collection tank from the bottom third valve (normally open at non-sampling) of the flash separation tank. When the liquid phase sample is collected, the third valve is closed, the fourth valve is opened, and the liquid phase automatically flows into the liquid phase receiver through the U-shaped conduit.
The parameters of the apparatus for on-line separation and analysis of Fischer-Tropsch reaction products in this example are as follows:
the height-diameter ratio of the flash separation tank is 8:1, and the taper angle of the taper part at the bottom of the flash separation tank is 60 degrees;
the diameter of the hydrophobic membrane is 1/3 of the diameter of the straight barrel section of the flash separation tank, the length of the hydrophobic membrane is 70% of the straight barrel section of the flash separation tank, and the included angle of the conical part is 60 degrees;
the supporting net adopts a double-layer stainless steel net to support and fix the hydrophobic film, fibrous barbs are arranged on the outer layer stainless steel net (the side close to the liquid blocking grid) at intervals of 1cm for assisting in foam breaking and flow guiding, and the length of the barbs is 0.5cm;
the liquid-blocking grille is made of stainless steel, the diameter of the liquid-blocking grille is 1/2 of that of the flash evaporation separation tank, and the inner side and the outer side of the grille are respectively provided with a plurality of spiral diversion trenches forming a downward included angle of 30 degrees;
the height-diameter ratio of the liquid phase collection tank is 1:2, the diameter of the blind hole at the bottom is 1cm, and the depth is 0.5cm.
The specific process conditions and separation results in this example are shown in table 1.
Comparative example 1
The procedure of example 1 was followed except that the apparatus for on-line separation and analysis of Fischer-Tropsch reaction products did not include a U-type separation unit, and the specific separation results are shown in Table 2.
Example 2
The specific process conditions and isolation results are shown in Table 1, following the procedure of example 1.
Comparative example 2
The procedure of example 2 was followed except that the apparatus for on-line separation and analysis of Fischer-Tropsch reaction products did not include a U-type separation unit, and the specific separation results are shown in Table 2.
Example 3
The specific process conditions and isolation results are shown in Table 1, following the procedure of example 1.
Comparative example 3
The procedure of example 3 was followed except that the apparatus for on-line separation and analysis of Fischer-Tropsch reaction products did not include a U-type separation unit, and the specific separation results are shown in Table 2.
TABLE 1 separation conditions and results for Fischer-Tropsch reaction products of examples 1-3
TABLE 2 separation conditions and results for Fischer-Tropsch reaction products of comparative examples 1-3
Example 4
The procedure of example 1 was followed except that the apparatus for on-line separation and analysis of the Fischer-Tropsch reaction product did not include a liquid phase receiver, and the specific separation results are shown in Table 3.
Comparative example 4
The procedure of example 1 was followed except that the first valve was not included in the apparatus for on-line separation and analysis of the Fischer-Tropsch reaction product, and the specific separation results are shown in Table 3.
Comparative example 5
The procedure of example 1 was followed except that the apparatus for on-line separation and analysis of Fischer-Tropsch reaction products did not include a U-shaped separation unit, a first valve and a liquid phase receiver, and the specific separation results are shown in Table 3.
TABLE 3 separation conditions and results of Fischer-Tropsch reaction products in example 4 and comparative examples 4-5
In tables 1 to 3, T 1 T is the temperature of 1/4 of the upper part of the first straight barrel section of the flash separation tank 2 T is the temperature at which the gas phase enters the analysis unit 3 For the temperature of the liquid phase in the liquid phase collection tank, P is the pressure of the flash separation tank.
As can be seen from the data in tables 1-3: the device provided by the invention can ensure that water is trapped in the liquid phase as much as possible, and the highest water content in the gas phase can reach 99.21 percent, so that the water content in the gas phase is very low, and the lowest water content is 0.79 percent, and therefore, the gas phase can be directly analyzed on line by adopting a gas chromatograph for a long time.
As can be seen from the data in table 4: the device provided by the invention improves the yield of the oil phase and the water phase in the liquid phase, reduces the loss of the sample, and improves the analysis accuracy;
TABLE 4 liquid phase yields in examples 1-4 and comparative examples 1-5
* Based on 100% of the mass of the liquid phase sample actually received in example 1; oil phase yield according to C 5+ The above calculation (C in gas phase 5+ The components are already accounted for).
The water content in the gas phase and the light component content in the liquid phase are obviously reduced after the U-shaped separation unit is arranged, the multiphase separation effect is obviously improved, and the problems of water-oil emulsification and mutual entrainment are avoided.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (18)
1. An apparatus for on-line separation and analysis of fischer-tropsch reaction products, the apparatus comprising:
a flash separation tank (3) in communication with the Fischer-Tropsch reactor (1) for separating the Fischer-Tropsch reaction product into a liquid phase and a gas phase; wherein, further be provided with U type separation unit (8) in flash distillation knockout drum (3), U type separation unit (8) are from interior to exterior includes in proper order: a hydrophobic membrane (801) for trapping moisture in the Fischer-Tropsch reaction product, a support net (802) for fixing the hydrophobic membrane, and a liquid blocking grid (803) for foam breaking and flow guiding;
a first valve (2) arranged on a connecting pipeline of the Fischer-Tropsch reactor (1) and the flash separation tank (3);
a gas phase outlet line (4) arranged at the top of the flash separation tank (3) for leading the gas phase out of the flash separation tank (3);
a second valve (6) arranged on the gas phase outlet line (4) for regulating the pressure of the flash separation tank (3);
an analysis unit (5) arranged downstream of the second valve (6) for measuring the composition in the gas phase; and
the liquid phase collecting unit is arranged at the bottom of the flash separation tank (3) and is used for collecting the liquid phase;
wherein the height-to-diameter ratio of the flash separation tank (3) is 7-9:1; the flash separation tank (3) comprises a first straight cylinder section and a first conical section arranged below the first straight cylinder section, the conical angle of the first conical section is 50-80 degrees, the hydrophobic membrane (801) comprises a second straight cylinder section and a second conical section arranged below the second straight cylinder section, and the conical angle of the second conical section is 50-80 degrees; the ratio of the inner diameter of the second straight cylinder section to the inner diameter of the first straight cylinder section is 0.3-0.6:1, the ratio of the length of the second straight cylinder section to the length of the first straight cylinder section is 0.6-0.8:1, and the ratio of the inner diameter of the liquid blocking grid (803) to the inner diameter of the first straight cylinder section is 0.4-0.8:1.
2. The device according to claim 1, wherein a cooling unit is arranged from the upper part 1/3 of the first straight cylinder section to the top part of the first straight cylinder section, and the cooling unit is a circulating water cooling device; and/or a heat preservation unit is arranged from 1/3 of the upper part of the first straight barrel section to the bottom part of the first straight barrel section.
3. The device according to claim 2, wherein the support net (802) is provided with foam breaking units, which are fibrous barbs.
4. A device according to claim 3, wherein the fibrous barbs have a length of 0.3-0.8cm.
5. The device according to claim 4, wherein the liquid-blocking grille (803) is provided on the inside and/or outside with flow-guiding grooves.
6. The apparatus of claim 5, wherein the flow guide grooves are a plurality of spiral flow guide grooves forming a downward angle.
7. The apparatus according to any one of claims 1 to 6, wherein the gas phase outlet line (4) is further provided with:
a pressure interlocking unit (7) connected with the second valve (6) and used for starting to adjust the opening degree of the second valve (6);
and the controller is connected with the pressure interlocking device (7) and the analysis unit (5) and is used for controlling the pressure interlocking device (7) based on the measurement result of the analysis unit (5).
8. The apparatus of any one of claims 1-6, wherein the liquid phase collection unit comprises:
and a liquid phase collection tank (15) communicated with the flash separation tank (3) and used for collecting liquid phase flowing out from the bottom of the flash separation tank (3).
9. The device according to claim 8, wherein a temperature control unit (16) is arranged in the liquid phase collection tank (15) for maintaining the temperature of the liquid phase;
and/or the height-to-diameter ratio of the liquid phase collection tank (15) is 1:1-3.
10. The apparatus of claim 8, wherein the liquid phase collection unit further comprises:
a liquid phase receiver (11) is communicated with the liquid phase collecting tank (15) through a U-shaped conduit (10).
11. The device according to claim 10, wherein the bottom of the liquid phase collection tank (15) is provided with a blind hole, one end of the U-shaped conduit (10) being arranged inside the blind hole; and/or the top of the liquid phase receiver (11) is provided with a gas collecting unit (13).
12. The apparatus of claim 9, wherein the liquid phase collection unit further comprises:
a liquid phase receiver (11) is communicated with the liquid phase collecting tank (15) through a U-shaped conduit (10).
13. The device according to claim 12, wherein the bottom of the liquid phase collection tank (15) is provided with a blind hole, one end of the U-shaped conduit (10) being arranged inside the blind hole; and/or the top of the liquid phase receiver (11) is provided with a gas collecting unit (13).
14. The apparatus according to any of the claims 10-13, wherein a third valve (14) is provided in the line connecting the flash separation tank (3) and the liquid phase collection tank (15); and/or
A fourth valve (12) is arranged on the U-shaped conduit (10).
15. A process for the on-line separation and analysis of Fischer-Tropsch reaction products, characterized in that it comprises the on-line separation and analysis of Fischer-Tropsch reaction products in an apparatus according to any one of claims 1 to 14,
the method comprises the following steps: flash separation, water interception, foam breaking and diversion are carried out on the Fischer-Tropsch reaction product at the same time, so that a gas phase and a liquid phase are obtained;
and respectively carrying out composition analysis on the gas phase and the liquid phase.
16. The process of claim 15, wherein the flash separation, water interception, foam breaking and diversion temperatures are from 0 to 180 ℃ and pressures are from 0.1 to 5MPa.
17. The method according to claim 15 or 16, wherein the method further comprises: measuring the water content in the gas phase, and increasing the pressure of the flash separation, water interception, foam breaking and diversion when the water content in the gas phase is higher than a predetermined value;
and/or the temperature of the gas phase is 20-100 ℃.
18. A process according to claim 15 or 16, wherein the temperature of the liquid phase is 20-60 ℃.
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| CN205027709U (en) * | 2015-06-01 | 2016-02-10 | 中国石油天然气股份有限公司 | ONLINE CHROMATOGRAM sampling device |
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| CN109806673A (en) * | 2019-03-06 | 2019-05-28 | 中国石油大学(北京) | A kind of gas-liquid separation device for gas defoaming |
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