CN108067167B - Slurry bed reaction system and Fischer-Tropsch synthesis reaction method - Google Patents
Slurry bed reaction system and Fischer-Tropsch synthesis reaction method Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/20—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium
- B01J8/22—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles with liquid as a fluidising medium gas being introduced into the liquid
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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
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
- B01J2208/00008—Controlling the process
- B01J2208/00017—Controlling the temperature
- B01J2208/00106—Controlling the temperature by indirect heat exchange
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Abstract
The invention relates to the field of Fischer-Tropsch synthesis, and particularly provides a slurry bed reaction system and a method, wherein the system comprises: the system comprises a slurry bed reactor, an internal heat exchange unit and an external heat exchange unit, wherein the external heat exchange unit comprises a steam drum and a heater which are sequentially connected in series, the heater is communicated with a water inlet at the lower part of the internal heat exchange unit, and the steam drum is communicated with a water outlet at the upper part of the internal heat exchange unit; the internal heat exchange unit comprises heat exchange tubes, and baffles are arranged in part or all of the heat exchange tubes and used for prolonging the retention time of heat exchange media in the internal heat exchange unit. The system of the invention can not only improve the heat exchange efficiency of the heat exchange unit in the reactor and ensure the uniform and stable temperature in the slurry bed reactor, but also timely and effectively remove the redundant heat brought by temperature runaway when the local temperature runaway of the catalyst occurs, thereby ensuring the yield of the target product and improving the operation safety of the device.
Description
Technical Field
The invention relates to the field of Fischer-Tropsch synthesis, in particular to a slurry bed reaction system and a Fischer-Tropsch synthesis reaction method.
Background
With the rising of the price of petroleum in recent years, people pay more and more attention to the development of a technology for producing alternative oil products, synthesis gas is produced by coal, natural gas or other substances, the synthesis gas is treated by water gas shift and synthesis gas purification processes according to the requirement of a Fischer-Tropsch synthesis catalyst on the synthesis gas, hydrocarbons are produced by Fischer-Tropsch synthesis by taking the treated synthesis gas as a raw material, meanwhile, oxygen-containing compounds are byproduct, and then the oil products are processed by adopting a mature petroleum processing technology to produce high-quality environment-friendly oil products. The development of the Fischer-Tropsch synthesis technology has very important significance for developing the production technology for replacing oil products.
The Fischer-Tropsch reaction is a strongly exothermic reaction. The distribution of the products of the Fischer-Tropsch synthesis and the activity of the catalyst are very sensitive to the temperature, and the maintenance of a relatively constant temperature in the reactor is very important for the smooth proceeding and safe operation of the reaction in the slurry bed reactor. Therefore, when the Fischer-Tropsch synthesis reaction is carried out, the heat in the slurry bed reactor needs to be uniformly and quickly removed out of the reactor.
In addition, local overheating and temperature runaway of the catalyst often occur in the Fischer-Tropsch synthesis reaction, and carbon deposition of the catalyst is caused and even deposited in a reactor, so that the catalyst is quickly deactivated, the yield of a target product is reduced, and the like. Therefore, in the Fischer-Tropsch synthesis reaction process, the design of the heat exchanger needs to consider not only that the heat in the reactor is uniformly and quickly removed out of the reactor, but also that enough measures and methods can be provided when the catalyst is locally overheated and subjected to temperature runaway, so that more heat caused by temperature runaway can be timely and effectively removed, the operation safety of the reactor is ensured, and the yield of a target product is improved.
In the prior art, the design of the heat exchanger mainly focuses on improving the structural design of the heat exchanger and improving the heat exchange efficiency.
CN101480595A discloses a pin fin type heat exchanger, the outer wall of heat exchange tubulation is installed horizontal pin fin, the pin fin number of installing on each heat exchange tubulation is 80 ~ 800, pin fin diameter is 1 ~ 10mm, length is in the range of 10 ~ 125 mm. The pin fin heat exchanger tube not only increases the heat exchange area, but also improves the flow velocity distribution of gas phase, liquid phase and solid phase in the slurry bed, and realizes the double functions of strengthening heat transfer and improving flow.
CN102212381A discloses an equipment system for Fischer-Tropsch synthesis reaction, which comprises a three-phase suspension bed Fischer-Tropsch synthesis reactor and a matched system thereof, wherein the three-phase suspension bed Fischer-Tropsch synthesis reactor is provided with a chilling distributor for injecting condensation products circulated back to the reactor and carrying out enhanced heat transfer on a filter area of the reactor; in addition, the system is also provided with a waste heat boiler, so that a hot gas stream of a high-temperature light reaction product discharged from the outlet of the reactor is subjected to heat exchange through the waste heat boiler firstly, partial heat is recovered, a small amount of solid catalyst carried in the gas stream can be removed, and the downstream condensation product is ensured to contain no catalyst.
CN101396647A discloses a novel heat exchanger suitable for a slurry bed reactor, wherein the heat exchanger part can adopt a one-section main heat exchanger or a two-section main heat exchanger. Because a larger space exists between the separation area components, a small heat exchanger element group can be arranged outside the upper main heat exchanger according to production requirements, and the function of adjusting the temperature of the space occupied by the liquid-solid separation area is achieved. The honeycomb duct is added in the heat exchanger, so that the thermal coupling of the upper and lower sections of heat exchangers is realized, the thermal load difference between the two sections is reduced, and the operation elasticity is increased, so that the heat exchange temperature can ensure the full reaction in the slurry bed reactor.
US4187902 discloses a heat exchanger for exchanging heat with a high-pressure cooling medium, which is mainly characterized in that a heat exchange tube array is long and is in a folded and bent shape, so that the heat exchange tube array plays a role in heat compensation in the heat exchange process, the heat exchange tube array can vibrate along with gas-liquid movement during heat exchange, and the deposition of precipitates on the tube array can be reduced by utilizing the vibration effect of the bent tube array to prevent the tube array from scaling, so that the heat exchange effect is improved. The size of the heat exchange tube array is not limited by the size of the reactor, any number of heat exchange tube arrays can be installed in the reactor according to production requirements, and then the size of the reactor body is determined according to the size of the heat exchanger.
CN101480595A discloses a pin fin type heat exchanger, which is mainly characterized in that a large number of horizontal pin fins are installed on the outer wall of a heat exchange tube array. The pin fin heat exchanger tube array can increase the heat exchange area and enhance the heat exchange capacity of the reactor; on the other hand, the pin fins on the outer wall of the heat exchange tubes can block the flow of gas-liquid phase fluid in the tower, inhibit the flow steepness effect (chimney effect) caused by common heat exchange tubes and improve the flow velocity distribution in the slurry bed.
However, the pin fin type heat exchanger has the characteristic of complex manufacture, and along with the increase of the size of the reactor, the length and the number of the pin fins on the tubes are increased, so that the production and manufacture difficulty is increased on the premise of ensuring the heat exchange effect, and meanwhile, the proportion of the cross section area of the heat exchange tubes to the cross section area of the reactor is increased, the distribution of fluid in the reactor is influenced, and the yield of a target product is reduced.
In addition, the Fischer-Tropsch reaction is a strong exothermic reaction, and once the Fischer-Tropsch synthesis reactor generates a temperature runaway phenomenon, the heat exchanger does not have a measure for quickly removing the redundant heat in time, and can cause test failure in severe cases.
Disclosure of Invention
The invention aims to provide a heat exchange system and a method suitable for Fischer-Tropsch synthesis slurry bed reaction, which can improve the heat exchange efficiency of a heat exchange unit in a slurry bed reactor, ensure the uniform and stable temperature in the slurry bed reactor, and can timely and effectively remove the redundant heat caused by temperature runaway when the local temperature runaway of a catalyst occurs, thereby ensuring the yield of a target product and improving the operation safety of the device.
To achieve the foregoing object, according to a first aspect of the present invention, there is provided a slurry bed reaction system comprising: the system comprises a slurry bed reactor, an internal heat exchange unit and an external heat exchange unit, wherein the internal heat exchange unit is arranged inside the slurry bed reactor, the external heat exchange unit is arranged outside the slurry bed reactor, the external heat exchange unit comprises a steam pocket and a heater which are sequentially connected in series, the heater is communicated with a water inlet at the lower part of the internal heat exchange unit, and the steam pocket is communicated with a water outlet at the upper part of the internal heat exchange unit; the internal heat exchange unit comprises heat exchange tubes, and baffles are arranged in part or all of the heat exchange tubes and used for prolonging the retention time of heat exchange media in the internal heat exchange unit.
According to a second aspect of the invention, there is provided a method of performing a fischer-tropsch synthesis reaction using a slurry bed reaction system according to the invention, the method comprising: water from the steam drum enters the internal heat exchange unit through the heater to exchange heat with the materials in the slurry bed reactor, the water after heat exchange enters the steam drum to be subjected to gas-liquid separation, and the separated water returns to the heater;
in the initial stage of the Fischer-Tropsch synthesis reaction, the heater heats water from a steam drum, and the heated hot water is used for heating materials in the slurry bed reactor until the materials in the slurry bed reactor reach the reaction temperature;
and after the materials in the slurry bed reactor reach the reaction temperature, the heater stops heating, so that water from the steam drum directly flows through the heater to enter the internal heat exchange unit for removing the heat of the materials in the slurry bed reactor.
According to the slurry bed reaction system, the external heat exchange unit is matched with the internal heat exchange unit, so that the heat exchange efficiency of the heat exchange unit in the slurry bed reactor can be improved, the uniform and stable temperature in the slurry bed reactor can be ensured, and the redundant heat caused by temperature runaway can be timely and effectively removed when the local temperature runaway of the catalyst occurs, so that the yield of a target product is ensured, and the operation safety of the device is improved. Thereby making the invention very suitable for industrial applications.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a slurry bed reaction system according to a preferred embodiment of the present invention;
FIG. 2 is a schematic structural view of a heat exchange tube according to a preferred embodiment of the present invention;
fig. 3 is a schematic structural view of a heat exchange tube according to a preferred embodiment of the present invention.
Description of the reference numerals
1: a slurry bed reactor; 2: a lower heat exchange unit;
3: a middle heat exchange unit; 4: an upper heat exchange unit;
5: a steam drum; 6: heating device
7: a pump; 8: pressure control valve
9: a water replenishing pipeline; 10: a pump;
11: a pipeline; 12: a pipeline;
13: a pipeline; 14: a pipeline;
15: a pipeline; 16: a valve;
17: and (4) a valve.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
As shown in fig. 1, the present invention provides a slurry bed reaction system comprising: the system comprises a slurry bed reactor 1, an internal heat exchange unit and an external heat exchange unit, wherein the internal heat exchange unit is arranged inside the slurry bed reactor 1, the external heat exchange unit is arranged outside the slurry bed reactor 1, the external heat exchange unit comprises a steam pocket 5 and a heater 6 which are sequentially connected in series, the heater 6 is communicated with a water inlet at the lower part of the internal heat exchange unit, and the steam pocket 5 is communicated with a water outlet at the upper part of the internal heat exchange unit; the internal heat exchange unit comprises heat exchange tubes, and baffles are arranged in part or all of the heat exchange tubes and used for prolonging the retention time of heat exchange media in the internal heat exchange unit.
According to the invention, in the specific operation process, water from the heater is pumped into the internal heat exchange unit in the slurry bed reactor through the pump, exchanges heat with slurry in the slurry bed reactor, and then returns to the steam pocket, after gas-liquid separation is carried out in the steam pocket, a water phase enters the heater for heating, then is pumped into the internal heat exchange unit through the pump, and returns to the steam pocket after heat exchange, and a standby pump can be started to forcibly accelerate and circulate back to the steam pocket according to the requirement, and the detailed description is carried out subsequently.
In the specific operation process, when the temperature in the slurry bed reactor reaches the reaction temperature, the heat release of the Fischer-Tropsch synthesis reaction tends to be stable, and after the water in the heat exchange tube absorbs the heat, part of the water is changed into water vapor, and then the water vapor returns to the steam pocket for gas-liquid separation.
According to a preferred embodiment of the present invention, baffles are provided in 20 to 70% of the heat exchange tubes of the internal heat exchange unit.
According to a preferred embodiment of the present invention, the internal heat exchange unit comprises a lower heat exchange unit 2, a middle heat exchange unit 3 and an upper heat exchange unit 4 which are arranged inside the slurry bed reactor 1;
the lower heat exchange unit 2, the middle heat exchange unit 3 and the upper heat exchange unit 4 respectively comprise a plurality of heat exchange tubes connected in parallel, and baffles are respectively arranged in part or all of the heat exchange tubes of the lower heat exchange unit 2 and the middle heat exchange unit 3 and used for prolonging the retention time of a heat exchange medium in the inner heat exchange units;
the lower heat exchange unit 2, the middle heat exchange unit 3 and the upper heat exchange unit 4 are connected in series and/or in parallel with each other with respect to the heater (6).
By adopting the arrangement, the system can ensure uniform and stable temperature in the slurry bed reactor, and can effectively remove redundant heat brought by temperature runaway in time when local temperature runaway of the catalyst occurs, so that the yield of a target product is ensured, and the operation safety of the device is improved.
According to the present invention, it is preferable that baffles are provided in 10 to 70%, preferably 20 to 50%, of the heat exchange tubes of the lower heat exchange unit 2. So set up, can realize guaranteeing the inside even stable temperature of slurry bed reactor and shift out the maximize cooperation of the unnecessary heat that the temperature runaway brought effectively.
According to a preferred embodiment of the invention, the cross-sectional area of each of said baffles cannot exceed 80%, preferably 70%, of the cross-sectional area inside the heat exchange tubes. So set up, can realize guaranteeing the inside even stable temperature of slurry bed reactor and shift out the maximize cooperation of the unnecessary heat that the temperature runaway brought effectively.
According to the invention, the baffle is used for reducing the speed of water flow in the heat exchange pipe, absorbing more heat and forcibly reducing the water temperature in the internal heat exchange unit, thereby preventing the occurrence of local temperature runaway in the slurry bed reactor.
According to the invention, the invention has no special requirements on the form of the heat exchange tube, and can be a suspended tube type heat exchange tube.
According to a preferred embodiment of the present invention, the diameter of the heat exchange tubes in the lower heat exchange unit 2 is smaller than the diameter of the heat exchange tubes in the middle heat exchange unit 3 and the upper heat exchange unit 4, and the number of the heat exchange tubes in the lower heat exchange unit 2 is greater than the number of the heat exchange tubes in the middle heat exchange unit 3 and the upper heat exchange unit 4. Therefore, the occurrence of local temperature runaway inside the slurry bed reactor can be more effectively prevented.
According to a preferred embodiment of the present invention, the diameter of the heat exchange tubes in the lower heat exchange unit 2 is 2-50mm smaller than the diameter of the heat exchange tubes in the middle heat exchange unit 3 and the upper heat exchange unit 4, respectively;
the diameter of the heat exchange tube in the lower heat exchange unit 2 is 10-200 mm; the diameters of the heat exchange tubes in the middle heat exchange unit 3 and the upper heat exchange unit 4 are respectively and independently 20-200 mm. By adopting the mode, heat exchange can be effectively carried out, and the temperature runaway phenomenon can be avoided.
According to a preferred embodiment of the present invention, the diameters of the heat exchange tubes in the middle heat exchange unit 3 and the upper heat exchange unit 4 and the diameters of the heat exchange tubes in the lower heat exchange unit 2 are respectively 2 to 10, preferably 2 to 5, and the number of the heat exchange tubes in the lower heat exchange unit and the number of the heat exchange tubes in the middle heat exchange unit 3 and the upper heat exchange unit 4 are respectively 2 to 5.
According to a preferred embodiment of the present invention, with respect to the heater (6), the lower heat exchange unit 2 is connected in parallel with the middle heat exchange unit 3, the middle heat exchange unit 3 is connected in series with the upper heat exchange unit 4, the heater 6 is respectively communicated with a water inlet of the lower heat exchange unit 2 and a water inlet of the middle heat exchange unit 3, and a water outlet of the lower heat exchange unit 2 and a water outlet of the upper heat exchange unit 4 are respectively communicated with the steam drum 5.
According to a preferred embodiment of the present invention, as shown in fig. 2 and 3, the heat exchange tube includes a plurality of baffles arranged in a staggered manner.
According to a preferred embodiment of the invention, the baffle is a straight plate (shown in fig. 2) or a barb structure (shown in fig. 3), and there is no particular requirement for the invention.
According to the method, baffles are arranged in part or all of the heat exchange tubes of the middle heat exchange unit 3, and are used for reducing the speed of water flow in the heat exchange tubes and prolonging the retention time of a heat exchange medium in the inner heat exchange unit, so that the heat exchange effect can be improved under the condition of not increasing the heat exchange area, more liquid water is converted into water vapor through heat absorption, and the latent heat can be fully utilized; the middle heat exchange unit is arranged in the filtering area of the slurry bed reactor, so that more heat in the filtering area can be absorbed, the heat transfer of the filtering area in the reactor is enhanced, and the temperature runaway caused by overheating of the Fischer-Tropsch synthesis catalyst in the filtering and separating operation is avoided.
According to a preferred embodiment of the present invention, a valve 16 and a valve 17 are connected in parallel on a pipeline of the steam drum 5 communicating with the upper water outlet of the internal heat exchange unit, and a pump 10 is provided on a branch of the valve 16 or the valve 17.
According to the invention, a standby pump 10 is arranged in front of the steam pocket 5, when the vapor resistance in the heat exchange tube is too large due to more gas phase and the vapor mixture in the heat exchange tube returns to the steam pocket 5, the pump 10 is opened, and the vapor mixture is forcibly pumped back to the steam pocket 5, so that the temperature runaway phenomenon is avoided.
According to a preferred embodiment of the invention, the steam drum 5 is provided with a water replenishment line 9. The make-up water line 9 is used to provide make-up water to the steam drum 5.
According to a preferred embodiment of the invention, the steam drum 5 is provided with a pressure control valve 8. The pressure control valve 8 is used for regulating and controlling the pressure of the steam drum 5.
According to the invention, during the specific operation, the temperature of the water in the steam drum is controlled by a pressure control valve on the steam drum, and the set value is the saturated vapor pressure of the water at the set temperature. And after the water in the heat exchange unit absorbs heat, when the pressure of the water vapor in the steam drum is lower than the set pressure, the pressure control valve is closed. When the pressure of the steam in the steam drum is higher than the set pressure, the pressure control valve is opened, and the steam is discharged to the public pipe network. The water vapor lost in the steam drum is replenished by make-up water.
According to a preferred embodiment of the invention, a pump 7 is provided on the line where the steam drum 5 and the heater 6 communicate.
When the system disclosed by the invention is used for carrying out Fischer-Tropsch synthesis reaction, the heat exchange efficiency of the heat exchange unit in the slurry bed reactor can be improved, the uniform and stable temperature in the slurry bed reactor can be ensured, and the redundant heat caused by temperature runaway can be timely and effectively removed when the local temperature runaway of the catalyst occurs, so that the yield of a target product is ensured, and the operation safety of the device is improved.
The invention provides a method for carrying out Fischer-Tropsch synthesis reaction by adopting a slurry bed reaction system, which comprises the following steps: water from the steam drum 5 enters the internal heat exchange unit through the heater 6 to exchange heat with the materials in the slurry bed reactor 1, the water after heat exchange enters the steam drum 5 to be subjected to gas-liquid separation, and the separated water returns to the heater 6;
in the initial stage of the Fischer-Tropsch synthesis reaction, the heater 6 heats water from a steam drum 5, and the heated hot water is used for heating the materials in the slurry bed reactor 1 until the materials in the slurry bed reactor 1 reach the reaction temperature;
after the material in the slurry bed reactor 1 reaches the reaction temperature, the heater 6 stops heating, so that water from the steam drum 5 directly flows through the heater 6 to enter the internal heat exchange unit for removing the heat of the material in the slurry bed reactor 1.
The method according to the invention, wherein the steam drum 5 is provided with a pressure control valve 8, and the pressure control valve 8 is provided with a pressure threshold in the range of 1.55-5.5 MPa.
The method according to the invention, wherein the pressure control valve 8 sets a pressure threshold in the range of 2-5 MPa.
According to the method, the temperature of water in the steam drum is controlled by a pressure control valve on the steam drum, and the set value is the saturated vapor pressure of the water at the set temperature. And after the water in the heat exchange unit absorbs heat, when the pressure of the water vapor in the steam drum is lower than the set pressure, the pressure control valve is closed. When the pressure of the steam in the steam drum is higher than the set pressure, the pressure control valve is opened, and the steam is discharged to the public pipe network. The water vapor lost in the steam drum is replenished by make-up water. The pressure control valve controls the pressure setting range to be 1.55-5.5MPa, preferably 2.0-5 MPa.
According to the process of the invention, the bottom of the reactor may also be chilled by controlling the temperature of the inlet gas to the reactor 1 to be below the reaction temperature. Preferably the temperature of the gas stream entering the reactor is 20 to 180 c, preferably 50 to 120 c, below the fischer-tropsch reaction temperature, by which means it is possible to maintain the temperature of the bottom of the reactor at the reaction temperature.
According to the method of the present invention, the final setting of the temperature of the water in the steam drum is related to the final reaction temperature in the slurry bed reactor. For the purposes of the present invention, it is generally preferred that the temperature of the water in the drum is from 10 to 80 ℃ below the reaction temperature, preferably from 5 to 60 ℃. By this means, it is possible to keep the temperature in the reactor stable.
According to the method of the present invention, the heater can set the heating rate as required, and generally, the heater can be set such that the temperature of the water flowing through is increased at a rate of 1-30 ℃/h. And preferably, at the beginning of the Fischer-Tropsch synthesis reaction, when the temperature is lower than 120 ℃, the heater is set to ensure that the temperature of water flowing through the heater is increased at a speed of 10-25 ℃/h; when the temperature in the slurry bed reactor rises to be more than 120 ℃, the heater is set to ensure that the temperature of the water flowing through the reactor rises at the speed of 5-20 ℃/h; when the temperature in the slurry bed reactor is raised to 200 ℃ or higher up to the reaction temperature finally set, the heater is set so that the temperature of the water flowing through is raised at a rate of 1-10 ℃/h.
For the sake of convenience, the slurry bed reaction system and the fischer-tropsch synthesis reaction method of the present invention will be described in a nested manner, but it should be understood that the slurry bed reaction system and the fischer-tropsch synthesis reaction method of the present invention may be combined with each other or may be independent of each other, and the present invention is not particularly limited thereto.
In one embodiment of the invention, the steam drum 5 is provided with a make-up water line 9 to make up for water losses caused by the water vapour discharge.
Wherein, the water replenishing pipeline 9 can be provided with a water replenishing valve so as to adjust the water quantity and switch.
According to the invention, water (usually a mixture of water and steam) after heat exchange of the internal heat exchange unit enters the steam drum for gas-liquid separation. To achieve this, the steam drum is typically provided with a pressure control valve, which pressure control valve 8 is opened to discharge excess water vapor when the water vapor pressure within the steam drum exceeds a set pressure (i.e. a pressure threshold). Preferably, the pressure control valve sets a pressure threshold in the range of 1.55-5.5MPa, more preferably in the range of 2-5 MPa; i.e. when the pressure of the water vapour in the steam drum is higher than a set pressure threshold, the pressure control valve is opened to discharge the excess water vapour. The set pressure value is the saturated vapor pressure at the set temperature, and when the residual vapor is discharged, the vapor in the vapor drum is reduced to the set temperature (usually, the set temperature is 10-80 ℃ lower than the Fischer-Tropsch synthesis reaction temperature, and preferably 5-60 ℃ lower).
According to the present invention, as shown in fig. 1, the heat exchange process of the present invention substantially comprises: after gas-liquid separation, the obtained water and the make-up water provided by the make-up water pipeline are pumped into a heater (without heating) together, and then are sent to an internal heat exchange unit positioned in the slurry bed reactor for heat exchange, the water after heat exchange circularly enters the steam drum again, and the circulation is repeated. The heat exchange process can not only remove heat in the reactor, but also provide heat for the reactor according to the requirement.
According to the invention, when the synthesis gas enters the slurry bed reactor 1 to perform contact reaction with the Fischer-Tropsch synthesis catalyst, wherein the temperature at the initial stage of the reaction is low, heat needs to be provided for the reaction through the internal heat exchange unit to promote the temperature to rise to the reaction temperature, and along with the rise of the temperature, the Fischer-Tropsch synthesis reaction proceeds, a large amount of reaction heat is released by the Fischer-Tropsch synthesis reaction, and at the moment, the internal heat exchange unit is mainly used for removing the heat; especially when the Fischer-Tropsch synthesis reaction has local temperature runaway phenomenon, a large amount of cooling water with lower temperature can be quickly gushed into the internal heat exchange unit to instantaneously take away the heat of the temperature runaway, so that the temperature runaway phenomenon is eliminated, the temperature in the reactor is kept relatively constant, and the catalyst is favorable for keeping the stability for a long time.
Therefore, at the initial stage of the Fischer-Tropsch synthesis reaction, the hot water provided by the heater provides heat for the materials in the slurry bed reactor, a large amount of reaction heat is gradually released in the Fischer-Tropsch synthesis reaction along with the temperature rise in the slurry bed reactor, and the heat exchange unit is gradually changed from the heater to the process of removing the reaction heat in the reactor; after the Fischer-Tropsch synthesis reaction reaches the reaction temperature, the water provided by the heater removes heat for the materials in the slurry bed reactor, the heater stops heating at the moment, and the main mode of heat removal is based on the latent heat of the water, namely the water at the same temperature absorbs the heat when passing through the heat exchange tubes in the slurry bed and is converted into the water vapor at the same temperature. Wherein the heater can set the heating rate according to the needs, generally, the heater can be set to heat the water flowing through at the rate of 1-30 ℃/h. And preferably, at the beginning of the Fischer-Tropsch synthesis reaction, when the temperature is lower than 120 ℃, the heater is set to ensure that the temperature of water flowing through the heater is increased at a speed of 10-25 ℃/h; when the temperature in the slurry bed reactor rises to be more than 120 ℃, the heater is set to ensure that the temperature of the water flowing through the reactor rises at the speed of 5-20 ℃/h; when the temperature in the slurry bed reactor is raised to 200 ℃ or higher up to the reaction temperature finally set, the heater is set so that the temperature of the water flowing through is raised at a rate of 1-10 ℃/h.
According to the present invention, the temperature of the water heated by the heater is preferably 150-.
According to the present invention, although the configuration of the internal heat exchange unit is not particularly limited in the present invention, in order to better match the heat exchange of the external heat exchange unit, it is preferable that the internal heat exchange unit includes a lower heat exchange unit (disposed at the lower part of the slurry bed reactor), a middle heat exchange unit (disposed at the middle part of the slurry bed reactor), and an upper heat exchange unit (disposed at the upper part of the slurry bed reactor) disposed inside the slurry bed reactor, and the lower heat exchange unit, the middle heat exchange unit, and the upper heat exchange unit are connected in series and/or in parallel with each other.
Preferably, the lower heat exchange unit is connected in parallel with the middle heat exchange unit, the middle heat exchange unit is connected in series with the upper heat exchange unit, the heater is respectively communicated with a water inlet of the lower heat exchange unit and a water inlet of the middle heat exchange unit, and a water outlet of the lower heat exchange unit and a water outlet of the upper heat exchange unit are respectively communicated with the steam drum. In this case, the water outlet of the middle heat exchange unit is communicated with the water inlet of the upper heat exchange unit. It can be understood that, in this arrangement, water coming out of the heater enters the lower heat exchange unit and the middle heat exchange unit from the pipeline 11 and the pipeline 12 respectively, water after heat exchange in the lower heat exchange unit enters the steam drum through the pipeline 13, water after heat exchange in the middle heat exchange unit enters the upper heat exchange unit again for heat exchange, and water after heat exchange in the upper heat exchange unit enters the steam drum through the pipeline 14.
Although the structures of the lower heat exchange unit, the middle heat exchange unit and the upper heat exchange unit can be the same or different, the Fischer-Tropsch reaction raw material gas at the bottom of the reactor has higher concentration, more violent reaction and more generated heat, so that more heat needs to be removed. Preferably, the diameter of the heat exchange tubes in the lower heat exchange unit is smaller than the diameter of the heat exchange tubes in the middle heat exchange unit and the upper heat exchange unit, and the number of the heat exchange tubes in the lower heat exchange unit is larger than the number of the heat exchange tubes in the middle heat exchange unit and the upper heat exchange unit. Under the condition, the diameter of the heat exchange tubes in the lower heat exchange unit is preferably 2-10mm smaller than that of the heat exchange tubes in the middle heat exchange unit and the upper heat exchange unit, and more preferably 2-5mm smaller.
Under the condition that this condition is satisfied, it is preferable that the heat exchange tubes in the lower heat exchange unit have a diameter of 10 to 200mm, more preferably 10 to 40 mm. Preferably, the diameters of the heat exchange tubes in the middle heat exchange unit and the upper heat exchange unit are respectively and independently 20-200mm, preferably 40-100 mm. By adopting the mode, heat exchange can be effectively carried out, and the temperature runaway phenomenon can be avoided.
According to a preferred embodiment of the present invention, the ratio of the diameter of the heat exchange tubes in the middle heat exchange unit 3 and the upper heat exchange unit 4 to the diameter of the heat exchange tubes in the lower heat exchange unit 2 is 2-10, preferably 2-5, and the ratio of the number of the heat exchange tubes in the lower heat exchange unit to the number of the heat exchange tubes in the middle heat exchange unit 3 and the upper heat exchange unit 4 is 2-5.
As described above, the slurry bed reaction system of the present invention, in cooperation with the internal heat exchange unit and the external heat exchange unit of the present invention, can not only improve the heat exchange efficiency of the internal heat exchange unit in the slurry bed reactor and ensure a uniform and stable temperature inside the slurry bed reactor, but also timely and effectively remove excess heat caused by temperature runaway when a local temperature runaway of the catalyst occurs, thereby ensuring the yield of a target product and improving the safety of device operation.
The present invention will be described in detail below by way of examples.
The system and method provided by the present invention will be further described with reference to the accompanying drawings, but the invention is not limited thereto. In order to highlight the process idea of the present invention, some equipments necessary for industrial application but well known to those skilled in the art, such as pumps, valves, filters, etc., are omitted from the drawings.
In the following examples:
carrying out Fischer-Tropsch synthesis reaction by using a slurry bed reaction system shown in FIG. 1, wherein the system comprises: the system comprises a slurry bed reactor 1, a lower heat exchange unit 2, a middle heat exchange unit 3, an upper heat exchange unit 4, a steam drum 5, a heater 6, a pump 7, a pressure control valve 8 and a water replenishing pipeline 9; the lower heat exchange unit 2, the middle heat exchange unit 3 and the upper heat exchange unit 4 are respectively arranged at the lower part, the middle part and the upper part in the slurry bed reactor 1, the lower heat exchange unit 2 and the middle heat exchange unit 3 are connected in parallel, and the middle heat exchange unit 3 and the upper heat exchange unit 4 are connected in series; the steam drum 5, the pump 7 and the heater 6 are sequentially connected in series; the heater 6 is communicated with the lower heat exchange unit 2 and the middle heat exchange unit 3 through pipelines 11 and 12 respectively; the steam drum 5 is communicated with the upper heat exchange unit 4 and the lower heat exchange unit 2 through a pipeline 13 and a pipeline 14 respectively; wherein, the pressure control valve 8 and the water replenishing pipeline 9 are arranged on the steam drum 5 to respectively adjust the pressure in the steam drum 5 and replenish water for the steam drum 5.
Wherein, a valve 16 and a valve 17 are connected in parallel on the pipeline 14 and the communicating pipeline of the steam pocket 5, and a pump is arranged on the branch of the valve 17.
The lower heat exchange unit 2 comprises 8 heat exchange tubes, wherein the middle 4 heat exchange tubes are provided with straight plate baffles which are distributed in a staggered mode;
the middle heat exchange unit 3 comprises 4 heat exchange tubes, wherein the middle 2 heat exchange tubes are provided with baffles which are arranged in a staggered manner;
the baffle plates are straight plates, and the cross sectional area of the baffle plates is 50% of that of the heat exchange tubes.
The diameter of the heat exchange tube in the lower heat exchange unit 2 is 20 mm; the diameter of the heat exchange tube in the middle heat exchange unit 3 is 60 mm; the diameter of the heat exchange tube in the upper heat exchange unit 4 is 60 mm.
The catalyst is an SFT418 Fischer-Tropsch synthesis iron catalyst independently developed by Shenhua group and is subjected to reduction treatment before use.
In the synthesis gas, CO and H2In a molar ratio of 1: 1.5.
example 1
This example illustrates the slurry bed reaction system and the Fischer-Tropsch synthesis reaction process of the present invention.
Adopting a slurry bed reaction system shown in FIG. 1, introducing Fischer-Tropsch synthesis raw material gas (synthesis gas) from the lower part of a slurry bed reactor 1, then reacting on the surface of a catalyst in a liquid wax environment, flowing out the reacted gas from the top of the reactor to the downstream for separation, and enabling the temperature rise rate of flowing water to be 20 ℃/h by a heater 6; when the temperature in the slurry bed reactor 1 reaches 120 ℃, a heater 6 is arranged to ensure that the temperature rise rate of the flowing water is 10 ℃/h; when the temperature in the slurry bed reactor 1 reaches 200 ℃, the heater 6 is arranged to ensure that the temperature rise rate of the flowing water is 5 ℃/h; when the temperature in the slurry bed reactor 1 reaches 250 ℃, determining that the temperature reaches the specified reaction temperature of the Fischer-Tropsch synthesis reaction, and closing the heater 6; wherein the threshold value of a pressure control valve 8 arranged on the steam pocket 5 is 4 MPa; the temperature of the water supplied to the steam drum 5 through the water replenishing line 9 is normal temperature (about 25 ℃);
after the specified Fischer-Tropsch synthesis reaction temperature is reached and within 300 hours before the reaction is carried out, the reaction temperature is kept stable, and the conversion rate of the feed gas CO is 98%. During the reaction for 300-500h, the temperature runaway phenomenon occurs for many times, the temperature in the filtering area in the reactor rises to 285 ℃ every time the temperature runaway is carried out, at the moment, the pump 10 is started to forcibly accelerate the flow rate of the medium in the heat exchange tube, after 10-20min, the temperature in the filtering area of the slurry bed returns to 250 ℃, and finally the conversion rate of the feed gas CO is still 98 percent by measurement, which indicates that the activity of the catalyst is not lost;
in the operation process:
the water in the steam drum 5 fills the water in the whole heat exchange system (comprising the inner heat exchange unit and the outer heat exchange unit) by the make-up water. Water in the steam drum 5 passes through the pump 7, passes through the heater 6, enters the reactor 1 through the pipelines 11 and 12, enters the lower heat exchange unit 2 through one pipeline 11, is converged through the pipeline 13 and the pipeline 14, and then returns to the steam drum 5 through the pump 10. The other path 12 enters the internal heat exchange unit 3, then enters the internal heat exchange unit 4, is converged by a pipeline 13 and a pipeline 14 and then returns to the steam drum 6 through the pump 10;
when the Fischer-Tropsch synthesis reaction begins, water in a steam drum 5 is powered by a pump 7, heated by a heater 6 and then enters a lower heat exchange unit 2, a middle heat exchange unit 3 and an upper heat exchange unit 4 in a reactor 1, and then slurry in the reactor is heated. Along with the temperature rise of the reactor 1, a large amount of reaction heat is gradually released in the Fischer-Tropsch synthesis reaction, the internal heat exchange unit is gradually changed from heating slurry in the reactor to removing heat in the slurry bed reactor, and the heater 6 is closed;
the temperature control of the water in the steam pocket 5 is controlled by a pressure control valve 8 (saturated vapor pressure of water at a set temperature). When the temperature of the water in the heat exchange unit does not rise to the set temperature after absorbing heat, the pressure control valve 8 is not opened. When the temperature of the water in the internal heat exchange unit exceeds the set temperature after absorbing heat, the pressure in the steam pocket exceeds the pressure controlled by the pressure control valve 8, the valve is opened, and the steam is discharged into the public pipe network. When the pressure in the drum 5 falls back to the pressure controlled by the pressure control valve 8, the valve 8 is closed again. The water vapour lost in the drum 5 is provided by make-up water;
when the local overheating and temperature runaway of the catalyst occurs inside the slurry bed reactor 1, the liquid water in the middle heat exchange unit absorbs more heat, so that the hot gas phase in the tube is too much, the gas resistance is too large, and the water flow speed is slow. At this time, the backup pump 10 is turned on to forcibly accelerate the water flow rate in the internal heat exchange unit and take away the excessive heat in the reactor. When the flying temperature is eliminated, the temperature in the reactor tends to be stable, and the standby pump 10 is optionally stopped.
Comparative example 1
The slurry bed reaction system shown in fig. 1 was employed, except that the pump 10 and the valve 17 were not provided, and the heat exchange tubes of the internal heat exchange units were not provided with baffles.
When the temperature in the slurry bed reactor reaches 250 ℃, determining that the temperature reaches the specified reaction temperature of the Fischer-Tropsch synthesis reaction, and closing the heater;
after the specified Fischer-Tropsch synthesis reaction temperature is reached, the reaction is stable within 200h before the reaction, the conversion rate of the feed gas CO is determined to be 98%, the temperature runaway phenomenon is generated for many times during 200-500h, the temperature in the filtering area in the reactor is increased to 285 ℃ each time the temperature runaway occurs, measures of reducing the temperature of the steam pocket and reducing the temperature of the feed gas are adopted, after 8-10h, the temperature in the filtering area of the slurry bed returns to 250 ℃, and the conversion rate of the feed gas CO is determined to be reduced to 90%, which indicates that the activity of the catalyst is lost.
From the results of comparative example 1 and example 1, it is understood that although the prior art can solve the problem of the runaway temperature, it takes a long time (8-10 hours) and reduces the activity of the catalyst, and the present invention can not only rapidly solve the problem of the runaway temperature (less than 1 hour) but also ensure the activity of the catalyst.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the technical features described in the above embodiments can be combined in any suitable manner, and the invention is not further described in various possible combinations.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (18)
1. A slurry bed reaction system, comprising: the heat exchanger comprises a slurry bed reactor (1), an internal heat exchange unit and an external heat exchange unit, wherein the internal heat exchange unit is arranged inside the slurry bed reactor (1), the external heat exchange unit is arranged outside the slurry bed reactor (1), the external heat exchange unit comprises a steam pocket (5) and a heater (6) which are sequentially connected in series, the heater (6) is communicated with a water inlet at the lower part of the internal heat exchange unit, and the steam pocket (5) is communicated with a water outlet at the upper part of the internal heat exchange unit; the internal heat exchange unit comprises heat exchange tubes, baffles are arranged in part or all of the heat exchange tubes and used for prolonging the retention time of heat exchange media in the internal heat exchange unit, a first valve (16) and a second valve (17) which are connected in parallel are arranged on a pipeline communicated with a water outlet in the upper part of the steam drum (5) and the water outlet in the upper part of the internal heat exchange unit, and a pump (10) is arranged on a branch of the first valve (16) or the second valve (17).
2. The slurry bed reaction system according to claim 1,
baffles are arranged in 20-70% of the heat exchange tubes of the internal heat exchange unit.
3. The slurry bed reaction system according to claim 2, wherein the internal heat exchange units comprise a lower heat exchange unit (2), a middle heat exchange unit (3) and an upper heat exchange unit (4) arranged inside the slurry bed reactor (1);
the lower heat exchange unit (2), the middle heat exchange unit (3) and the upper heat exchange unit (4) respectively comprise a plurality of heat exchange tubes connected in parallel, and baffles are respectively arranged in part or all of the heat exchange tubes of the lower heat exchange unit (2) and the middle heat exchange unit (3);
the lower heat exchange unit (2), the middle heat exchange unit (3) and the upper heat exchange unit (4) are connected in series and/or in parallel with each other with respect to the heater (6).
4. The slurry bed reaction system according to claim 3,
baffles are arranged in 10-70% of the heat exchange tubes of the lower heat exchange unit (2) and the middle heat exchange unit (3);
the diameter of the heat exchange tube in the lower heat exchange unit (2) is smaller than that of the heat exchange tubes in the middle heat exchange unit (3) and the upper heat exchange unit (4);
the number of the heat exchange tubes in the lower heat exchange unit (2) is larger than that of the heat exchange tubes in the middle heat exchange unit (3) and the upper heat exchange unit (4).
5. The slurry bed reaction system according to claim 4,
baffles are arranged in 20-50% of the heat exchange tubes of the lower heat exchange unit (2) and the middle heat exchange unit (3);
the diameters of the heat exchange tubes in the lower heat exchange unit (2) and the middle heat exchange unit (3) and the upper heat exchange unit (4) are respectively 2-50mm smaller than the diameters of the heat exchange tubes in the middle heat exchange unit and the upper heat exchange unit;
the diameter of the heat exchange tube in the lower heat exchange unit (2) is 10-200 mm; the diameters of the heat exchange tubes in the middle heat exchange unit (3) and the upper heat exchange unit (4) are respectively and independently 20-200 mm.
6. The slurry bed reaction system according to claim 4, wherein the heat exchange tube diameter in the middle heat exchange unit (3) and the upper heat exchange unit (4) and the heat exchange tube diameter in the lower heat exchange unit (2) are each 2-10.
7. The slurry bed reaction system according to claim 6, wherein the heat exchange tube diameter in the middle heat exchange unit (3) and the upper heat exchange unit (4) and the heat exchange tube diameter in the lower heat exchange unit (2) are each 2-5.
8. The slurry bed reaction system according to claim 4, wherein the number of heat exchange tubes in the lower heat exchange unit (2) and the number of heat exchange tubes in the middle heat exchange unit (3) and the upper heat exchange unit (4) are each 2-5.
9. The slurry bed reaction system according to claim 3, wherein, relative to the heater (6), the lower heat exchange unit (2) is connected in parallel with the middle heat exchange unit (3), the middle heat exchange unit (3) is connected in series with the upper heat exchange unit (4), the heater (6) is respectively communicated with a water inlet of the lower heat exchange unit (2) and a water inlet of the middle heat exchange unit (3), and a water outlet of the lower heat exchange unit (2) and a water outlet of the upper heat exchange unit (4) are respectively communicated with the steam drum (5).
10. The slurry bed reaction system according to any one of claims 1-9, wherein the heat exchange tubes comprise a plurality of baffles arranged in a staggered arrangement.
11. The slurry bed reaction system according to claim 10, wherein the cross-sectional area of each baffle plate cannot exceed 80% of the cross-sectional area within the heat exchange tube.
12. The slurry bed reaction system according to claim 11, wherein the cross-sectional area of each baffle plate cannot exceed 70% of the cross-sectional area within the heat exchange tube.
13. A process for carrying out a fischer-tropsch synthesis reaction using the slurry bed reaction system of any one of claims 1 to 12, the process comprising: water from the steam drum (5) enters the internal heat exchange unit through the heater (6) to exchange heat with the materials in the slurry bed reactor (1), the water after heat exchange enters the steam drum (5) to be subjected to gas-liquid separation, and the separated water returns to the heater (6);
in the initial stage of the Fischer-Tropsch synthesis reaction, the heater (6) heats water from a steam drum (5), and the heated hot water is used for heating materials in the slurry bed reactor (1) until the materials in the slurry bed reactor (1) reach the reaction temperature;
after the materials in the slurry bed reactor (1) reach the reaction temperature, the heater (6) stops heating, so that water from the steam pocket (5) directly flows through the heater (6) to enter the internal heat exchange unit for removing the heat of the materials in the slurry bed reactor (1).
14. A method according to claim 13, wherein the steam drum (5) is provided with a pressure control valve (8), and the pressure control valve (8) is provided with a pressure threshold in the range of 1.55-5.5 MPa.
15. A method according to claim 14, wherein the pressure control valve (8) is arranged with a pressure threshold in the range of 2-5 MPa.
16. The method of any one of claims 13-15,
the temperature of the gas flow entering the slurry bed reactor (1) is 20-180 ℃ lower than the temperature of the Fischer-Tropsch synthesis reaction;
the temperature of water in the steam drum is 10-80 ℃ lower than the temperature of Fischer-Tropsch synthesis reaction;
at the beginning of the Fischer-Tropsch synthesis reaction, when the temperature is lower than 120 ℃, the heater (6) is set to ensure that the temperature of the water flowing through the heater rises at the speed of 10-25 ℃/h; when the temperature in the slurry bed reactor (1) rises to be more than 120 ℃, the heater (6) is set to increase the temperature of the water flowing through at the rate of 5-20 ℃/h; when the temperature in the slurry bed reactor (1) rises to 200 ℃ or higher up to the reaction temperature finally set, the heater (6) is set so that the temperature of the water flowing therethrough rises at a rate of 1-10 ℃/h.
17. The process as claimed in claim 16, wherein the temperature of the gas stream entering the slurry bed reactor (1) is 50-120 ℃ lower than the fischer-tropsch synthesis reaction temperature.
18. The process of claim 16, wherein the temperature of the water in the steam drum is 5-60 ℃ lower than the fischer-tropsch synthesis reaction temperature.
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