CN109046183B - Fischer-Tropsch synthesis fixed bed reactor thermal control system - Google Patents
Fischer-Tropsch synthesis fixed bed reactor thermal control system Download PDFInfo
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Abstract
The invention provides a Fischer-Tropsch synthesis fixed bed reactor heat control system, which comprises a fixed bed reactor, a catalyst bed and a heat exchange system, wherein the fixed bed reactor is used for contacting hot synthesis gas with the catalyst to generate Fischer-Tropsch synthesis reaction; the synthesis gas preheater is used for carrying out primary heat exchange on the synthesis gas and steam to obtain condensate water formed by the heat exchange of the synthesis gas and the steam which are preheated primarily; a steam drum for vapor-liquid separation of a mixture of recycled superheated water and steam, pressure control of the steam, and supplying the steam into the syngas preheater, supplying the recycled superheated water to the reactor to absorb reaction heat, and receiving condensed water and a mixture of the superheated water and the steam; a syngas heat exchanger for subjecting the primarily preheated syngas to a second heat exchange with a hot material to obtain the hot syngas for supply to the fixed bed reactor. The system can realize the high-efficiency utilization and energy recovery of the heat in the system and realize the high-efficiency cyclic utilization of the water in the system.
Description
Technical Field
The invention relates to a Fischer-Tropsch synthesis fixed bed reactor thermal control system.
Background
The Fischer-Tropsch synthesis is a technological process for generating liquid fuel by using synthesis gas (hydrogen and carbon monoxide) as a raw material under the conditions of a catalyst (an iron system or a cobalt system) and proper reaction conditions, and is one of the methods for efficiently converting and utilizing non-petroleum carbon-containing resources.
The fixed bed reactor is a common traditional reactor type in the fields of chemical industry, petrifaction and energy, and has the characteristics of flexible and various forms, simple operation and the like. In the industrial application of the fixed bed reactor, the catalyst is generally filled in a reaction tube, raw material gas is contacted with the catalyst for reaction, a heat transfer medium passes through a shell layer of the reactor, and the heat of reaction is removed by wall heat exchange at the wall of the reaction tube.
If the fixed bed reactor is applied to the Fischer-Tropsch reaction process, if heat conduction is not timely, large temperature gradients can be generated in the axial direction and the radial direction of the reaction tube, particularly, hot spots are easily formed in the center of the reaction tube, so that carbon deposition of the catalyst is caused, the catalyst is finally inactivated, even the phenomenon of temperature runaway occurs, and the reaction process is difficult to control. Therefore, effective measures must be taken to remove the heat generated in the fixed bed reactor in a timely manner.
In order to reduce the axial and radial temperature gradients of a catalyst bed layer, in the prior art, on one hand, a constant-temperature heat-conducting medium is arranged outside a reaction pipe to take away reaction heat; on the other hand, the inner diameter of the reaction tube is reduced as much as possible, and the distance for transferring the reaction heat in the catalyst bed layer to the outside is shortened, so that the reaction heat is taken away by the heat-conducting medium as soon as possible. For large fixed bed reactors, a drum system is typically employed to accomplish this: circulating superheated water from the steam pocket enters a heat taking medium channel of the fixed bed reactor, reaction heat transferred by the reaction channel is absorbed and then vaporized, and steam generated by vaporization is discharged to a public engineering system. However, the existing steam drum system needs to consume a large amount of water, and the heat is not fully utilized; in addition, the heat transfer effect of the fixed bed reactor is yet to be further improved.
Disclosure of Invention
In view of the above, the invention provides a thermal control system for a fischer-tropsch synthesis fixed bed reactor, which can reduce the radial and axial temperature difference of the reactor, remove reaction heat in time, realize efficient utilization and energy recovery of heat in the system, and realize efficient cyclic utilization of water in the system.
In order to achieve the purpose, the invention adopts the following technical scheme:
a Fischer-Tropsch synthesis fixed bed reactor thermal control system comprises,
the fixed bed reactor is used for contacting hot synthesis gas with a catalyst to generate a Fischer-Tropsch synthesis reaction so as to obtain a hot material containing a reaction product and unreacted synthesis gas; the fixed bed reactor is provided with a superheated water inlet for receiving circulating superheated water; a heat transfer medium channel communicated with a circulating superheated water inlet is arranged in the fixed bed reactor, and part of the circulating superheated water is vaporized into steam after absorbing reaction heat generated by Fischer-Tropsch synthesis reaction in the heat transfer medium channel to form a mixture of the circulating superheated water and the steam;
the synthesis gas preheater is used for carrying out primary heat exchange on synthesis gas to be preheated and steam to obtain primarily preheated synthesis gas and condensed water formed by heat exchange of the steam;
a syngas heat exchanger for second heat exchange of the primarily preheated syngas obtained by the syngas preheater with the hot material obtained by the fixed bed reactor to obtain hot syngas for supply to the fixed bed reactor;
a drum for supplying steam for the first heat exchange into the synthesis gas preheater and supplying the circulated superheated water to the fixed bed reactor to absorb reaction heat, and for receiving the condensed water formed in the synthesis gas preheater and a mixture of the circulated superheated water and steam formed in the fixed bed reactor, and performing vapor-liquid separation on the mixture of the circulated superheated water and steam and controlling steam pressure;
preferably, in the fixed bed reactor, the portion of the circulated superheated water vaporized after absorbing the heat of reaction while flowing through the heat transfer medium passage is 1 to 90% by weight, preferably 10 to 70% by weight, more preferably 20 to 50% by weight.
Preferably, the fixed bed reactor comprises a tower body, a plurality of reaction tubes which are arranged in parallel at intervals are arranged in the tower body along the axial direction, and radial radiators are arranged in the reaction tubes; the heat medium channel comprises channels formed by spaces between adjacent reaction tubes and between the reaction tubes and the inner wall of the tower body; the whole radial radiator extends along the axial direction of the reaction tube, and comprises a plurality of radiating fins extending along the radial direction of the reaction tube, and the inner cavity of the reaction tube is divided into a plurality of independent catalyst filling cavities; more preferably, the material of the radial heat sink is aluminum material, copper material, steel material or aluminum alloy, and more preferably, aluminum material.
Preferably, radial heat sinks are arranged inside the reaction tube: (I) the axial heat which is difficult to remove can be led out towards the wall surface of the reactor tower body through the heat dissipation material with better heat conduction effect, so that the problem of large radial temperature gradient of the fixed bed reactor is solved; (II) one reaction tube (with a diameter of 10-80mm) can be regarded as a collection of a plurality of traditional tubular reactor arrays (with a diameter of 19-25mm), and each single area cut by the radiator can be regarded as an independent traditional tubular reactor array.
Preferably, a thermocouple sleeve is arranged at the axis of the radial radiator, the radial radiator comprises an inner ring radiating area and an outer ring radiating area which are concentric, and a plurality of radiating fins extending from the axis to the outer ring radiating area along the radial direction are arranged in the inner ring radiating area; a plurality of radiating fins extending along the radial direction are arranged in the outer ring radiating area; the inner cavity of the reaction tube is divided into a plurality of independent catalyst filling cavities by the radiating fins of the inner ring radiating area and the outer ring radiating area;
further preferably, the inner cavity of the reaction tube is divided into 6 to 30 independent catalyst-filled cavities.
In some preferred embodiments, the plurality of fins of the inner ring heat dissipation area are distributed in a shape like a Chinese character 'mi' as a whole.
Preferably, the inner ring radiating area is uniformly divided into a plurality of catalyst filling cavities with the same radial cross-sectional area by radiating fins; the outer ring radiating area is divided into a plurality of catalyst filling cavities with the same radial cross-sectional area by radiating fins; further preferably, the radial cross-sectional areas of the catalyst filling cavities of the inner ring heat dissipation area and the outer ring heat dissipation area are equal;
it is further preferred that the inner radius R of the inner ring heat-dissipating zone is 0.55 to 0.65 times the inner radius R of the entire reaction tube.
Preferably, a plurality of reaction tubes are uniformly arranged in the tower body at intervals; preferably, one of the reaction tubes is arranged along the axis of the tower body to serve as a central tube, and the other reaction tubes are uniformly arranged around the central tube at intervals; further preferably, the distance L between the central axes of any two adjacent reaction tubes is 3 to 10 times the inner radius R of the reaction tube.
In some preferred embodiments, the upper part or the top of the tower body is provided with a synthesis gas inlet for inputting the hot synthesis gas; and a hot material outlet for discharging the hot material is arranged at the bottom or the lower part of the tower body.
Preferably, a gas pre-distributor is arranged in the tower body and is directly connected with the synthesis gas inlet; a gas distribution plate is arranged in a space between the gas pre-distributor and the top of the reaction tube; the gas pre-distributor and the gas distribution plate are used for uniformly distributing hot synthesis gas input from the synthesis gas inlet in a radial direction before entering the reaction tube. The gas pre-distributor and the gas distribution plate are arranged in the reactor, and the synthesis gas at the synthesis gas inlet is uniformly distributed along the radial direction and then enters the reaction tube to participate in the reaction, so that the problem of nonuniform radial distribution (large central gas amount and small wall gas amount) when the synthesis gas flows in the tower body of the reactor is solved, the utilization rate of the catalyst can be improved, and the radial and axial temperature difference of the reactor is reduced.
Preferably, a circulating superheated water inlet of the fixed bed reactor is arranged at the position, close to the lower part of the reaction tube, of the side wall of the tower body;
specifically, the fixed bed reactor is also provided with a superheated water-steam mixture outlet for outputting the circulating superheated water-steam mixture from the heat transfer medium channel; preferably, the superheated water-steam mixture outlet is arranged on the side wall of the tower body close to the top of the reaction tube;
in particular, the steam drum is provided with a steam inlet connected to the superheated water-steam mixture outlet of the fixed bed reactor, so that the circulating superheated water and steam mixture produced in the fixed bed reactor is circulated into the steam drum.
Preferably, a condensate water tank and a steam drum water replenishing pump are further arranged between the synthesis gas preheater and the steam drum, and the condensate water tank is connected with a condensate water outlet of the synthesis gas preheater and is used for storing condensate water obtained by the synthesis gas preheater; the steam drum water replenishing pump is used for pumping the condensed water in the condensed water tank to the steam drum;
preferably, a superheated water pump is connected between the steam drum and the fixed bed reactor and used for pumping circulating superheated water in the steam drum to the fixed bed reactor.
In some preferred embodiments, a syngas inlet temperature control loop is connected to the syngas inlet of the fixed bed reactor for controlling the temperature of the syngas to be fed into the syngas inlet; the steam outlet of the steam drum is connected with a pressure control valve and a fixed bed reactor temperature control loop for controlling the opening degree of the valve;
preferably, the steam supplied to the synthesis gas preheater by the steam drum is medium-low pressure steam, the temperature is 200-285 ℃, and the pressure is 1.5-7.0 MPa.
The technical scheme provided by the invention has the following beneficial effects:
according to the system, the steam in the steam drum and the synthesis gas are subjected to primary heat exchange to preheat the synthesis gas, and the synthesis gas is further subjected to secondary heat exchange by using hot materials discharged by the fixed bed reactor to obtain hot synthesis gas for Fischer-Tropsch synthesis reaction, so that heat in the system is fully utilized. Meanwhile, in the first heat exchange, steam from the steam pocket exchanges heat with synthesis gas to be converted into condensate water, the condensate water is recycled to the steam pocket, the condensate water is used as circulating superheated water to be input into the fixed bed reactor to absorb reaction heat after reaching the overheat temperature in the steam pocket, and then the condensate water is converted into steam.
The invention utilizes the steam discharged by the steam drum, particularly the medium-low pressure steam (the temperature is 220-.
In the system, preferably, a radial radiator is arranged in a reaction tube of the fixed bed reactor, and the inner cavity of the reaction tube is divided into a plurality of independent catalyst filling cavities; more preferably, the reactor comprises an inner ring heat dissipation area and an outer ring heat dissipation area which are concentric, so that better heat transfer effect can be achieved, and the radial and axial temperature difference of the reactor is reduced to a greater extent.
Drawings
FIG. 1 is a schematic diagram of a Fischer-Tropsch synthesis fixed bed reactor thermal control system in one embodiment;
FIG. 2 is a schematic diagram of a radial heat sink within a reactor tube according to one embodiment;
FIG. 3 is a schematic diagram showing the arrangement of reaction tubes in a fixed bed reactor in one embodiment.
FIG. 4 is a schematic side view of a gas pre-distributor;
FIG. 5 is a schematic top view of a gas pre-distributor;
FIG. 6 is a schematic top view of a gas distribution plate.
Detailed Description
In order to better understand the technical solution of the present invention, the following examples are further provided to illustrate the present invention, but the present invention is not limited to the following examples.
The invention provides a Fischer-Tropsch synthesis fixed bed reactor heat control system, which is shown in figure 1 and mainly comprises a fixed bed reactor 1, a synthesis gas preheater 3, a steam drum 2 and a synthesis gas heat exchanger 7. The fixed bed reactor 1 is used for contacting hot synthesis gas with a catalyst to generate a Fischer-Tropsch synthesis reaction so as to obtain a hot material containing a reaction product and unreacted synthesis gas; the fixed bed reactor 1 is provided with a superheated water inlet for receiving circulating superheated water; the fixed bed reactor 1 is provided with a heat transfer medium channel communicated with a circulating superheated water inlet, and part (for example, 1-90%, preferably 10-70%, and more preferably 20-50%) of the circulating superheated water absorbs the reaction heat generated by the Fischer-Tropsch synthesis reaction in the heat transfer medium channel and is vaporized into steam to form a mixture of the circulating superheated water and the steam. And the synthesis gas preheater 3 is used for carrying out primary heat exchange on the synthesis gas to be preheated and the steam from the steam drum 2 to obtain the synthesis gas which is preliminarily preheated and condensed water formed by the heat exchange of the steam. A syngas heat exchanger 7 for second heat exchange of the primarily preheated syngas obtained by the syngas preheater 3 with the hot material obtained by the fixed bed reactor 1 to obtain hot syngas for supply to the fixed bed reactor 1. A steam drum 2 for supplying steam for the first heat exchange into the syngas preheater 3 and supplying circulated superheated water to the fixed bed reactor to absorb reaction heat, and for receiving condensed water formed in the syngas preheater and a mixture of the circulated superheated water and the steam formed in the fixed bed reactor, and performing vapor-liquid separation on the mixture of the circulated superheated water and the steam and controlling steam pressure. A heat transfer medium channel communicated with a superheated water inlet is arranged in the fixed bed reactor 1, circulating superheated water enters the heat transfer medium channel through a hot water inlet to absorb reaction heat generated by Fischer-Tropsch synthesis reaction, in the process, part of superheated water is vaporized into steam, and unvaporized superheated water and vaporized steam form a water-vapor mixture (namely, the mixture of circulating superheated water and steam) and flow out of the reactor 1 through an outlet (or called as a superheated water-steam mixture outlet) of the heat transfer medium channel in the reactor 1. The steam drum 2 is also provided with a water-steam mixture inlet which is connected with the superheated water-steam mixture outlet of the fixed bed reactor 1, so that the superheated water and the steam flowing out of the fixed bed reactor 1 can be recycled into the steam drum 2 for utilization.
The fixed bed reactor 1 mainly comprises a tower body, a plurality of reaction tubes 10 are arranged in the tower body along the axial direction, and the reaction tubes 10 are arranged in parallel at intervals. And a radial radiator 23 is provided in each reaction tube 10. The radial heat sink 23 is integrally arranged in the reaction tube 10 to extend in the axial direction of the reaction tube 10, and the radial heat sink 23 includes a plurality of fins 16, 17 extending in the radial direction of the reaction tube 10 and extending in the axial direction of the reaction tube 10 in the longitudinal direction, so that the inner cavity of the reaction tube 10 is divided into a plurality of independent catalyst-filled cavities 12 (or catalyst-filled regions), and the catalyst-filled cavities 12 are used for filling the catalyst. In some embodiments, the height of the radial heat sink 23 is the same as the height of the reaction tube 10. The radial radiator 23 is arranged in the reaction tube 10, the inner cavity of the reaction tube 10 is divided into a plurality of independent catalyst filling cavities, and the axis heat which is most difficult to remove can be guided out towards the wall surface direction through the radiating material with better heat conducting effect, so that the problem of large radial temperature gradient of the tubular fixed bed reactor 1 is solved; one reactor tube 10 can be regarded as a collection of a plurality of conventional tubular reactors (typically 19-25mm in diameter), and each individual zone cut by the radial heat sinks 23 can be regarded as a separate conventional tubular reactor, which helps to reduce the number of reactor tubes 10 in the reactor column, reduce the reactor manufacturing cost, and facilitate reactor scale-up and catalyst loading.
In some preferred embodiments, the axial center of the radial heat sink 23 is provided with a thermocouple sleeve 15, and the radial heat sink 23 specifically includes an inner ring heat dissipation area 14 and an outer ring heat dissipation area 13, and the two heat dissipation areas are concentrically arranged. Preferably, the radial heat sink 23 is coaxial with the reaction tube 10. Wherein, a plurality of radiating fins 17 are arranged in the inner ring radiating area 14, and the radiating fins extend from the axial center of the radial radiator 23 along the radial direction towards the outer ring radiating area and extend to the edge where the inner ring radiating area and the outer ring radiating area are connected, namely the outer edge of the inner ring radiating area 14; preferably, the heat dissipation fins of the inner ring heat dissipation area 14 are integrally distributed in a shape like a Chinese character 'mi', and the core of the Chinese character 'mi' is the axis provided with the thermocouple sleeve. A plurality of fins 16 are also provided in the outer annular heat-dissipating region 13 and extend in the radial direction from the outer edge of the inner annular heat-dissipating region to the inner wall of the reaction tube 10. Thus, the inner cavity of the reactor tube 10 is divided into a plurality of independent catalyst-packed cavities 12 by the fins in the inner and outer ring heat-dissipating zones. In a more preferred embodiment, the inner cavity of the reaction tube 10 is divided into 6 to 30 independent catalyst-filled cavities. In a more preferred embodiment, the inner ring heat dissipation area is uniformly divided into a plurality of catalyst filling cavities with the same radial cross-sectional area (referring to the radial direction of the reaction tube) by the heat dissipation fins; the outer ring radiating area is divided into a plurality of catalyst filling cavities with the same radial (referring to the radial direction of the reaction tube) cross section area by radiating fins; preferably, the radial (referring to the radial direction of the reaction tube) cross-sectional areas of the catalyst-filled cavities in the inner heat dissipation area and the outer heat dissipation area are equal. In some preferred embodiments, the inner radius R of the inner annular heat-dissipating section is 0.55 to 0.65 times the inner radius R of the entire reaction tube 10, so that the radial cross-sectional areas of the catalyst-loading cavity of the inner annular heat-dissipating section and the catalyst-loading cavity of the outer annular heat-dissipating section are substantially the same, which facilitates uniform radial temperature of the catalyst bed. Specifically, the radial radiator may be provided with an annular rib plate, which is located between the inner wall of the reaction tube and the axis thereof and is coaxial with the reaction tube, thereby integrally dividing the heat dissipation area of the radial radiator into an inner ring heat dissipation area and an outer ring heat dissipation area.
The material of the radial heat sink 23 is preferably aluminum, copper, steel or aluminum alloy, and more preferably aluminum, so as to obtain a better heat dissipation effect. In some embodiments, the length of the thermocouple well 15 is the same as the height of the center tube; preferably, the thermocouple well is a stainless steel tube, such as 1/4 inch or 3/8 inch stainless steel tube. The thermocouple sleeve is used for inserting a temperature measuring thermocouple therein, and is used for measuring the reaction temperature of the central tube and the catalyst bed layer in the reaction tube 10 and monitoring the distribution state of the temperature of the catalyst bed layer in the reaction tube 10 in the axial direction.
In the preferred embodiment, a plurality of reaction tubes 10 are arranged in parallel at regular intervals in the column of the fixed-bed reactor 1. In some preferred embodiments, referring to fig. 2, one reaction tube 10 of the plurality of reaction tubes 10 is arranged along the axial center of the tower body as a central tube 10-1, and the remaining reaction tubes 10 are uniformly spaced around the central tube 10-1; in a preferred embodiment, the distance L between the central axes of two adjacent reaction tubes 10 is 3-10 times, such as 4 times, the inner radius R of the reaction tube 10, so as to ensure the flow area requirement of the heat transfer channel, and improve the effective utilization of the volume of the reactor, so that the overall structure of the reactor is compact, and the investment is saved.
Specifically, the fixed bed reactor 1 of the present invention has a syngas inlet disposed at the upper portion or top of the tower body, wherein the syngas inlet is used for inputting hot syngas for the fischer-tropsch synthesis reaction. A syngas inlet temperature control loop 9 is also preferably connected to the syngas inlet for controlling the temperature of the syngas from the syngas heat exchanger 7. The bottom or the lower part of the tower body is provided with a hot material outlet for discharging products obtained by the reaction and unreacted synthesis gas. The hot material outlet is connected to a syngas heat exchanger 7 for heat exchange with the primarily preheated syngas II from the syngas preheater 3 for further preheating of the syngas II.
In some preferred embodiments, a gas pre-distributor 21 and a gas distribution plate 22 are also provided within the column. Wherein the gas pre-distributor 21 is directly connected to the syngas inlet and the gas distribution plate 22 is provided in the space between the gas pre-distributor 21 and the top of the reaction tube 10, i.e. in the inner cavity of the tower body in the space. Through the action of the gas pre-distributor 21 and the gas distribution plate 22, the synthesis gas is uniformly distributed in the radial direction before entering the reaction tube 10 after entering the tower body from the synthesis gas inlet; the synthesis gas is uniformly distributed along the radial direction and then enters the reaction tube 10 to participate in the reaction, so that the problem of nonuniform radial distribution (large central gas amount and small wall gas amount) when the synthesis gas flows in the tower body of the reactor is solved, the utilization rate of the catalyst can be improved, and the radial and axial temperature difference of the reactor is reduced. The specific structure of the gas predistributor and the gas distribution plate is not particularly limited as long as the effect of uniformly distributing the gas in the radial direction is achieved. For example, in some preferred embodiments, referring to fig. 4-5, the gas pre-distributor 21 has elongated holes 18 on its side wall, which may be 4-12, etc., and circular holes 19 on its bottom, which may be 2-6, preferably with a bottom opening area 0.3-0.6 times the side wall opening area; referring to fig. 6, the gas distribution plate may be provided with a plurality of uniformly distributed circular holes 20, the diameter of the holes may be 0.1-6.0mm, more preferably 1.0-3.0mm, and the area of the holes is preferably 5-70%, more preferably 15-55% of the cross-sectional area of the fixed bed reactor 1; by adopting the gas pre-distributor and the gas distribution plate with the preferred structures, better gas distribution effect can be achieved.
Specifically, the circulating superheated water inlet is arranged at the position, close to the lower part of the reaction tube 10, on the side wall of the tower body; the superheated water-steam mixture outlet is arranged at the position of the side wall of the tower body close to the top of the reaction tube 10, and the superheated water enters the tower body from the circulating superheated water inlet at the lower part and then enters a channel 11 (namely a heat transfer medium channel 11) between the reaction tubes 10 or between the reaction tubes 10 and the side wall of the tower body, so that the reaction heat transferred from the reaction tubes 10 is absorbed and gasified into steam, and the steam is output from the superheated water-steam mixture outlet at the upper part. In particular, the superheated water-steam mixture outlet is connected to the steam drum 2, in particular to the steam-steam mixture inlet of the steam drum 2, so that the circulating superheated water-steam mixture will be circulated to the steam drum 2 for further use. A superheated water pump is connected between the steam pocket 2 and the superheated water inlet of the fixed bed reactor 1, and superheated water (or called as circulating superheated water) in the steam pocket 2 is pumped into the fixed bed reactor 1 through the superheated water pump.
Specifically, a condensate water tank 4 and a steam drum water replenishing pump 5 are also arranged between the synthesis gas preheater 3 and the steam drum 2, and the condensate water tank 4 is connected with a condensate water outlet of the synthesis gas preheater 3 and is used for storing condensate water obtained by the synthesis gas preheater 3; the steam pocket water replenishing pump 5 is used for pumping the condensed water in the condensed water tank to the steam pocket 2 for recycling, and the condensed water can further generate superheated water after reaching the overheat temperature in the steam pocket 2 and is used as a heat transfer medium in the fixed bed reactor 1.
In some embodiments, a pressure control valve and a fixed bed reactor temperature control loop 8 are connected to a steam outlet of the steam drum 2, an opening degree of the pressure control valve is controlled by the pressure control loop 8, after the steam pressure in the steam drum 2 exceeds a set value, the pressure control valve is opened, and the steam in the steam drum 2 leaves the steam drum 2 through the valve and is input into the synthesis gas preheater 3 to perform first heat exchange with the synthesis gas. The use of a pressure control circuit to control the opening of the pressure control valve is conventional in the art and will not be described in detail. Preferably, the steam supplied to the synthesis gas preheater 3 from the steam drum 2 is medium and low pressure steam, the temperature is 220-285 ℃, and the pressure is 1.5-7.0 MPa.
The Fischer-Tropsch synthesis fixed bed reactor heat control system mainly comprises the following working processes: the synthesis gas to be preheated is introduced from the synthesis gas preheater 3, and after the first heat exchange with the steam discharged from the steam drum 2, the second heat exchange with the hot materials discharged from the fixed bed reactor 1 is continuously carried out in the synthesis gas heat exchanger 7. The steam after the first heat exchange is condensed to form condensed water, the condensed water enters a condensed water tank 4, the condensed water is sent back to the steam drum 2 by a steam drum water replenishing pump 5, the condensed water returning to the steam drum 2 reaches an overheat temperature in the steam drum 2, and the condensed water and the overheat water in the steam drum become circulating overheat water. Circulating superheated water is sent into the fixed bed reactor 1 by the superheated water pump 6, part of the circulating superheated water is vaporized after absorbing reaction heat and is changed into steam, and the mixture of the unvaporized circulating superheated water and the steam enters from the upper part of the fixed bed reactor 1 and returns to the steam drum 2, so that the cyclic utilization of water in the system is realized, and the purposes of heat transfer are achieved.
The hot synthesis gas obtained after the two heat exchanges enters from the synthesis gas inlet at the upper part of the fixed bed reactor 1, the Fischer-Tropsch synthesis reaction is carried out in the fixed bed reactor 1, the reaction product and the unreacted synthesis gas (hot material) flow out from the lower part of the fixed bed reactor 1, and the reaction product and the synthesis gas are discharged out of the system after the heat exchange with the synthesis gas through the synthesis gas heat exchanger 7. Part of the circulating superheated water absorbs the Fischer-Tropsch synthesis reaction heat and then is vaporized and enters the steam drum 2, so that the constant temperature operation of the fixed bed reactor 1 is ensured, the unvaporized circulating superheated water and vaporized steam enter the steam drum 2 together and are separated from the water and the steam, and when the pressure in the steam drum exceeds a set value, the steam leaves the steam drum through a pressure control valve (the opening of the valve is controlled by a fixed bed reactor pressure control loop 8), and the water circulation in a steam-condensation-steam drum water replenishing system is started. Superheated water (namely circulating superheated water) in the steam pocket is pumped to the heat transfer medium channel of the reactor by the superheated water pump, and the circulation of the heat taking system of the reactor is started.
For the convenience of understanding, the following description is given for the example of the heat regulation process of the fischer-tropsch synthesis fixed bed reactor using the system of the present invention, but it should not be understood that the technical solution of the present invention is limited thereto:
the fixed bed reactor 1 has a diameter of 0.42m, a total height of 2.5m, reaction tubes 10 having a length of 2.0m and a diameter of 60mm, the number of reaction tubes 10 being 7, and the arrangement thereof is shown in FIG. 2. An aluminum radiator is disposed in the reaction tube 10, and the structure is shown in fig. 3.
The activated spherical catalyst SFT814 (manufactured by Zhejiang tide new materials Co., Ltd.) in a total amount of 17.3L was packed in the reaction tube 10 with a particle size range of 30-120 μm and a normal temperature synthesis gas (hydrogen 21.8Nm3H, carbon monoxide 7.3Nm3And h) introducing from the upper part of the synthesis gas preheater 3, performing first heat exchange with steam discharged from the steam drum 2, and then performing second heat exchange with hot materials (products) discharged from the fixed bed reactor 1 in the synthesis gas heat exchanger 7 until the temperature of the synthesis gas reaches 235 ℃ (the opening of the synthesis gas inlet temperature control loop 9 controls 25-30% of the valve).
The steam pressure existing together with water, namely the saturated steam pressure of water and the temperature have a one-to-one correspondence relationship, namely the vaporization temperature of water is determined by controlling a certain steam pressure. The principle of the steam pocket is to control the temperature of the superheated water by controlling the pressure of the saturated water vapor. And the circulated superheated water is used as a heat transfer medium in the reactor, and once the temperature of the heat transfer medium used as the low-temperature end is fixed, the temperature of the catalyst bed used as the high-temperature end is fixed to a corresponding value according to the heat transfer characteristic. The steam pocket is used for controlling the reaction temperature of the Fischer-Tropsch synthesis by adopting the saturated steam pressure of the steam pocket according to the principle. The working principle of the steam drum is well known in the prior art, and the detailed description is omitted.
The synthesis gas is subjected to Fischer-Tropsch synthesis reaction under the action of a catalyst, and simultaneously releases a large amount of heat. In order to control the reaction temperature in the reactor to a certain value, the steam temperature is changed by adjusting the pressure of the steam drum. In the embodiment, the temperature of the reactor is controlled to be 250 ℃, the pressure of a steam drum is controlled to be 3.1MPa, the temperature of the circulating superheated water is 235 ℃, the flow rate of the circulating superheated water is 1.5t/h, the circulating superheated water absorbs reaction heat after passing through the reactor, and 41kg of the superheated water is vaporized into steam with the same temperature as the superheated water.
Condensed water formed after the condensation of the steam after the first heat exchange enters a condensed water tank 4, then is sent back to the steam drum 2 by a steam drum water replenishing pump 5, and the condensed water returned to the steam drum 2 is sent to the fixed bed reactor 1 by a superheated water pump 6 after reaching the superheated temperature (235 ℃) in the steam drum 2; part of the superheated water absorbs the reaction heat and is vaporized into steam, and the steam is discharged from the upper part of the fixed bed reactor 1 and enters the steam drum 2, so that the cyclic utilization of the water in the system is realized.
The hot synthesis gas after twice heat exchange enters the fixed bed reactor 1 from the synthesis gas inlet at the upper part of the fixed bed reactor 1 to carry out the Fischer-Tropsch synthesis reaction (at 235 ℃), and the reaction product flows out from the lower part of the reactor 1 (hot material). The heat generated by the Fischer-Tropsch synthesis reaction is absorbed and taken away by the vaporization of superheated water, so that the constant temperature operation of the fixed bed reactor is ensured, the circulated superheated water and the vaporized steam enter the steam pocket 2, and the steam leaves the steam pocket through a valve (the opening of the valve is controlled by the temperature control loop 8 of the fixed bed reactor) after the pressure in the steam pocket exceeds a set value (for example, 3.1 MPa).
The maximum radial temperature difference of the fixed bed reactor is 2.4 ℃ and the maximum axial temperature difference is 3.7 ℃ through detection.
It will be appreciated by those skilled in the art that modifications or adaptations to the invention may be made in light of the teachings of the present specification. Such modifications or adaptations are intended to be within the scope of the present invention as defined in the claims.
Claims (10)
1. A Fischer-Tropsch synthesis fixed bed reactor thermal control system is characterized by comprising,
the fixed bed reactor is used for contacting hot synthesis gas with a catalyst to generate a Fischer-Tropsch synthesis reaction so as to obtain a hot material containing a reaction product and unreacted synthesis gas; the fixed bed reactor is provided with a superheated water inlet for receiving circulating superheated water; a heat transfer medium channel communicated with a circulating superheated water inlet is arranged in the fixed bed reactor, and part of the circulating superheated water is vaporized into steam after absorbing reaction heat generated by Fischer-Tropsch synthesis reaction in the heat transfer medium channel to form a mixture of the circulating superheated water and the steam;
the synthesis gas preheater is used for carrying out primary heat exchange on synthesis gas to be preheated and steam to obtain primarily preheated synthesis gas and condensed water formed by heat exchange of the steam;
a syngas heat exchanger for second heat exchange of the primarily preheated syngas obtained by the syngas preheater with the hot material obtained by the fixed bed reactor to obtain hot syngas for supply to the fixed bed reactor;
a drum for supplying steam for the first heat exchange into the synthesis gas preheater and supplying the circulated superheated water to the fixed bed reactor to absorb reaction heat, and for receiving the condensed water formed in the synthesis gas preheater and a mixture of the circulated superheated water and steam formed in the fixed bed reactor, and performing vapor-liquid separation on the mixture of the circulated superheated water and steam and controlling steam pressure;
the fixed bed reactor comprises a tower body, a plurality of reaction tubes which are arranged in parallel at intervals are arranged in the tower body along the axial direction, and radial radiators are arranged in the reaction tubes; the heat transfer medium channel comprises channels formed by spaces between adjacent reaction tubes and between the reaction tubes and the inner wall of the tower body;
the whole radial radiator extends along the axial direction of the reaction tube, and comprises a plurality of radiating fins extending along the radial direction of the reaction tube, and the inner cavity of the reaction tube is divided into a plurality of independent catalyst filling cavities;
the heat radiator comprises an inner ring heat dissipation area and an outer ring heat dissipation area which are concentric, and a plurality of radiating fins extending from the axis to the outer ring heat dissipation area along the radial direction are arranged in the inner ring heat dissipation area; a plurality of radiating fins extending along the radial direction are arranged in the outer ring radiating area; the inner cavity of the reaction tube is divided into 6-30 independent catalyst filling cavities by the radiating fins of the inner ring radiating area and the outer ring radiating area; the plurality of radiating fins of the inner ring radiating area are integrally distributed in a shape like a Chinese character 'mi';
the inner ring radiating area is uniformly divided into a plurality of catalyst filling cavities with the same radial cross-sectional area by radiating fins; the outer ring radiating area is divided into a plurality of catalyst filling cavities with the same radial cross-sectional area by radiating fins; and the radial cross-sectional areas of the catalyst filling cavities of the inner ring heat dissipation area and the outer ring heat dissipation area are equal.
2. A fischer-tropsch synthesis fixed bed reactor thermal control system as claimed in claim 1, wherein in the fixed bed reactor the portion of the circulated superheated water which absorbs heat of reaction as it flows through the heat transfer medium passage is vaporised by 10 to 70 wt%; the material of the radial radiator is aluminum material, copper material, steel material or aluminum alloy.
3. A fischer-tropsch synthesis fixed bed reactor thermal control system as claimed in claim 2, wherein in the fixed bed reactor the portion of the circulated superheated water that absorbs heat of reaction as it flows through the heat transfer medium passage is vaporised by 20 to 50 wt%; the material of the radial radiator is aluminum material.
4. A fischer-tropsch synthesis fixed bed reactor thermal control system as claimed in claim 3, wherein the inner radius R of the inner annulus heat rejection zone is from 0.55 to 0.65 times the inner radius R of the entire reactor tube.
5. Fischer-Tropsch synthesis fixed bed reactor thermal control system according to any one of claims 2-4,
a plurality of reaction tubes are uniformly arranged in the tower body at intervals;
one of the reaction tubes is arranged along the axis of the tower body to serve as a central tube, and the other reaction tubes are uniformly arranged around the central tube at intervals; the distance L between the central axes of any two adjacent reaction tubes is 3-10 times of the radius R in the reaction tubes.
6. Fischer-Tropsch synthesis fixed bed reactor thermal control system according to claim 5,
the upper part or the top of the tower body is provided with a synthesis gas inlet for inputting the hot synthesis gas;
and a hot material outlet for discharging the hot material is arranged at the bottom or the lower part of the tower body.
7. Fischer-Tropsch synthesis fixed bed reactor thermal control system according to claim 6,
a gas pre-distributor is arranged in the tower body and is directly connected with the synthesis gas inlet; a gas distribution plate is arranged in a space between the gas pre-distributor and the top of the reaction tube; the gas pre-distributor and the gas distribution plate are used for uniformly distributing hot synthesis gas input from the synthesis gas inlet in a radial direction before entering the reaction tube.
8. Fischer-Tropsch synthesis fixed bed reactor thermal control system according to claim 7,
a circulating superheated water inlet of the fixed bed reactor is arranged at the position of the side wall of the tower body close to the lower part of the reaction tube;
the fixed bed reactor is also provided with a superheated water-steam mixture outlet for outputting the circulating superheated water-steam mixture from the heat transfer medium channel; the superheated water-steam mixture outlet is arranged on the side wall of the tower body and close to the top of the reaction tube;
the steam drum is provided with a steam-steam mixture inlet connected to the superheated water-steam mixture outlet of the fixed bed reactor for circulating the circulating superheated water and steam mixture produced in the fixed bed reactor into the steam drum.
9. Fischer-Tropsch synthesis fixed bed reactor thermal control system according to claim 8,
a condensate water tank and a steam pocket water replenishing pump are also arranged between the synthesis gas preheater and the steam pocket, and the condensate water tank is connected with a condensate water outlet of the synthesis gas preheater and is used for storing condensate water obtained by the synthesis gas preheater; the steam drum water replenishing pump is used for pumping the condensed water in the condensed water tank to the steam drum;
and a superheated water pump is connected between the steam drum and the fixed bed reactor and used for pumping circulating superheated water in the steam drum to the fixed bed reactor.
10. Fischer-Tropsch synthesis fixed bed reactor thermal control system according to claim 9,
a synthesis gas inlet temperature control loop is connected to a synthesis gas inlet of the fixed bed reactor and is used for controlling the temperature of hot synthesis gas to enter the synthesis gas inlet;
the steam outlet of the steam drum is connected with a pressure control valve and a fixed bed reactor temperature control loop for controlling the opening degree of the valve;
the steam supplied to the synthesis gas preheater by the steam drum is medium-low pressure steam, the temperature is 200-285 ℃, and the pressure is 1.5-7.0 MPa.
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