CN113244866B - Device and method for synthesizing light hydrocarbon through microwave-assisted gas catalysis - Google Patents
Device and method for synthesizing light hydrocarbon through microwave-assisted gas catalysis Download PDFInfo
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- CN113244866B CN113244866B CN202110526900.XA CN202110526900A CN113244866B CN 113244866 B CN113244866 B CN 113244866B CN 202110526900 A CN202110526900 A CN 202110526900A CN 113244866 B CN113244866 B CN 113244866B
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
- B01J19/122—Incoherent waves
- B01J19/126—Microwaves
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
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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
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
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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
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
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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
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00139—Controlling the temperature using electromagnetic heating
- B01J2219/00141—Microwaves
Abstract
The invention discloses a device and a method for synthesizing light hydrocarbon by microwave-assisted gas catalysis, and relates to the technical field of light hydrocarbon synthesis by microwave-assisted gas catalysis. The device is characterized in that a plurality of gas storage tanks are arranged, the gas outlet of each gas storage tank is connected with a gas preheating device through a gas transmission pipeline, and a control valve and a pressure gauge are arranged on the gas transmission pipeline; the vertical microwave heating body of the vertical microwave heating device is composed of a reaction tube, a heat preservation layer and a shell which are coaxially arranged, a microwave generating device is arranged on the outer side wall of the shell, a mounting bracket on the outer side wall of the shell is fixed in a fixing frame, the shell is arranged in the fixing frame in a hanging manner, an air inlet tube is arranged at the top of the reaction tube, an air outlet tube is arranged on the side wall of the bottom of the reaction tube, the air inlet tube is connected with a gas transmission pipeline, and the air outlet tube is connected with a cooling device; the reaction tube is internally provided with a clapboard, and wave-absorbing materials are arranged above the clapboard. The microwave and wave-absorbing material are used for heating quickly and uniformly, so that the catalytic synthesis of gas is accelerated, and the selectivity and the conversion rate of light hydrocarbon in reaction products are improved.
Description
Technical Field
The invention relates to the technical field of light hydrocarbon synthesis by microwave-assisted gas catalysis, in particular to a device and a method for light hydrocarbon synthesis by microwave-assisted gas catalysis.
Background
The existing combustible light hydrocarbon is mainly obtained by petroleum cracking, the demand of the light hydrocarbon is gradually increased along with the development of chemical industry, and the petroleum energy is increasingly deficient and is difficult to meet the market demand. The low carbonization means that carbon resources are utilized to the maximum extent and carbon dioxide emission is reduced to the maximum extent, and the scientific concept of green carbon is more and more developed in recent yearsThe more interesting it is. Wherein carbonaceous resources such as biomass, natural gas, coal and the like are converted into CO, H2And then, the carbon resource of the high-carbon resource is coupled with the hydrogen resource of the low-carbon resource, so that the carbon emission in the utilization process of the traditional high-carbon resource can be greatly reduced. In the process of preparing light hydrocarbon, CO and H are mainly passed through2The mixed gas is catalytically synthesized at high temperature, and the uniformity of heating in the process directly influences the conversion rate of the reaction and the completion rate of the reaction. Therefore, it is necessary to develop a device with high heating rate and good uniformity to improve the gas synthesis efficiency.
Disclosure of Invention
The invention aims to provide a device and a method for synthesizing light hydrocarbon by microwave-assisted gas catalysis, which solve the problems of CO and H in the prior art2Low conversion rate and low production efficiency in the process of catalytically synthesizing light dydrocarbon at high temperature.
In order to solve the technical problems, the invention adopts the following technical scheme: a device for synthesizing light hydrocarbon by microwave-assisted gas catalysis comprises a plurality of gas storage tanks, a gas preheating device, a vertical microwave heating device, a cooling device and a light hydrocarbon collecting device which are sequentially connected, wherein the gas storage tanks are connected, the gas outlet of each gas storage tank is connected with the gas preheating device through a gas transmission pipeline, and a control valve and a pressure gauge are arranged on the gas transmission pipeline; the vertical microwave heating device comprises a vertical microwave heating body, a fixing frame and a control system, wherein the vertical microwave heating body is composed of a reaction tube, a heat preservation layer and a shell which are coaxially arranged, a microwave generating device is arranged on the outer side wall of the shell, an installing support is arranged on the outer side wall of the shell and fixed in the fixing frame, the shell is arranged in the fixing frame in a hanging manner, an air inlet tube is arranged at the top of the reaction tube, an air outlet tube is arranged on the side wall of the bottom of the reaction tube and connected with an air conveying pipeline, and the air outlet tube is connected with a cooling device; the reaction tube is internally provided with a clapboard, and a wave-absorbing carrier mixed with a catalyst is arranged above the clapboard.
The further technical proposal is that two infrared temperature measuring devices are distributed on the outer side wall of the shell along the length direction; the microwave generating device is provided with two groups along the length direction of the shell, wherein one group comprises two microwave generating devices and is arranged opposite to the infrared temperature measuring device, the other group comprises three microwave generating devices, the plane where the connecting lines are located is vertical to the plane where the connecting lines of the infrared temperature measuring devices are located, and the other group is uniformly distributed along the length direction of the shell.
The control system adjusts the power of the microwave generating devices according to the temperature measured by the infrared temperature measuring device, wherein the power of three microwave generating devices which are nearest to the upper position, the relative position and the lower position of the infrared temperature measuring device is adjusted according to the temperature measured by the infrared temperature measuring device positioned above; and adjusting the power of the two microwave generating devices which are nearest to the relative position of the infrared temperature measuring device and the lower position according to the temperature measured by the infrared temperature measuring device positioned below.
According to a further technical scheme, the top of the shell is hermetically connected with a first circulating water-cooling sleeve, the top of the first circulating water-cooling sleeve is hermetically connected with a first fixed pipe, the top of the first fixed pipe is hermetically provided with an air inlet pipe, the tail end of the air inlet pipe is lower than the first circulating water-cooling sleeve, and one end of the reaction pipe penetrates through the first circulating water-cooling sleeve and then is hermetically inserted into the first fixed pipe.
The bottom of the shell is connected with a second circulating water-cooling sleeve in a sealing mode, the bottom of the second circulating water-cooling sleeve is connected with a second fixing pipe in a sealing mode, the side wall of the second fixing pipe is connected with an air outlet pipe, a K-type thermocouple is arranged at the bottom of the second fixing pipe, and the other end of the reaction pipe penetrates through the second circulating water-cooling sleeve and then is connected into the second fixing pipe in a sealing mode in an inserted mode.
The further technical scheme is that the first circulating water cooling sleeve is composed of an inner pipe and an outer pipe which are coaxially arranged, a cooling water containing cavity is formed between the inner pipe and the outer pipe, a water inlet pipe and a water outlet pipe are respectively arranged on the side wall of the outer pipe, and the water inlet pipe and the water outlet pipe are respectively connected with a water outlet and a water inlet of the circulating water cooler.
A plurality of grooves are arranged on the inner side wall of the first fixed pipe in parallel, and sealing rings are arranged in the grooves.
The further technical scheme is that the fixing frame comprises a frame, a top plate and an opening and closing door, the frame is formed by mutually connecting an upright post and a cross beam, the top plate is arranged at the top of the frame, the opening and closing door is hinged to the upright post of the frame and covers four side faces of the frame, and the top plate is provided with a yielding hole of the vertical microwave heating body.
The invention also relates to a method for synthesizing light hydrocarbon by microwave-assisted gas catalysis, which is characterized by comprising the following steps:
s1, granulating and pelletizing Fe-based catalyst powder and silicon carbide powder according to a mass ratio of 1: 3-5, filling the mixture into a reaction tube, and introducing N2Air in the pipe is removed, and N is continuously introduced2Heating to 300-350 ℃, and introducing H2Pretreating the catalyst for 2-3 h; the particle size of the granulated and pelletized Fe-based catalyst powder and silicon carbide powder is 8-25 mm;
s2, cooling the reaction tube to 290-340 ℃, introducing the synthesis gas into a gas preheating device, preheating to 150-200 ℃, introducing into the reaction tube, raising the temperature to 320-350 ℃ at a heating rate of 5-10 ℃/min, and reacting for 19-30 h;
and S3, enabling the product to enter a cooling device from an air outlet pipe for cooling, and then collecting the product in a light hydrocarbon collecting device, wherein the cooling temperature is 140-145 ℃.
The further technical proposal is that H in the synthesis gas is2And the molar ratio of the CO gas is 1-2.
Compared with the prior art, the invention has the beneficial effects that:
1. the reaction gas is preheated by the gas preheating device, so that the problem of low direct heating rate is solved; the microwave and wave-absorbing material are used for heating quickly and uniformly, so that the catalytic synthesis of gas is accelerated, and the selectivity and the conversion rate of light hydrocarbon in reaction products are improved.
2. Through the dismantlement and the change of circulating water cooling sleeve pipe, fixed pipe, realize the fast switch-over of reaction tube, can change into new or reaction tube that the pipe diameter is littleer. In order to avoid the phenomenon that the sealing piece between the fixed pipe and the reaction pipe is damaged due to overhigh temperature in the pipe in the reaction process, the two ends of the reaction pipe are cooled through the circulating water cooling sleeve.
3. In order to make the temperature field in the reaction tube more uniform, the microwave generating devices are uniformly distributed along the length direction of the shell; in order to enable the temperature measurement to be more accurate, a K-type thermocouple is arranged at the bottom of the reaction tube, two infrared temperature measuring devices are distributed on the shell, and the temperature in the reaction tube is strictly monitored through multipoint temperature measurement.
4. The opening and closing doors are arranged on the four sides of the frame, so that the microwave heating device in the frame can be maintained and overhauled conveniently in all directions.
5. Silicon carbide is used as wave absorbing material and Fe-based catalyst in N2And H2The catalyst is pretreated in a reducing atmosphere to promote the activation of the catalyst, so that the inherent performance of the catalyst is fully exerted, and the activation energy of the reaction is reduced. And introducing the synthesis gas subjected to preheating treatment into a reaction tube, and carrying out catalytic reaction at 320-350 ℃ to obtain gaseous light hydrocarbon serving as fuel.
6. The device and the method adopt a high-temperature Fischer-Tropsch synthesis technology to prepare light hydrocarbon by utilizing synthesis gas, do not depend on a production mode of taking petroleum as a raw material any more, reduce the consumption of petroleum resources, and combine with a microwave heating technology to enable reactants to be integrally heated from inside to outside, so that the integral heating rate is more efficient, and the conversion rate and the production rate are greatly improved.
Drawings
Fig. 1 is a schematic diagram of the structure of the present invention.
FIG. 2 is a schematic structural view of a vertical microwave heating apparatus according to the present invention.
FIG. 3 is a schematic structural view of the vertical microwave heating apparatus of the present invention without the door being opened or closed.
FIG. 4 is a schematic structural view of a vertical microwave heating body according to the present invention.
Fig. 5 is a cross-sectional view taken along line C-C of fig. 4.
Fig. 6 is an enlarged view of a portion a in fig. 5.
Fig. 7 is an enlarged view of the portion B in fig. 5.
In the figure: 1-gas storage tank, 2-gas preheating device, 3-vertical microwave heating device, 301-reaction tube, 302-heat preservation layer, 303-shell, 304-microwave generating device, 305-mounting bracket, 306-fixing bracket, 307-gas inlet tube, 308-gas outlet tube, 309-clapboard, 310-infrared temperature measuring device, 311-frame, 312-top plate, 313-opening and closing door, 4-cooling device, 5-light hydrocarbon collecting device, 6-control valve, 7-pressure gauge, 8-gas transmission pipeline, 9-wave absorbing carrier mixed with catalyst, 10-first circulating water cooling sleeve, 11-first fixing tube, 12-second circulating water cooling sleeve, 13-second fixing tube, 14-K type thermocouple, 15-circulating cooling water machine, 16-sealing ring.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
Fig. 1 shows a device for synthesizing light hydrocarbon by microwave-assisted gas catalysis, which comprises two gas storage tanks 1, wherein one gas storage tank 1 is used for supplying CO, and the other gas storage tank 1 is used for supplying hydrogen. The gas outlet of each gas storage tank 1 is respectively connected with the gas preheating device 2 through a gas transmission pipeline 8, so that the adding amount of the reaction gas is conveniently controlled, a control valve 6 and a pressure gauge 7 are arranged on the gas transmission pipeline 8, and a flow meter can be designed. The gas preheating device 2 is connected to the gas inlet pipe 307 of the vertical microwave heating device 3 through a pipe.
As shown in fig. 2 and 3, the vertical microwave heating device 3 includes a vertical microwave heating body, a fixing frame 306 and a control system. As shown in fig. 4 and 5, the vertical microwave heating body is composed of a reaction tube 301, an insulating layer 302, and a housing 303, which are coaxially disposed. The reaction tube 301 is a quartz glass tube, the heat insulation layer 302 is made of polycrystalline mullite material, and the thickness is 60-70 mm. The shell 303 can be made of stainless steel, and the effective heating length is 600-800 mm. The outer side wall of the shell 303 is provided with a microwave generating device 304, the microwave generating device 304 comprises a microwave emitter and a microwave power supply, wherein the microwave emitter consists of a magnetron, a waveguide, a circulator, a tuner, a water load and a director, the microwave working frequency is about 2450 +/-50 MHZ, and the total power is 0-6500W. 5 microwave power supplies of 1KW, 5 magnetrons of 1KW and WYBJ-05-08 waveguide are adopted, and the heating temperature range of gas materials is between 25 and 1000 ℃. Two infrared temperature measuring devices 310 are distributed on the outer side wall of the shell 303 along the length direction of the shell; the microwave generating devices 304 are arranged in two groups along the length direction of the shell 303, wherein one group is two and is arranged opposite to the infrared temperature measuring device 310, the other group is three and is uniformly distributed along the length direction of the shell 303, and the plane where the connecting lines of the three microwave generating devices 304 are arranged is vertical to the plane where the connecting lines of the infrared temperature measuring device 310 are arranged.
The control system adjusts the power of the microwave generating devices 304 according to the temperature measured by the infrared temperature measuring device 310, wherein the power of the three microwave generating devices 304 nearest to the upper, relative and lower positions of the infrared temperature measuring device 310 is adjusted according to the temperature measured by the infrared temperature measuring device 310 located above; based on the temperature measured by the lower infrared temperature measuring device 310, the power of a total of two microwave generating devices 304 located at the relative position of the infrared temperature measuring device 310 and nearest to the lower position is adjusted. The temperature control mode enables the temperature field in the reaction tube 301 to be more uniform and the temperature control to be more accurate.
The fixed frame 306 comprises a frame 311, a top plate 312 and an opening and closing door 313, the frame 311 is made of aluminum alloy materials and is formed by connecting upright posts and cross beams, the top plate 312 is arranged at the top of the frame 311, the opening and closing door 313 is hinged on the upright posts of the frame 311 and covers four side faces of the frame 311, and the top plate 312 is provided with a yielding hole of the vertical microwave heating body. Be provided with installing support 305 on the casing 303 lateral wall, installing support 305 fixes on the crossbeam in mount 306, and the unsettled setting of casing 303 is in mount 306, and reaction tube 301 top is provided with intake pipe 307, is provided with outlet duct 308 on the lateral wall of reaction tube 301 bottom, and outlet duct 308 is connected with cooling device 4, and cooling device 4 passes through the pipeline and is connected with lighter hydrocarbons collection device 5. A partition plate 309 is arranged in the reaction tube 3, a wave-absorbing carrier 9 mixed with a catalyst is arranged above the partition plate 309, and a silicon carbide ball is adopted as a wave-absorbing material.
As shown in fig. 6, the top of the housing 303 is hermetically connected with a first circulating water cooling sleeve 10, the top of the first circulating water cooling sleeve 10 is hermetically connected with a first fixed pipe 11, the top of the first fixed pipe 11 is hermetically provided with an air inlet pipe 307, one end of the reaction tube 301 passes through the first circulating water cooling sleeve 10 and then is hermetically inserted into the first fixed pipe 11, a plurality of grooves are arranged in parallel on the inner side wall of the first fixed pipe 11, and a sealing ring 16 is arranged in each groove.
As shown in fig. 7, the bottom of the housing 303 is hermetically connected to a second circulating water-cooling sleeve 12, the bottom of the second circulating water-cooling sleeve 12 is hermetically connected to a second fixing tube 13, the sidewall of the second fixing tube 13 is connected to an air outlet tube 308, the bottom of the second fixing tube 13 is provided with a K-type thermocouple 14, and the other end of the reaction tube 301 passes through the second circulating water-cooling sleeve 12 and then is hermetically inserted into the second fixing tube 13. A plurality of grooves are arranged on the inner side wall of the second fixed pipe 13 in parallel, and sealing rings 16 are arranged in the grooves.
Such setting is convenient for the change of reaction tube 301, and when the reaction tube 301 that the pipe diameter is littleer needs to be changed, will first fixed pipe 11 pull down, can take out reaction tube 301, change the first circulating water cooling jacket pipe 10, second circulating water cooling jacket pipe 12, the fixed pipe 13 of second that correspond the pipe diameter size again after, with the reaction tube 301 of little pipe diameter good dress back, again with the first fixed pipe 11 of corresponding pipe diameter good can. For the convenience device, each circulating water-cooling sleeve and each fixed pipe are sealed and fixed by a flange and a sealing ring. The gas inlet pipe 307 and the K-type thermocouple 14 are also fixed by flanges and extend into the reaction tube 301. When the quartz glass tube is aged and needs to be replaced by a new reaction tube 301, the first fixing tube 11 and the air inlet pipe 307 are detached, so that the reaction tube 301 can be replaced, and the replacement mode is simple and quick.
Example 2
S1, 36g of Fe-based catalyst (K-S-Zn)0.69Fe2.31O4) Mixing 144g of silicon carbide and the mixture in a ratio of 1:4, granulating to obtain spherical solid with the particle size of 8-12 mm, filling the spherical solid into a reaction tube 301, and introducing N at a flow rate of 90mL/min2Air in the pipe is removed, and N is continuously introduced2And the temperature is raised to 350 ℃, H is introduced2Pretreating the catalyst by N in the reaction tube2And H2The volume ratio is 1:1, and the pretreatment time is 2 h.
S2, stopping introducing H2While continuously introducing N2Then, the reaction tube 301 is naturally cooled to 340 ℃, and the reaction is stoppedAdding N2. Synthesis gas (H)2/CO 2) was introduced into the gas preheating device 2, preheated to 150 ℃, introduced into the reaction tube 301 at 45mL/min, and the synthesis gas addition was stopped when the pressure in the reaction tube 301 reached 0.2 Mpa. And the circulating cooling water is started, and the temperature difference between the water inlet pipe and the water outlet pipe of the first circulating water-cooling sleeve 10 and the second circulating water-cooling sleeve 12 is kept at 8-20 ℃. The temperature of the reactant in the reaction tube 301 is raised to 350 ℃ at the temperature raising rate of 5 ℃/min, and the reaction is carried out for 30 h.
And S3, after the reaction is finished, enabling the product to enter a cooling device 4 from an air outlet pipe 308 for cooling, and then collecting the product in a light hydrocarbon collecting device 5, wherein the cooling temperature is 145 ℃. The product contains 18.7% of CH47.2% of C2～4Alkane, 39.6% C2～4Olefin, 27.8% C5+Hydrocarbon, 6.7% oxygenate, CO conversion 51.5%.
Example 3
S1, mixing 10g of Fe-based catalysts (Fe/NCTs) and 50g of silicon carbide powder in a ratio of 1:5, granulating to obtain spherical solids with the particle size of 8-12 mm, filling the spherical solids into a reaction tube 301, and introducing N at a flow rate of 15mL/min2Air in the pipe is removed, and N is continuously introduced2And the temperature is raised to 340 ℃, H is introduced2Pretreating the catalyst by N in the reaction tube2And H2The volume ratio is 1:1, and the pretreatment time is 3 h.
S2, stopping introducing H2While continuously introducing N2Then, the reaction tube 301 is naturally cooled to 290 ℃ and the addition of N is stopped2. Synthesis gas (H)2and/CO is 1), introducing the gas preheating device 2, preheating to 180 ℃, introducing the gas into the reaction tube 301 at a rate of 45mL/min, stopping adding the synthesis gas when the air pressure in the reaction tube 301 reaches 0.2Mpa, starting circulating cooling water, and keeping the temperature difference between the water inlet pipe and the water outlet pipe of the first circulating water-cooling sleeve 10 and the second circulating water-cooling sleeve 12 at 8-20 ℃. The temperature of the reactant in the reaction tube 301 is increased to 300 ℃ at the temperature increasing rate of 10 ℃/min, and the reaction is carried out for 19 h.
And S3, after the reaction is finished, enabling the product to enter a cooling device 4 from an air outlet pipe 308 for cooling, and then collecting the product in a light hydrocarbon collecting device 5, wherein the cooling temperature is 140 ℃. The product contains 22.2% of CH45.7% of C2～4Alkane, 46.7% C2～4Olefin, 25.4% C5+The conversion of hydrocarbons, CO was 14.4%.
Example 4
S1, 30g of Fe-based catalyst (FeMn)15Na16) Mixing with 90g of silicon carbide powder in a ratio of 1:3 for granulation to obtain spherical solid with the particle size of 10-20 mm, filling the spherical solid into a reaction tube 301, and introducing N at a flow rate of 30mL/min2Air in the pipe is removed, and N is continuously introduced2And the temperature is raised to 300 ℃, H is introduced2Pretreating the catalyst by N in the reaction tube2And H2The volume ratio is 1:1, and the pretreatment time is 2.5 h.
S2, stopping introducing H2While continuously introducing N2Then, the reaction tube 301 is naturally cooled to 300 ℃, and N addition is stopped2. Synthesis gas (H)2and/CO ═ 2) is introduced into the gas preheating device 2, the gas is introduced into the reaction tube 301 at a rate of 30mL/min after being preheated to 200 ℃, when the air pressure in the reaction tube 301 reaches 0.2Mpa, the addition of the synthesis gas is stopped, the circulating cooling water is started, and the temperature difference between the water inlet pipe and the water outlet pipe of the first circulating water cooling sleeve 10 and the second circulating water cooling sleeve 12 is kept at 8-20 ℃. The temperature of the reactant in the reaction tube 301 is raised to 320 ℃ at the temperature raising rate of 8 ℃/min, and the reaction is carried out for 24 hours.
And S3, after the reaction is finished, enabling the product to enter a cooling device 4 from an air outlet pipe 308 for cooling, and then collecting the product in a light hydrocarbon collecting device 5, wherein the cooling temperature is 143 ℃. The product contains 10.39% of CH44.53% of C2～4Alkane, 30.18% C2～4Olefin, 54.90% C5+The conversion of hydrocarbon, CO was 96.47%.
Although the invention has been described herein with reference to a number of illustrative embodiments thereof, it should be understood that numerous other modifications and embodiments can be devised by those skilled in the art that will fall within the spirit and scope of the principles of this disclosure. More particularly, various variations and modifications are possible in the component parts or arrangements within the scope of the disclosure, the drawings and the appended claims. In addition to variations and modifications in the component parts or arrangements, other uses will also be apparent to those skilled in the art.
Claims (5)
1. The utility model provides a device of synthetic light hydrocarbon of microwave-assisted gas catalysis which characterized in that: the device comprises a plurality of gas storage tanks (1), a gas preheating device (2), a vertical microwave heating device (3), a cooling device (4) and a light hydrocarbon collecting device (5) which are connected in sequence, wherein the gas storage tanks (1) are provided with a plurality of gas outlets, each gas outlet of each gas storage tank (1) is connected with the gas preheating device (2) through a gas transmission pipeline (8), and a control valve (6) and a pressure gauge (7) are arranged on each gas transmission pipeline (8); the vertical microwave heating device (3) comprises a vertical microwave heating body, a fixing frame (306) and a control system, wherein the vertical microwave heating body is composed of a reaction tube (301), a heat insulation layer (302) and a shell (303) which are coaxially arranged, a microwave generating device (304) is arranged on the outer side wall of the shell (303), a mounting bracket (305) is arranged on the outer side wall of the shell (303), the mounting bracket (305) is fixed in the fixing frame (306), the shell (303) is arranged in the fixing frame (306) in a hanging manner, an air inlet tube (307) is arranged at the top of the reaction tube (301), an air outlet tube (308) is arranged on the side wall of the bottom of the reaction tube (301), one end of the air inlet tube (307) is connected with the air conveying pipeline (8), and the air outlet tube (308) is connected with the cooling device (4); a partition plate (309) is arranged in the reaction tube (301), and a wave-absorbing carrier (9) mixed with a catalyst is arranged above the partition plate (309);
the top of the shell (303) is hermetically connected with a first circulating water-cooling sleeve (10), the top of the first circulating water-cooling sleeve (10) is hermetically connected with a first fixed pipe (11), the top of the first fixed pipe (11) is hermetically provided with an air inlet pipe (307), and the other end of the air inlet pipe (307) is lower than the first circulating water-cooling sleeve (10); one end of the reaction tube (301) passes through the first circulating water-cooling sleeve (10) and then is hermetically inserted in the first fixed tube (11);
the bottom of the shell (303) is hermetically connected with a second circulating water-cooling sleeve (12), the bottom of the second circulating water-cooling sleeve (12) is hermetically connected with a second fixed pipe (13), the side wall of the second fixed pipe (13) is connected with an air outlet pipe (308), the bottom of the second fixed pipe (13) is provided with a K-type thermocouple (14), and the other end of the reaction pipe (301) penetrates through the second circulating water-cooling sleeve (12) and then is hermetically inserted in the second fixed pipe (13);
a plurality of grooves are arranged on the inner side walls of the first fixing pipe (11) and the second fixing pipe (13) in parallel, and sealing rings (16) are arranged in the grooves;
two infrared temperature measuring devices (310) are distributed on the outer side wall of the shell (303) along the length direction; the microwave generating devices (304) are provided with two groups along the length direction of the shell (303), wherein one group is two and is arranged opposite to the infrared temperature measuring device (310), the other group is three, the plane where the connecting line is positioned is vertical to the plane where the connecting line of the infrared temperature measuring device (310) is positioned, and the other group is uniformly distributed along the length direction of the shell (303); the control system adjusts the power of the microwave generating devices (304) according to the temperature measured by the infrared temperature measuring devices (310), wherein the power of three microwave generating devices (304) which are nearest to the upper, relative and lower positions of the infrared temperature measuring devices (310) is adjusted according to the temperature measured by the infrared temperature measuring devices (310) which are positioned above; according to the temperature measured by the infrared temperature measuring device (310) positioned below, adjusting the power of the total two microwave generating devices (304) which are positioned at the relative position of the infrared temperature measuring device (310) and are nearest to the position below;
the wave-absorbing carrier (9) is prepared by granulating and pelletizing Fe-based catalyst powder and silicon carbide powder according to a mass ratio of 1: 3-5.
2. The device of claim 1, wherein the microwave-assisted gas catalytic synthesis of light hydrocarbons comprises: the first circulating water cooling sleeve (10) is composed of an inner pipe and an outer pipe which are coaxially arranged, a cooling water containing cavity is formed between the inner pipe and the outer pipe, a water inlet pipe and a water outlet pipe are respectively arranged on the side wall of the outer pipe, and the water inlet pipe and the water outlet pipe are respectively connected with a water outlet and a water inlet of the circulating water cooling machine (15).
3. The device of claim 1, wherein the microwave-assisted gas catalytic synthesis of light hydrocarbons comprises: the fixed frame (306) comprises a frame (311), a top plate (312) and an opening and closing door (313), the frame (311) is formed by connecting upright posts and cross beams, the top plate (312) is arranged at the top of the frame (311), the opening and closing door (313) is hinged on the upright posts of the frame (311) and covers four side faces of the frame (311), and the top plate (312) is provided with a yielding hole of the vertical microwave heating body.
4. The method for catalytically synthesizing light hydrocarbons with microwave-assisted gas for the device for catalytically synthesizing light hydrocarbons with microwave-assisted gas according to claim 1, wherein the method comprises the following steps: the method comprises the following steps:
s1, granulating and pelletizing Fe-based catalyst powder and silicon carbide powder according to a mass ratio of 1: 3-5, filling the granulated and pelletized Fe-based catalyst powder and silicon carbide powder into a reaction tube (301), and introducing N2Air in the pipe is removed, and N is continuously introduced2Heating to 300-350 ℃, and introducing H2Pretreating the catalyst for 2-3 h; the particle size of the granulated and pelletized Fe-based catalyst powder and silicon carbide powder is 8-25 mm;
s2, cooling the reaction tube (301) to 290-340 ℃, introducing the synthesis gas into a gas preheating device (2), preheating to 150-200 ℃, introducing into the reaction tube (301), raising the temperature to 320-350 ℃ at a temperature rise rate of 5-10 ℃/min, and reacting for 19-30 h;
s3, cooling the product entering the cooling device (4) from the air outlet pipe (308), and collecting the product in the light hydrocarbon collecting device (5) at the cooling temperature of 140-145 ℃.
5. The method for synthesizing light hydrocarbon under the catalysis of microwave-assisted gas for the device for synthesizing light hydrocarbon under the catalysis of microwave-assisted gas according to claim 4, wherein the method comprises the following steps: h in the synthesis gas2And the molar ratio of the CO gas is 1-2.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219384A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Catalyst for reaction of one-step conversion into low carbon olefin hydrocarbon with synthesis gas |
| CN101396647A (en) * | 2007-09-29 | 2009-04-01 | 中科合成油技术有限公司 | Gas-liquid-solid three-phase suspended bed reactor for f-t synthesis and use thereof |
| CN103331171A (en) * | 2013-07-08 | 2013-10-02 | 华东理工大学 | Preparation method and applications of catalyst used for preparing light olefin from synthesis gas |
| CN105817254A (en) * | 2016-04-19 | 2016-08-03 | 江南大学 | Application of iron-based catalyst with porous film structure in Fischer-Tropsch reaction |
| CN107206341A (en) * | 2014-11-24 | 2017-09-26 | 南非大学 | A kind of fixed bed reactors |
| CN107723015A (en) * | 2017-11-06 | 2018-02-23 | 南昌大学 | A kind of device of downdraft fast pyrogenation biomass |
| CN109046416A (en) * | 2018-10-19 | 2018-12-21 | 中国科学技术大学先进技术研究院 | A kind of Fe3O4@χ-Fe5C2/Zn2SiO4Nanocatalyst and its preparation method and application |
| CN213141937U (en) * | 2020-09-21 | 2021-05-07 | 昆明理工大学 | Novel microwave heating catalysis biomass gasification's reaction device |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5427741A (en) * | 1993-05-19 | 1995-06-27 | Cem Corporation | Pressure resistant reinforcing means for containers for materials to be microwave heated |
| CN100441732C (en) * | 2002-05-08 | 2008-12-10 | Btu国际公司 | Plasma-assisted reinforced coating |
| US7662530B2 (en) * | 2005-06-24 | 2010-02-16 | Ricoh Company, Ltd. | Image forming apparatus and image forming method |
| CN101827638B (en) * | 2007-08-03 | 2016-07-13 | 埃尔西韦公司 | Porous body and method |
| FR2923732B1 (en) * | 2007-11-16 | 2011-03-04 | Nicolas Ugolin | METHOD USING PLASMA-COUPLED SOLAR THERMAL ENERGY TO PRODUCE LIQUID FUEL AND DIHYDROGEN FROM BIOMASS OR FOSSIL CHARCOAL (P-SL AND P-SH PROCESS) |
| JP4774564B2 (en) * | 2008-10-07 | 2011-09-14 | 住友化学株式会社 | Method for producing aluminum titanate ceramic powder |
| CA2812031A1 (en) * | 2010-09-10 | 2012-03-15 | Geoffrey A. Ozin | Photoactive material |
| DE102012010542A1 (en) * | 2011-12-20 | 2013-06-20 | CCP Technology GmbH | METHOD AND APPARATUS FOR GENERATING SYNTHESEGAS |
| WO2014207096A1 (en) * | 2013-06-27 | 2014-12-31 | Sicat | Method for manufacturing shaped beta-sic mesoporous products and products obtained by this method |
| CA2916875C (en) * | 2015-01-08 | 2021-01-05 | Alfred Y. Wong | Conversion of natural gas to liquid form using a rotation/separation system in a chemical reactor |
| CN109277057A (en) * | 2017-05-05 | 2019-01-29 | 储晞 | A kind of reactor assembly producing granular materials and method |
| CN107715987A (en) * | 2017-09-28 | 2018-02-23 | 刘军 | A kind of breaker roll roller tooth of biomass fuel crusher and preparation method thereof |
| CN111551031A (en) * | 2020-05-09 | 2020-08-18 | 中国华能集团有限公司 | Tubular furnace test system and method for catalytic oxidation of CO in coal-fired flue gas |
-
2021
- 2021-05-14 CN CN202110526900.XA patent/CN113244866B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101219384A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Catalyst for reaction of one-step conversion into low carbon olefin hydrocarbon with synthesis gas |
| CN101396647A (en) * | 2007-09-29 | 2009-04-01 | 中科合成油技术有限公司 | Gas-liquid-solid three-phase suspended bed reactor for f-t synthesis and use thereof |
| CN103331171A (en) * | 2013-07-08 | 2013-10-02 | 华东理工大学 | Preparation method and applications of catalyst used for preparing light olefin from synthesis gas |
| CN107206341A (en) * | 2014-11-24 | 2017-09-26 | 南非大学 | A kind of fixed bed reactors |
| CN105817254A (en) * | 2016-04-19 | 2016-08-03 | 江南大学 | Application of iron-based catalyst with porous film structure in Fischer-Tropsch reaction |
| CN107723015A (en) * | 2017-11-06 | 2018-02-23 | 南昌大学 | A kind of device of downdraft fast pyrogenation biomass |
| CN109046416A (en) * | 2018-10-19 | 2018-12-21 | 中国科学技术大学先进技术研究院 | A kind of Fe3O4@χ-Fe5C2/Zn2SiO4Nanocatalyst and its preparation method and application |
| CN213141937U (en) * | 2020-09-21 | 2021-05-07 | 昆明理工大学 | Novel microwave heating catalysis biomass gasification's reaction device |
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