CN111205153A - Carbon three-fraction liquid-phase hydrogenation reaction device and method - Google Patents
Carbon three-fraction liquid-phase hydrogenation reaction device and method Download PDFInfo
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- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
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Abstract
The invention provides a carbon three-fraction liquid-phase hydrogenation reaction device, which comprises: the device comprises a liquid phase hydrogenation reactor and a micron bubble generator which is arranged outside the liquid phase hydrogenation reactor and connected with a material inlet of the liquid phase hydrogenation reactor; the micron bubble generator comprises a cylinder body, an air inlet arranged at a first port of the cylinder body, a liquid feed inlet arranged on the side wall of the cylinder body and an ultrasonic pipeline which is arranged at a second port of the cylinder body and is coaxially communicated with the cylinder body; an ultrasonic vibrator is arranged on the side wall of the ultrasonic pipeline, and the port of the ultrasonic pipeline is connected with the material inlet of the liquid phase hydrogenation reactor. The liquid phase hydrogenation reaction device provided by the invention has a simple structure, is convenient to operate, is beneficial to industrial production, can improve the efficiency of industrial production, and can greatly improve the mass transfer efficiency between gas and liquid phases by premixing the reaction materials by the micron bubble generator before the reaction materials enter the liquid phase hydrogenation reactor for hydrogenation reaction, thereby improving the conversion rate of the catalytic hydrogenation of the propine and the propadiene in the carbon three-fraction.
Description
Technical Field
The invention relates to the field of carbon three-fraction liquid-phase hydrogenation, in particular to a carbon three-fraction liquid-phase hydrogenation reaction device and a carbon three-fraction liquid-phase hydrogenation reaction method using the same.
Background
Steam cracking of petroleum hydrocarbons is the most important method for preparing polyolefin monomers such as propylene. Acetylenes and dienes produced during propylene production are detrimental impurities affecting propylene polymerization, which inhibit the activity of the propylene polymerization catalyst, increase catalyst consumption, reduce the properties of the propylene polymer product and must be removed. The industry generally adopts a catalytic selective hydrogenation method and a solvent absorption method to remove alkynes and dienes in pyrolysis gas. The catalytic selective hydrogenation method has the advantages of simple process flow, high propylene selectivity, few byproducts and no environmental pollution, is a preferred method of green chemical technology, and is increasingly commonly applied.
In the traditional hydrocarbon steam cracking process, the liquid phase selective hydrogenation method of the carbon three-fraction comprises the following steps: fresh carbon three-fraction containing propyne and propadiene extracted from the top of the depropanizing tower enters a selective hydrogenation reactor after hydrogen preparation, a carbon three-liquid phase selective hydrogenation catalyst is filled in the hydrogenation reactor, the fed material passes through a selective hydrogenation catalyst bed layer from top to bottom, and a reaction product is discharged from the bottom of the reactor for subsequent secondary treatment. The liquid phase selective hydrogenation of the carbon three-fraction mainly adopts a fixed bed reactor, a gas-liquid-solid three-phase coexisting reaction system is formed in the reactor, and the reaction efficiency depends on the interphase mass transfer speed of the gas-liquid-solid three-phase. Because the gas phase needs to be dissolved in the liquid phase to be subjected to adsorption reaction with the solid phase (catalyst), the distribution mode of the gas phase in the liquid phase has great influence on the mass transfer efficiency of the reactor and the catalytic hydrogenation effect.
GB1175709A discloses a liquid phase catalytic hydrogenation device for benzene hydrogenation to ethylene. In the liquid phase catalytic hydrogenation equipment, hydrogen and liquid are introduced into a hydrogenation reactor, pass through a catalyst bed layer and a pore plate at the upper part of the reactor, a gas phase is separated from a gas phase separation chamber at the middle part of the reactor and is discharged out of the reactor through a pipeline, the gas phase also continuously passes through the catalyst bed layer and the pore plate at the lower part of the reactor and is contacted with hydrogen flowing reversely, and the liquid after hydrogenation flows out of the bottom of the reactor. Although the heat exchange energy consumption can be reduced by the middle gas extraction, the gas-liquid separation mode discharges gas phase by adopting a mode of opening the side wall of the reactor, so that materials of the reactor can not uniformly pass through the catalyst bed layer easily, the hydrogen concentration of the catalyst bed layer is unevenly distributed, a large amount of wall flow and bias flow are generated, and the mass transfer efficiency between gas and liquid phases and the hydrogenation efficiency of the catalyst are reduced.
CN105582854A discloses a fixed bed hydrogenation reactor and an application method thereof. The fixed bed reactor adopts a gas-liquid phase product pre-separation technology for gas phase extraction at the axis position, and the inner wall of the reactor is provided with a plurality of layers of baffle plates. The reactor is provided with a pre-distributor, a gas-liquid distribution plate, a catalyst bed layer, a gas-liquid phase separation chamber and a liquid phase outlet collector arranged at the bottom of the reactor in sequence from top to bottom along the axial direction of the reactor, a gas phase discharge port is positioned at the upper part of the gas-liquid phase separation chamber, and a baffle plate is arranged at the upward or downward direction of the gas phase discharge port. In the hydrogenation operation, liquid phase materials and hydrogen are mixed and then enter from an inlet at the upper part of the cylinder, and are uniformly distributed with a gas phase and a liquid phase through a pre-distributor and a gas-liquid distribution disc, and then hydrogenation reaction is carried out through a catalyst bed layer. Although the reactor improves the operation stability of a hydrogenation system, improves the gas-liquid distribution state in the reactor, and eliminates the problems of wall flow, bias flow and the like, the reactor has a complex structure, is not easy to operate in the industrial production process, and is not beneficial to the improvement of the production efficiency.
Disclosure of Invention
Aiming at the defect of low gas-liquid phase mass transfer efficiency of a carbon three-fraction liquid phase hydrogenation reaction device in the prior art, the invention provides a carbon three-fraction liquid phase hydrogenation reaction device and a method. The carbon three-fraction liquid-phase hydrogenation reaction device provided by the invention is simple in structure, and can greatly improve the mass transfer efficiency between gas and liquid phases and improve the conversion rate of catalytic hydrogenation of propyne and propadiene in the carbon three-fraction.
The invention provides a carbon three-fraction liquid-phase hydrogenation reaction device, which comprises: the device comprises a liquid-phase hydrogenation reactor and a micron bubble generator which is arranged outside the liquid-phase hydrogenation reactor and connected with a material inlet of the liquid-phase hydrogenation reactor;
the micron bubble generator comprises a cylinder body, an air inlet arranged at a first port of the cylinder body, a liquid feed inlet arranged on the side wall of the cylinder body and an ultrasonic pipeline which is arranged at a second port of the cylinder body and is coaxially communicated with the cylinder body; and the side wall of the ultrasonic pipeline is provided with an ultrasonic vibrator, and the port of the ultrasonic pipeline is connected with the material inlet of the liquid phase hydrogenation reactor.
In a second aspect of the present invention, a method for performing liquid phase hydrogenation by using the above liquid phase hydrogenation reaction apparatus is provided, wherein a carbon three-cut fraction containing propyne and propadiene and a hydrogen stream are contacted with a selective hydrogenation catalyst in the liquid phase hydrogenation reaction apparatus under selective hydrogenation conditions to perform selective hydrogenation, so as to obtain a hydrogenation material.
The liquid phase hydrogenation reaction device provided by the invention has a simple structure, is convenient to operate, is beneficial to industrial production, can improve the efficiency of industrial production, and can greatly improve the mass transfer efficiency between gas and liquid phases by premixing the reaction materials by the micron bubble generator before the reaction materials enter the liquid phase hydrogenation reactor for hydrogenation reaction, thereby improving the conversion rate of the catalytic hydrogenation of the propine and the propadiene in the carbon three-fraction.
Drawings
FIG. 1 is a schematic diagram of a liquid-phase hydrogenation reaction apparatus for three carbon fractions according to the present invention;
FIG. 2 is a schematic diagram of another carbon three-fraction liquid-phase hydrogenation reaction device provided by the invention;
FIG. 3 is a schematic diagram of a prior art carbon three-cut liquid phase hydrogenation reactor;
fig. 4 is a schematic structural diagram of a micro bubble generator provided by the present invention.
FIG. 5 is a side view of a micro bubble generator of the present invention.
Description of the reference numerals
1-hydrogenation reactor cylinder 2-hydrogenation reactor outlet 3-catalyst bed layer
4-hydrogenation reactor inlet 5-micron bubble generator 6-pump
7-micron bubble generator cylinder 8-first port 9-second port
10-liquid feed inlet 11-ultrasonic pipeline 12-ultrasonic vibrator
13-air intake
Detailed Description
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.
In a first aspect, the present invention provides a carbon three-fraction liquid-phase hydrogenation apparatus, as shown in fig. 1, including: a liquid phase hydrogenation reactor and a micron bubble generator 11 (the specific structure is shown in figure 4) which is arranged outside the liquid phase hydrogenation reactor and is connected with the material inlet 4 of the liquid phase hydrogenation reactor;
as shown in fig. 4, the micro bubble generator 11 comprises a cylinder 7, an air inlet 13 arranged at a first port 8 of the cylinder, a liquid feed inlet 10 arranged on the side wall of the cylinder, and an ultrasonic pipeline 11 arranged at a second port 9 of the cylinder and coaxially communicated with the cylinder; an ultrasonic vibrator 12 is arranged on the side wall of the ultrasonic pipeline, and the port of the ultrasonic pipeline is connected with the material inlet 4 of the liquid phase hydrogenation reactor.
In the invention, a liquid feed port 10 on the micro-bubble generator 11 is connected with an external liquid pipeline, liquid materials continuously enter a cavity in the cylinder from the liquid feed port 10 and rotate at a high speed in the cavity, and the liquid materials entering the cavity move from the inner wall of the cylinder to a central area along the circumferential direction of the cavity on one hand and move towards a second port 9 of the cylinder along the central axis of the cylinder on the other hand; because the liquid material circles round at a high speed in the cavity of the cylinder body, the axis area at the center of the cavity in the cylinder body generates a certain vacuum degree, at the moment, external air enters from the air inlet 13 and forms an air column in the axis area of the cavity in the cylinder body, and the liquid material continuously enters and rotates at a high speed, extrudes and cuts the air column, so that the air entering the cavity of the cylinder body is decomposed into a plurality of micro bubbles. When the gas-liquid mixture moves to the ultrasonic pipeline 11 along the axial direction of the cavity in the cylinder, liquid molecules are subjected to an external pulling acting force under the vibration of the ultrasonic vibrator 12, stress generated by the liquid molecules under the external pulling action is concentrated and acts on the micro-bubbles, and the micro-bubbles are further broken into micro-bubbles with smaller sizes. The bubbles broken twice by gas-liquid phase physical cutting and ultrasonic wave fragmentation have smaller size, and are beneficial to increasing the contact area between phases in the multiphase mass transfer process, thereby improving the mass transfer efficiency between phases.
In the present invention, the ratio of the cross-sectional area of the ultrasonic conduit 11 to the cross-sectional area of the cylinder 7 is preferably 0.04 to 0.64: 1, more preferably 0.16 to 0.36: 1; the ratio of the length of the ultrasonic pipe 11 to the length of the cylinder 7 is preferably 0.1 to 0.9: 1, more preferably 0.2 to 0.5: 1.
in the present invention, the number of the ultrasonic vibrators 12 on the ultrasonic conduit wall is preferably 4 to 30, more preferably 12 to 20.
According to the present invention, the ultrasonic vibrators 12 may be disposed on the inner wall or the outer wall of the ultrasonic pipeline or both, and the ultrasonic vibrators may be randomly arranged or arranged according to a set arrangement manner.
In the present invention, the liquid feed port 10 is arranged tangentially to the circumference of the barrel 7 (as shown in fig. 5), so that the liquid material enters the barrel inner cavity tangentially from the liquid feed port 10. When liquid materials enter the cavity in the barrel body from the liquid feeding hole 10, the liquid flowing direction of the liquid materials in the liquid feeding hole 10 is tangent to the inner wall of the barrel body 7, namely, the liquid materials entering from the liquid feeding hole 10 enter the cavity in the barrel body through the tangential direction of the inlet, so that the flow velocity of the liquid materials entering the cavity in the barrel body from the liquid material inlet 10 is close to the flow velocity of the liquid materials rotating in the cavity in the barrel body, and the liquid collision friction loss is reduced to the minimum. Preferably, the aspect ratio of the cross section of the liquid feed port is 1.5 or more, and the ratio of the cross-sectional area of the liquid feed port 3 to the cross-sectional area of the barrel 1 is 0.1 to 0.3: 1.
in the invention, when the material inlet 4 of the liquid phase hydrogenation reactor is positioned at the bottom of the liquid phase hydrogenation reactor, the micron bubble generator 11 is horizontally arranged and the ultrasonic pipeline is connected with the material inlet 4 through the pump 12, and at this time, a gas-liquid mixture in the micron bubble generator 11 enters the liquid phase hydrogenation reactor under the action of the pump 12. When the material inlet 4 of the liquid phase hydrogenation reactor is positioned at the top of the liquid phase hydrogenation reactor, the length direction of the cylinder body of the micron bubble generator 11 is vertical to the horizontal plane, and at the moment, the gas-liquid mixture in the micron bubble generator 11 enters the liquid phase hydrogenation reactor under the action of gravity.
According to the invention, the liquid phase hydrogenation reactor is a fixed bed reactor, a catalyst bed layer 3 is arranged in the fixed bed reactor, preferably, the height of the catalyst bed layer is 800-: 1-1: 2.
the second aspect of the invention provides a method for carrying out liquid phase hydrogenation on a carbon three-fraction by using the carbon three-fraction liquid phase hydrogenation reaction device, which comprises the step of contacting a carbon three-fraction a containing propyne and propadiene and hydrogen b with a selective hydrogenation catalyst in a liquid phase hydrogenation reactor under a selective hydrogenation condition to carry out selective hydrogenation to obtain a hydrogenation material c, wherein preferably, the selective hydrogenation condition is that the molar ratio of the hydrogen to the propyne and the propadiene is 0.5-1.5, the reaction pressure is 1-4MPa, the inlet temperature is 5-50 ℃, and the outlet temperature is 20-80 ℃.
In the present invention, the hydrogenation catalyst may be any catalyst which can be used in selective liquid phase hydrogenation of carbon three-cut, preferably, the selective hydrogenation catalyst comprises a carrier and a main active component loaded on the carrier, wherein the carrier is one or more of alumina, silica, titania, zinc oxide, molecular sieve, silicon carbide, calcium carbonate, kaolin and cordierite, and the main active component element is at least one selected from palladium, ruthenium and platinum elements; preferably, the content of the main active component is 0.01 to 1% by weight, more preferably 0.01 to 0.5% by weight, calculated as element, based on the total amount of the selective hydrogenation catalyst.
Preferably, the selective hydrogenation catalyst further comprises a co-active component supported on a carrier, the co-active component element being selected from one or more of alkali metal elements, alkaline earth metal elements, transition metal elements, rare earth elements and group VA metal elements, preferably one or more of silver, copper, zinc, potassium, sodium, magnesium, calcium, beryllium, tin, lead, cadmium, strontium, barium, radium, manganese, zirconium, molybdenum and germanium elements.
According to the invention, the content of the co-active component is preferably from 0.01 to 2% by weight, preferably from 0.01 to 1% by weight, calculated as element, based on the total amount of the selective hydrogenation catalyst.
In the present invention, the catalyst particles preferably have a particle size of 10 to 25 μm.
In the invention, the vibration frequency of the ultrasonic vibrator is preferably 15kHz-25kHz, and the power density is preferably 0.5-2.5W/m2。
The following detailed description is provided for the purpose of illustrating the embodiments and the advantageous effects thereof, and is intended to help the reader to clearly understand the spirit of the present invention, but not to limit the scope of the present invention.
Example 1
A liquid phase hydrogenation reaction device (the ratio of the area of the cross section of an ultrasonic wave pipeline of a micron bubble generator to the area of the cross section of a cylinder body is 0.25: 1, the ratio of the length of the ultrasonic wave pipeline of the micron bubble generator to the area of the cross section of the cylinder body is 0.4: 1, the ratio of a liquid feeding hole to the area of the cross section of the cylinder body is 0.2: 1, the number of ultrasonic vibrators is 16, and the ultrasonic vibrators are uniformly distributed on the ultrasonic wave pipeline at equal intervals) shown in figure 1 is selected for carrying out carbon three-fraction liquid phase. The liquid carbon three fraction a containing propyne and propadiene (wherein the sum of the molar contents of the propyne and the propadiene is 3%) enters from a liquid material inlet 10 of a micron bubble generator, hydrogen b enters from a gas inlet 13 of the micron bubble generator, the mixture of the two enters a liquid phase hydrogenation reactor through an ultrasonic pipeline 11, and the molar fraction of the propyne and the propadiene at the inlet of the liquid phase hydrogenation reactor is 0.025. The height of the catalyst bed layer in the liquid phase hydrogenation reactor is 2000mm, the diameter is 1000mm, and the catalyst is BC-L-83 provided by Beijing chemical research institute of China petrochemical industry.
The catalytic hydrogenation reaction conditions are as follows: the weight hourly space velocity of the liquid phase is 60h-1The molar ratio of the hydrogen to the propyne to the allene is 1.0, the reaction pressure is 2MPa, the inlet temperature is 36 ℃, and the outlet temperature is 55 ℃. The vibration frequency of the ultrasonic vibrator is 20kHz, and the power density is 1.5W/m2。
Under the conditions, the mole fraction of the propyne and the propadiene at the outlet of the liquid phase hydrogenation reactor is 0.00007, and the conversion rate of the propyne and the propadiene is 99.72%.
Wherein, the conversion rate of the propine and the propadiene refers to the percentage of the difference of the carbon three-component content at the inlet and the outlet of the reactor in the carbon three-component content at the inlet of the reactor.
Example 2
A liquid phase hydrogenation reaction device (the ratio of the area of the cross section of an ultrasonic wave pipeline of a micron bubble generator to the area of the cross section of a cylinder body is 0.36: 1, the ratio of the length of the ultrasonic wave pipeline of the micron bubble generator to the area of the cross section of the cylinder body is 0.2: 1, the ratio of a liquid feeding hole to the area of the cross section of the cylinder body is 0.3: 1, the number of ultrasonic vibrators is 12, and the ultrasonic vibrators are uniformly distributed on the ultrasonic wave pipeline at equal intervals) shown in figure 1 is selected for carrying out carbon three-fraction liquid phase. The liquid carbon three fraction a containing propyne and propadiene (wherein the sum of the molar contents of the propyne and the propadiene is 3%) enters from a liquid material inlet 10 of a micron bubble generator, hydrogen b enters from a gas inlet 13 of the micron bubble generator, the mixture of the two enters a liquid phase hydrogenation reactor through an ultrasonic pipeline 11, and the molar fraction of the propyne and the propadiene at the inlet of the liquid phase hydrogenation reactor is 0.025. The height of the catalyst bed layer in the liquid phase hydrogenation reactor is 1000mm, the diameter is 1000mm, and the catalyst is BC-L-83 provided by Beijing chemical research institute of China petrochemical industry.
The catalytic hydrogenation reaction conditions are as follows: the weight hourly space velocity of the liquid phase is 80h-1The molar ratio of the hydrogen to the propyne and the propadiene is 1.5, the reaction pressure is 2.5MPa, the inlet temperature is 40 ℃, and the outlet temperature is 58 ℃. The vibration frequency of the ultrasonic vibrator is 15kHz, and the power density is 1.0W/m2。
Under the conditions, the mole fraction of the propyne and the propadiene at the outlet of the liquid phase hydrogenation reactor is 0.00009, and the conversion rate of the propyne and the propadiene is 99.64 percent.
Example 3
A liquid phase hydrogenation reaction device (the ratio of the area of the cross section of an ultrasonic wave pipeline of a micron bubble generator to the area of the cross section of a cylinder body is 0.16: 1, the ratio of the length of the micron bubble generator to the area of the cross section of the cylinder body is 0.5: 1, the ratio of a liquid feeding hole to the area of the cross section of the cylinder body is 0.1: 1, the number of ultrasonic vibrators is 20, and the liquid phase hydrogenation reaction device is a fixed bed reactor) shown in figure 1 is selected for carrying out carbon three-fraction liquid phase hydrogenation reaction. The liquid carbon three fraction a containing propyne and propadiene (wherein the sum of the molar contents of the propyne and the propadiene is 3%) enters from a liquid material inlet 10 of a micron bubble generator, hydrogen b enters from a gas inlet 13 of the micron bubble generator, the mixture of the two enters a liquid phase hydrogenation reactor through an ultrasonic pipeline 11, and the molar fraction of the propyne and the propadiene at the inlet of the liquid phase hydrogenation reactor is 0.025. The height of a catalyst bed layer in the liquid phase hydrogenation reactor is 2500mm, the diameter is 1600mm, and the catalyst is BC-L-83 provided by Beijing chemical research institute of China petrochemical industry.
The catalytic hydrogenation reaction conditions are as follows: the weight hourly space velocity of the liquid phase is 40h-1The molar ratio of hydrogen to propyne to propadiene was 0.8, the reaction pressure was 3MPa, the inlet temperature was 30 ℃ and the outlet temperature was 60 ℃.
The vibration frequency of the ultrasonic vibrator is 25kHz, and the power density is 2.3W/m2。
Under the conditions, the mole fraction of the propyne and the propadiene at the outlet of the liquid phase hydrogenation reactor is detected to be 0.00005, and the conversion rate of the propyne and the propadiene is detected to be 99.8%.
Example 4
A liquid phase hydrogenation reaction device (the ratio of the area of the cross section of the ultrasonic wave pipeline of the micron bubble generator to the area of the cross section of the cylinder body is 0.25: 1, the ratio of the length of the ultrasonic wave pipeline of the micron bubble generator to the area of the cross section of the cylinder body is 0.4: 1, the ratio of the area of the liquid feed port to the area of the cross section of the cylinder body is 0.2: 1, the number of ultrasonic vibrators is 16, and the ultrasonic vibrators are uniformly distributed on the ultrasonic wave pipeline at equal intervals) shown in figure 2 is selected for carrying out carbon three-. The liquid carbon three fraction a containing propyne and propadiene (wherein the sum of the molar contents of the propyne and the propadiene is 3%) enters from a liquid material inlet 10 of a micron bubble generator, hydrogen b enters from a gas inlet 13 of the micron bubble generator, the mixture of the two enters a liquid phase hydrogenation reactor through an ultrasonic pipeline 11, and the molar fraction of the propyne and the propadiene at the inlet of the liquid phase hydrogenation reactor is 0.025. The height of the catalyst bed layer in the liquid phase hydrogenation reactor is 2000mm, the diameter is 1000mm, and the catalyst is BC-L-83 provided by Beijing chemical research institute of China petrochemical industry.
The catalytic hydrogenation reaction conditions are as follows: the weight hourly space velocity of the liquid phase is 60h-1The molar ratio of the hydrogen to the propyne to the allene is 1.0, the reaction pressure is 2MPa, the inlet temperature is 36 ℃, and the outlet temperature is 55 ℃. The vibration frequency of the ultrasonic vibrator is 20kHz, and the power density is 1.5W/m2。
Under the conditions, the mole fraction of the propyne and the propadiene at the outlet of the liquid phase hydrogenation reactor is 0.000072, and the conversion rate of the propyne and the propadiene is 99.71 percent.
Comparative example 1
Selecting a liquid phase hydrogenation reaction device shown in figure 3 to carry out carbon three-fraction liquid phase hydrogenation reaction, wherein the liquid phase hydrogenation reactor is a fixed bed reactor. Mixing a liquid carbon three fraction a containing propyne and propadiene (wherein the sum of the molar contents of the propyne and the propadiene is 3%) and hydrogen b, and then feeding the mixture into a liquid phase hydrogenation reactor. The mole fraction of the propyne and the propadiene at the inlet of the liquid phase hydrogenation reactor was 0.025. The height of a catalyst bed layer in the liquid phase hydrogenation reactor is 2000mm, the diameter is 1000mm, the catalyst is BC-L-83 provided by Beijing chemical research institute of China petrochemical industry, and the catalytic hydrogenation reaction conditions are as follows: the weight hourly space velocity of the liquid phase is 60h-1The molar ratio of the hydrogen to the propyne to the allene is 1.0, the reaction pressure is 2MPa, the inlet temperature is 36 ℃, and the outlet temperature is 55 ℃.
Under the conditions, the mole fraction of the propyne and the propadiene at the outlet of the liquid phase hydrogenation reactor is 0.0005, and the conversion rate of the propyne and the propadiene is 98 percent.
Comparative example 2
Is selected fromThe liquid phase hydrogenation reaction apparatus shown in fig. 3 performs a carbon three-fraction liquid phase hydrogenation reaction, wherein the liquid phase hydrogenation reactor is a fixed bed reactor. Mixing a liquid carbon three fraction a containing propyne and propadiene (wherein the sum of the molar contents of the propyne and the propadiene is 3%) and hydrogen b, and then feeding the mixture into a liquid phase hydrogenation reactor. The mole fraction of the propyne and the propadiene at the inlet of the liquid phase hydrogenation reactor was 0.025. The height of a catalyst bed layer in the liquid phase hydrogenation reactor is 1000mm, the diameter is 500mm, the catalyst is BC-L-83 provided by Beijing chemical research institute of China petrochemical industry, and the catalytic hydrogenation reaction conditions are as follows: the weight hourly space velocity of the liquid phase is 80h-1The molar ratio of the hydrogen to the propyne to the allene is 1.5, the reaction pressure is 3MPa, the inlet temperature is 40 ℃, and the outlet temperature is 58 ℃.
Under the conditions, the mole fraction of the propyne and the propadiene at the outlet of the liquid phase hydrogenation reactor is 0.0009, and the conversion rate of the propyne and the propadiene is 96.4 percent.
Comparative example 3
Selecting a liquid phase hydrogenation reaction device shown in figure 3 to carry out carbon three-fraction liquid phase hydrogenation reaction, wherein the liquid phase hydrogenation reactor is a fixed bed reactor. Mixing a liquid carbon three fraction a containing propyne and propadiene (wherein the sum of the molar contents of the propyne and the propadiene is 3%) and hydrogen b, and then feeding the mixture into a liquid phase hydrogenation reactor. The mole fraction of the propyne and the propadiene at the inlet of the liquid phase hydrogenation reactor was 0.025. The height of a catalyst bed layer in the liquid phase hydrogenation reactor is 2500mm, the diameter is 1600mm, the catalyst is BC-L-83 provided by Beijing chemical research institute of China petrochemical industry, and the catalytic hydrogenation reaction conditions are as follows: the weight hourly space velocity of the liquid phase is 40h-1The molar ratio of hydrogen to propyne to propadiene was 0.8, the reaction pressure was 3MPa, the inlet temperature was 30 ℃ and the outlet temperature was 60 ℃.
Under the conditions, the mole fraction of the propyne and the propadiene at the outlet of the liquid phase hydrogenation reactor is 0.0003, and the conversion rate of the propyne and the propadiene is 98.8 percent.
Therefore, under the same carbon three-fraction liquid-phase hydrogenation conditions, when the carbon three-fraction liquid-phase hydrogenation reaction device is applied to carbon three-fraction liquid-phase hydrogenation, the mixing degree of the gas phase and the liquid phase can be improved, the gas-liquid phase mass transfer efficiency can be further improved, and the conversion rate of propyne and propadiene in the carbon three-fraction can be improved when the carbon three-fraction liquid-phase hydrogenation reaction device is applied to carbon three-fraction liquid-phase hydrogenation.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (10)
1. A carbon three-fraction liquid-phase hydrogenation reaction device is characterized by comprising: the device comprises a liquid-phase hydrogenation reactor and a micron bubble generator which is arranged outside the liquid-phase hydrogenation reactor and connected with a material inlet of the liquid-phase hydrogenation reactor;
the micro bubble generator comprises a cylinder body, an air inlet arranged at a first port of the cylinder body, a liquid feed inlet arranged on the side wall of the cylinder body and an ultrasonic pipeline which is arranged at a second port of the cylinder body and is coaxially communicated with the cylinder body; and the side wall of the ultrasonic pipeline is provided with an ultrasonic vibrator, and the port of the ultrasonic pipeline is connected with the material inlet of the liquid phase hydrogenation reactor.
2. The carbon three-fraction liquid-phase hydrogenation reaction device according to claim 1, wherein a ratio of a cross-sectional area of the ultrasonic pipe to a cross-sectional area of the cylinder is 0.04 to 0.64: 1, preferably 0.16 to 0.36: 1; the ratio of the length of the ultrasonic pipeline to the length of the cylinder is 0.1-0.9: 1, preferably 0.2 to 0.5: 1.
3. the carbon three-fraction liquid-phase hydrogenation reaction device according to claim 1 or 2, wherein the number of the ultrasonic vibrators on the wall of the ultrasonic pipeline is 4-30, preferably 12-20.
4. The carbon three-fraction liquid-phase hydrogenation reaction device according to claim 3, wherein the ultrasonic vibrators are arranged on the outer wall of the ultrasonic pipeline and are uniformly distributed on the outer wall of the ultrasonic pipeline at equal intervals.
5. The carbon three-fraction liquid-phase hydrogenation reaction device according to claim 1, wherein the liquid feed port is arranged tangentially to the circumference of the cylinder so that liquid material enters the cylinder inner cavity tangentially from the liquid feed port.
6. The carbon three-fraction liquid-phase hydrogenation reaction device according to claim 1 or 5, wherein the ratio of the cross-sectional area of the liquid feed port to the cross-sectional area of the cylinder is 0.1 to 0.3: 1.
7. the carbon three-fraction liquid-phase hydrogenation reaction device according to claim 1, wherein when the material inlet of the liquid phase hydrogenation reactor is located at the bottom of the liquid phase hydrogenation reactor, the micron bubble generator is horizontally arranged and the ultrasonic pipeline is connected with the material inlet through a pump.
8. A carbon three-fraction liquid-phase hydrogenation reaction device according to claim 1, wherein when the material inlet of the liquid phase hydrogenation reactor is located at the top of the liquid phase hydrogenation reactor, the length direction of the cylinder of the micron bubble generator is perpendicular to the horizontal plane.
9. The carbon three-fraction liquid-phase hydrogenation reaction device according to claim 1, wherein the liquid-phase hydrogenation reactor is a fixed bed reactor, a catalyst bed layer is arranged in the fixed bed reactor, the height of the catalyst bed layer is 800-2500mm, and the diameter-height ratio is 1: 1-1: 2.
10. a method for carrying out liquid phase hydrogenation on a carbon trisection by using the liquid phase hydrogenation reaction device for the carbon trisection according to any one of claims 1 to 9, characterized in that a carbon trisection containing propyne and propadiene and hydrogen are contacted with a selective hydrogenation catalyst in the liquid phase hydrogenation reaction device for selective hydrogenation under selective hydrogenation conditions to obtain a hydrogenation material.
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| CN104874315A (en) * | 2014-02-28 | 2015-09-02 | 中石化洛阳工程有限公司 | Microbubble generator for reinforced hydrogenation technology |
| CN105582854A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Fixed bed hydrogenation reactor and application method thereof |
| CN106608805A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | C3 fraction liquid phase selective hydrogenation method |
| CN111203142A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Micron bubble generator |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104874315A (en) * | 2014-02-28 | 2015-09-02 | 中石化洛阳工程有限公司 | Microbubble generator for reinforced hydrogenation technology |
| CN105582854A (en) * | 2014-10-21 | 2016-05-18 | 中国石油化工股份有限公司 | Fixed bed hydrogenation reactor and application method thereof |
| CN106608805A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | C3 fraction liquid phase selective hydrogenation method |
| CN111203142A (en) * | 2018-11-22 | 2020-05-29 | 中国石油化工股份有限公司 | Micron bubble generator |
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