CN116410773A - Moving bed device and method for preparing low-carbon olefin by hydrocarbon oil pyrolysis - Google Patents
Moving bed device and method for preparing low-carbon olefin by hydrocarbon oil pyrolysis Download PDFInfo
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- CN116410773A CN116410773A CN202111681476.2A CN202111681476A CN116410773A CN 116410773 A CN116410773 A CN 116410773A CN 202111681476 A CN202111681476 A CN 202111681476A CN 116410773 A CN116410773 A CN 116410773A
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Classifications
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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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
- C10G11/16—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "moving bed" method
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
Abstract
The invention provides a moving bed device and a method for preparing light olefins by hydrocarbon oil pyrolysis, wherein the moving bed device comprises a moving bed reactor, and the moving bed reactor comprises: the gas distribution plate is horizontally arranged in the radial direction of the moving bed reactor; the catalyst baffle plate is horizontally arranged in the radial direction of the moving bed reactor and is positioned below the gas distribution plate, and the gas distribution plate and the catalyst baffle plate divide the moving bed reactor into a feeding area, a reaction area and a hydrocarbon oil product area to be conveyed from top to bottom in sequence; a catalyst inlet arranged at the top of the moving bed reactor and extending to the reaction zone through a first pipeline; a hydrocarbon oil raw material inlet arranged at the upper part of the moving bed reactor; the hydrocarbon oil product outlet is arranged in a region to be conveyed of the hydrocarbon oil product; the catalyst outlet is arranged at the bottom of the moving bed reactor and is positioned in the region where the hydrocarbon oil products are to be conveyed. The device reduces the problems of back mixing of hydrocarbon oil raw materials and dead zones in the reactor.
Description
Technical Field
The invention belongs to the technical field of catalytic cracking, and particularly relates to a moving bed device for preparing low-carbon olefin by catalytic cracking of hydrocarbon oil and a method for preparing low-carbon olefin by catalytic cracking of hydrocarbon oil by using the moving bed device.
Background
The catalyst has short reaction life, and the yield of the target low-carbon olefin product is greatly affected by the secondary conversion reaction. The fixed bed reactor is adopted, the flow of fluid in the bed layer is close to plug flow, the back mixing of materials is small, the mechanical abrasion of the catalyst is small, the catalyst is beneficial to catalytic cracking to improve the selectivity of the low-carbon olefin, but the regeneration and replacement of the catalyst are inconvenient. With fluidized bed reactors, the catalyst can be removed from the apparatus in large quantities, facilitating catalyst regeneration. However, the back mixing of the airflow and the bed particles is easy to generate secondary reaction, the yield of the catalytic pyrolysis low-carbon olefin is relatively reduced, and the catalyst particles are mutually and violently collided to cause the loss of the catalyst, generate dust and interfere the operation of the device. While moving bed reactors have the form of fluid-solid phase contacting reactors, solid materials are gravity fed into or removed from the reactor, during which the fluid reacts with the solid materials in contact, such that the operating performance of the moving bed reactor and the requirements for the catalyst are between fixed and fluidized beds. Compared with a fixed bed, the moving bed reactor has the characteristics of small pressure drop, easy catalyst regeneration operation, low investment and the like; compared with a fluidized bed, the moving bed reactor has the characteristics of small back mixing proportion, low catalyst abrasion pulverization degree, capability of changing the residence time of solids and fluid in a larger range, better operation flexibility and the like, and further has the catalytic cracking application advantage.
Although moving bed reactors find application in catalytic reaction processes such as continuous reforming, xylene isomerization, etc., they have less application in catalytic cracking. In many cases, variations in process flow or operating conditions, even minor changes, can have a significant impact on the conversion of the feedstock and the selectivity of the product. Aiming at the reaction property of preparing the low-carbon olefin by catalytic cracking of the hydrocarbon oil, the development and design of the device environment and the process flow matched with the reaction property are particularly important. In addition, the facility cost of the device, the flexibility of ethylene and propylene production regulation and control are also considered, so that the capital expenditure is controlled, and the market demand is met. Therefore, the design and the adoption of the reactor which is suitable for preparing the low-carbon olefin by the catalytic pyrolysis of the hydrocarbon oil such as naphtha, diesel oil and the like reduce dead areas and back mixing in the reactor, improve the utilization efficiency of the catalyst and promote the hydrocarbon oil to produce the low-carbon olefin more, and are the technical problems to be solved in the field.
CN110603311a discloses a process for catalytically cracking naphtha using a radial flow moving bed reactor system. The process is carried out by mixing naphtha with water or a drying gas to form a feed mixture, passing in a radially inward or radially outward flow through one or more radial flow moving bed reactors, and contacting catalyst particles under reaction conditions to produce light olefins; the method has the advantages that the raw material feeding direction is perpendicular to the catalyst flow direction, a special fluid distributor is required to be arranged in the radial direction of the reactor, and the problem of uneven distribution of carbon deposition of the catalyst on the same raw material feeding surface exists for a tank reactor. And unreacted raw materials and products enter the next reactor together, so that secondary reaction is easy to occur.
CN112774581a devised a plate-type cross-flow moving bed capable of loading and unloading catalyst intermittently and continuously. The catalyst filling area of the reactor is provided with a gas phase central tube, a plurality of plates surrounding the gas phase central tube, a gap rotary feeding disc arranged at the upper end of the gas phase central tube and a gap rotary discharging disc structure arranged at the lower end of the gas phase central tube, wherein the plates are axially (annularly) and equidistantly arranged in parallel along the outer tube wall of the gas phase central tube, a plate-type channel is formed between the adjacent plates, and gaps consistent with the cross section shape of the plate-type channel are formed in the gap rotary feeding disc and the gap rotary discharging disc, so that the loading and unloading uniformity of the catalyst is ensured, and the problem of uneven axial distribution of gas flow is effectively avoided; the design is along the feeding direction, and the feeding face of raw materials increases gradually, and its velocity of flow reduces, easily produces side reaction, and catalyst utilization efficiency is lower.
CN201586519U designs a gas-solid moving bed reactor, adjusts the discharge of catalyst through baffle adjust knob, and its baffle cloth has the aperture, and the reactor of being convenient for gets into the reaction zone of top for the reactor arrangement space is comparatively loose. And the valve is adopted to adjust the discharging and discharging of the catalyst, so that the abrasion of the catalyst is reduced; the reactor has larger dead zone of the reactor and lower utilization efficiency of the catalyst.
CN201423274Y and CN101683602B, the series of patents disclose a moving bed reactor device for continuous reaction and regeneration of catalyst, whose device constituent units are arranged from top to bottom into weighing hopper, upper lock hopper, moving bed reactor, lower lock hopper and catalyst regeneration reactor, and its lock hopper is used for connecting and closing the upper and lower device constituent units, and is equipped with inert gas inlet and outlet for replacement and pressure relief of lock hopper. The design is convenient for the catalyst to continuously participate in the reaction and regeneration; however, the reactor also has a large dead zone, and the catalyst utilization efficiency is low.
Disclosure of Invention
The invention mainly aims to provide a moving bed device and a method for preparing low-carbon olefin by cracking hydrocarbon oil, so as to overcome the defects of dead zone and back mixing problems, low catalyst utilization efficiency, low-carbon olefin yield and the like in the process of preparing low-carbon olefin by cracking hydrocarbon oil in the prior art.
In order to achieve the above object, the present invention provides a moving bed apparatus for producing light olefins by hydrocarbon oil pyrolysis, the moving bed apparatus comprising a moving bed reactor, the moving bed reactor comprising:
the gas distribution plate is arranged in the moving bed reactor and is horizontally arranged in the radial direction of the moving bed reactor;
the catalyst baffle plate is arranged below the gas distribution plate in the moving bed reactor and horizontally arranged in the radial direction of the moving bed reactor, and the gas distribution plate and the catalyst baffle plate divide the moving bed reactor into a feeding zone, a reaction zone and a hydrocarbon oil product zone to be conveyed from top to bottom in sequence;
a catalyst inlet arranged at the top of the moving bed reactor and extending to the reaction zone through a first pipeline;
a hydrocarbon oil raw material inlet arranged at the upper part of the moving bed reactor;
a hydrocarbon oil product outlet arranged in a region to be transported of the hydrocarbon oil product;
the catalyst outlet is arranged at the bottom of the moving bed reactor and is positioned in the region where the hydrocarbon oil products are to be conveyed.
The moving bed device provided by the invention, wherein the catalyst inlet is arranged at the top end of the moving bed reactor, and the first pipeline extends along the axial direction of the moving bed reactor and stretches into the reaction zone; the hydrocarbon oil raw material inlet is arranged along the radial direction of the moving bed reactor, so that the hydrocarbon oil raw material enters the moving bed reactor in a direction perpendicular to the flowing direction of the catalyst.
The moving bed device provided by the invention is characterized in that the moving bed reactor is also provided with a catalyst distribution plate which is arranged in the reaction zone so as to uniformly disperse the catalyst into the reaction zone to form a catalyst bed.
The moving bed device comprises a catalyst distribution plate, a catalyst distribution plate and a catalyst treatment device, wherein the catalyst distribution plate comprises at least one layer of arc surface plates which are arranged in a step manner; the ratio of the cambered surface height to the cambered surface width of at least one layer of cambered surface plate is less than or equal to 0.5, and the cambered surface width of at least one layer of cambered surface plate is more than 1.2 times of the diameter of the first pipeline.
The moving bed device of the invention, whereinThe arc panel adjacent to the first pipeline in the at least one layer of arc panels is a first layer of arc panel; the first layer of arc panel is an arc surface, the at least one layer of arc panel except the first layer of arc panel is a spherical ring, and the relation between the number k of the rings in the arc panel with the spherical ring and the number n of the layers of the arc panel is k=2 n-2 The method comprises the steps of carrying out a first treatment on the surface of the The arc plates of the lower layer are uniformly distributed on two sides of the arc plate of the upper layer, and the arc extension lines of the arc plates of the upper layer are intersected at the arc points of the arc plates of the lower layer.
The moving bed device provided by the invention has the advantages that the height difference of two adjacent layers of arc panels is more than 1.2 times of the height of at least one layer of the two adjacent layers of arc panels, and the distance between the same layers of arc panels is more than 10 times of the diameter of catalyst particles.
The moving bed device provided by the invention is characterized in that the catalyst baffle plate is provided with a plurality of catalyst blanking holes; the diameter of the catalyst blanking hole is 0.1-5 times of the diameter of the first pipeline; the catalyst discharging holes are symmetrical with the center point of the catalyst distribution plate in a center.
The moving bed device of the invention, wherein the moving bed reactor further comprises a first valve, which is arranged close to the catalyst baffle plate, so as to control whether the catalyst passes through the catalyst baffle plate or not by adjusting the first valve.
The moving bed device provided by the invention, wherein the hydrocarbon oil product outlet is arranged along the radial direction of the moving bed reactor, so that the hydrocarbon oil product flows out along the radial direction of the moving bed reactor.
The moving bed device provided by the invention, wherein the gas distribution plate is a metal powder metallurgy plate, and the porosity is more than or equal to 55%; the catalyst baffle is a metal powder metallurgy plate, and the porosity is more than or equal to 55%; the catalyst distribution plate is a metal powder metallurgy plate, and the porosity is more than or equal to 55%.
The moving bed device also comprises a stripping distributor, a catalyst buffer tank and a catalyst regenerator;
the stripping distributor is connected with the catalyst outlet;
the catalyst buffer tank is provided with a circulating catalyst inlet and a circulating catalyst outlet;
the catalyst regenerator is provided with a regenerated catalyst inlet and a regenerated catalyst outlet, the circulating catalyst inlet and the regenerated catalyst inlet are respectively connected with the stripping distributor, and the circulating catalyst outlet and the regenerated catalyst outlet are respectively connected with the catalyst inlet.
The moving bed device provided by the invention is characterized in that a catalyst baffle plate and a regeneration air inlet are arranged in the catalyst regenerator, and the regeneration air inlet is arranged below the catalyst baffle plate in the axial direction of the moving bed reactor.
The moving bed device of the invention, wherein, in the axial direction of the moving bed reactor, the moving bed reactor is positioned between the stripping distributor and the catalyst buffer tank, and the moving bed reactor is positioned between the stripping distributor and the catalyst regenerator.
In order to achieve the above purpose, the invention also provides a method for preparing low-carbon olefin by cracking hydrocarbon oil, which uses the moving bed device and comprises the following steps:
the catalyst enters the moving bed reactor from a catalyst inlet, and a catalyst bed layer is formed in a reaction zone;
hydrocarbon oil raw materials enter the moving bed reactor from a hydrocarbon oil raw material inlet, move downwards along the axial direction of the moving bed reactor through a gas distribution plate and contact the catalyst bed layer, and are converted into low-carbon olefin;
the low-carbon olefin and unreacted hydrocarbon oil raw materials pass through the catalyst baffle plate and flow out from the hydrocarbon oil product outlet.
The invention relates to a method for preparing low-carbon olefin by hydrocarbon oil pyrolysis, wherein a catalyst subjected to carbon deposition enters a region to be conveyed of hydrocarbon oil products through a catalyst baffle plate, enters a stripping distributor through a catalyst outlet, and then enters a catalyst buffer tank and/or a catalyst regenerator for preheating and/or regeneration under the stripping action; after being preheated or regenerated, the carbon deposition catalyst enters the moving bed reactor through the catalyst inlet and is recycled.
The invention relates to a method for preparing low-carbon olefin by cracking hydrocarbon oil, wherein the hydrocarbon oil raw material is hydrocarbon fraction with the boiling point of 30-350 ℃; the hydrocarbon oil raw material enters the moving bed reactor after being preheated, the preheating temperature is 200-400 ℃, and the feeding airspeed of the hydrocarbon oil raw material is 1-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the catalyst bed layer of the moving bed reactor is 560-640 ℃, and the pressure of the catalyst bed layer is 0-0.1MPa.
The invention relates to a method for preparing low-carbon olefin by hydrocarbon oil pyrolysis, wherein the preheating temperature of a catalyst buffer tank is 600-680 ℃, and the catalyst regeneration temperature of a catalyst regenerator is 600-680 ℃.
The invention has the beneficial effects that:
the device reduces the back mixing problem of the hydrocarbon oil raw material through the arrangement of the catalyst baffle, the feeding direction of the hydrocarbon oil raw material is the same as the moving direction of the catalyst, the hydrocarbon oil raw material axially contacts with the catalyst bed, and the back mixing problem of the hydrocarbon oil raw material and the dead zone problem inside the reactor are further reduced.
The device is used for cracking hydrocarbon oil raw materials, has higher yield of low-carbon olefin, namely higher yield of ethylene and propylene products, especially ethylene product yield, and breaks through the limitation that the conventional catalytic cracking device only produces propylene in a rich way and has extremely low ethylene yield.
Drawings
FIG. 1 is a schematic diagram of a moving bed apparatus according to an embodiment of the present invention.
FIG. 2 is a schematic view of a catalyst baffle according to one embodiment of the present invention.
Fig. 3 is a schematic side view of an arc panel according to an embodiment of the invention.
Fig. 4 is a schematic top view of an arc panel according to an embodiment of the invention.
Wherein, the reference numerals:
1. a moving bed reactor;
2. a stripping distributor;
3. a catalyst buffer tank;
4. a catalyst regenerator;
5. a hydrocarbon oil feedstock inlet;
6. a hydrocarbon oil product outlet;
7. a catalyst inlet;
8. a feed zone;
9. a gas distribution plate;
10. a catalyst distribution plate;
11. a reaction zone;
12. a catalyst baffle;
13. a first valve;
14. a hydrocarbon oil product to be transported zone;
15. a catalyst outlet;
16. a catalyst outlet control valve;
17. a stripping gas inlet;
18. a circulating catalyst inlet;
19. an exhaust port;
20. a catalyst outlet;
21. a regenerated catalyst inlet;
22. a catalyst feed inlet;
23. a regeneration tail gas discharge port;
24. a catalyst baffle;
25. a regeneration air inlet;
26. a regenerated catalyst outlet;
27. a catalyst inlet control valve.
201. A first layer of arc panels;
202. a second layer of arc panels;
203. catalyst channels;
204. a third arc panel;
205. an upper arc panel;
206. tangent line of the edge of the upper cambered surface plate;
207. the next arc panel.
301. A catalyst baffle body;
302. catalyst blanking hole.
Detailed Description
The following embodiments are provided by carrying out the embodiments of the present invention on the premise of the embodiments of the present invention, and the detailed implementation process is given, but the scope of protection of the present invention is not limited to the following embodiments, and structures or processes not specifically described in the following embodiments are generally according to conventional techniques in the art.
The present invention provides a moving bed apparatus, please refer to fig. 1, the moving bed apparatus of the present invention is used for preparing low-carbon olefins by hydrocarbon oil pyrolysis, in a first embodiment, the moving bed apparatus of the present invention comprises a moving bed reactor 1, the moving bed reactor 1 comprises:
the gas distribution plate 9 is arranged in the moving bed reactor 1 and is horizontally arranged in the radial direction of the moving bed reactor 1;
the catalyst baffle 12 is arranged below the gas distribution plate 9 in the moving bed reactor 1, is horizontally arranged in the radial direction of the moving bed reactor 1, and the gas distribution plate 9 and the catalyst baffle 12 divide the moving bed reactor 1 into a feeding zone 8, a reaction zone 11 and a hydrocarbon oil product to-be-conveyed zone 14 from top to bottom in sequence;
a catalyst inlet 7 disposed at the top of the moving bed reactor 1 and extending to the reaction zone 11 through a first line;
a hydrocarbon oil raw material inlet 5 arranged at the upper part of the moving bed reactor 1;
a hydrocarbon oil product outlet 6 arranged in a hydrocarbon oil product to-be-conveyed region 14;
the catalyst outlet 15 is arranged at the bottom of the moving bed reactor 1 and is positioned in the hydrocarbon oil product to-be-conveyed area 14.
In one embodiment, the moving bed reactor 1 of the present invention is in the shape of a cylindrical tank with a hemispherical top and a conical bottom.
The invention is characterized in that a catalyst inlet 7 is arranged at the top end of the moving bed reactor 1, a first pipeline extends along the axial direction of the moving bed reactor and stretches into the reaction zone, so that the catalyst flows into the moving bed reactor 1 along the gravity direction and passes through a gas distribution plate 9 to enter a reaction zone 11 through the first pipeline. In one embodiment, a catalyst inlet control valve 27 is arranged at the catalyst inlet 7, and the front end and the rear end of the catalyst inlet control valve 27 are provided with inert gas back-blowing structures for gas sealing at the top of the moving bed reactor.
In one embodiment, the gas distribution plate 9 of the present invention is disposed at an upper inner section of the moving bed reactor 1, and divides the reactor into a feed zone 8 and a reaction zone along the axial direction of the moving bed reactor 1, wherein the feed zone 8 is disposed above the gas distribution plate 9, and the reaction zone is disposed below the gas distribution plate 9, such that the hydrocarbon oil raw material entering the feed zone 8 along the radial direction of the moving bed reactor 1 flows downward along the axial direction of the moving bed reactor 1 into the reaction zone. In another embodiment, the gas distribution plate 9 is a metal powder metallurgy plate, the porosity is not less than 55%, but the invention is not limited thereto.
The catalyst baffle 12 is arranged at the lower section of the interior of the moving bed reactor 1, and the reaction zone of the moving bed reactor 1 is further divided into a reaction zone 11 and a hydrocarbon oil product to-be-conveyed zone 14 along the axial direction of the moving bed reactor 1, wherein the reaction zone 11 is positioned above the catalyst baffle 12, and the hydrocarbon oil product to-be-conveyed zone 14 is positioned below the catalyst baffle 12. Unreacted hydrocarbon oil feedstock and cracked products are directed axially downwardly along the moving bed reactor 1 from the reaction zone 11 into the hydrocarbon oil product to-be-transported zone 14, while catalyst baffles 12 block catalyst particles from being directed axially downwardly along the moving bed reactor 1 into the hydrocarbon oil product to-be-transported zone 14.
In one embodiment, please refer to fig. 2, fig. 2 is a schematic diagram of a catalyst baffle according to an embodiment of the present invention. The catalyst baffle 12 of the present invention includes a catalyst baffle body 301 and a catalyst discharge hole 302, so that the carbon deposited catalyst can be discharged from the catalyst discharge hole 302.
In another embodiment, the catalyst baffle plate 12 of the present invention is provided with a plurality of catalyst feed holes 302, and the plurality of catalyst feed holes 302 are centrally symmetric about the center point of the catalyst baffle plate 12. In one embodiment, the plurality of catalyst feed holes 302 of the present invention are arranged in a cross-shape. The diameter of the catalyst blanking hole 302 of the present invention is 0.1 to 5 times the diameter of the first line connected to the catalyst inlet 7. The catalyst discharging hole 302 is in a flat plate shape, and the position of the catalyst baffle plate 12 except the catalyst discharging hole 302 is higher than the catalyst discharging hole 302, so that the generated height difference can ensure the downward flow of the catalyst.
In yet another embodiment, the catalyst guard 12 of the present invention is made of metal powder metallurgy plate with a porosity of 55% or more.
In one embodiment, a first valve 13 is further disposed at the catalyst baffle 12 of the present invention, for example, the first valve 13 is disposed closely to the catalyst baffle 12 and is disposed corresponding to the catalyst discharging hole 302, so as to control whether the catalyst passes through the catalyst baffle 12 by adjusting the first valve 13.
In one embodiment, the moving bed reactor 1 of the present invention is further provided with a catalyst distribution plate 10 disposed in the reaction zone 11, for example, in the upper portion of the reaction zone 11, adjacent to the outlet of the first pipeline, so as to uniformly disperse the catalyst into the reaction zone 11 to form a catalyst bed.
In another embodiment, the catalyst distribution plate 10 of the present invention comprises at least one arc panel, for example, a multi-layered arc panel, which is arranged in steps, so that the catalyst particles are equally likely to be dispersed along the arc panel of the catalyst distribution plate 10, thereby forming a uniform catalyst bed in the reaction zone 11. The arc panels adjacent to the first pipeline in the multi-layer arc panels are first-layer arc panels, and the distance between the first-layer arc panels and the first pipeline is larger than or equal to the radius of the first pipeline.
Referring to fig. 3, fig. 3 is a schematic distribution diagram, specifically a cross-sectional diagram, of an arc panel according to an embodiment of the invention. The ratio of the cambered surface height H to the cambered surface width D of the cambered surface panel is less than or equal to 0.5, and the cambered surface width D of the cambered surface panel is more than 1.2 times of the diameter of the first pipeline.
In yet another embodiment, the first arc panel is an arc surface, that is, a part of the surface of a sphere, and at least one arc panel except the first arc panel is an arc surface ring, that is, a ring formed by winding an arc around a circle. Referring to fig. 4, a schematic top view of an arc panel according to an embodiment of the invention is shown. The top view of the first arc plate 201 is disc-shaped, the top view of the other arc plates is circular, for example, the top view of the second arc plate 202 is annular, hollow catalyst channels 203 are formed in the middle, and the top view of the third arc plate 204 is double-annularTwo hollowed-out catalyst channels 203 are formed. The relation between the number k of rings in the cambered surface plate with spherical rings and the number n of layers of the cambered surface plate is k=2 n-2 The method comprises the steps of carrying out a first treatment on the surface of the The arc panels 207 of the next layer are uniformly distributed on both sides of the arc panel 205 of the previous layer, and the edge tangent 206 of the arc panel of the previous layer is intersected at the arc midpoint or the position near the arc midpoint of the arc panel of the next layer, so that the catalyst on the arc panel of the previous layer moves downwards through the catalyst channels 203 of the arc panel of the next layer.
In still another embodiment, the height difference between two adjacent arc panels is more than 1.2 times of the height of at least one arc panel in the two adjacent arc panels, for example, the height difference between the two adjacent arc panels is the difference between the highest points of the two adjacent arc panels; the distance between the cambered surface plates on the same layer is more than 10 times of the diameter of the catalyst particles, for example, the distance between two cambered surface rings or the distance between the cambered surface rings and the center point of the cambered surface plates on the same layer in the radial direction of the moving bed reactor 1.
In one embodiment, the catalyst distribution plate is a metal powder metallurgy plate, the porosity is not less than 55%, but the invention is not limited thereto.
The invention can realize uniform catalyst blanking through the arrangement of the catalyst distribution plate, has a buffering function and reduces the abrasion loss of the catalyst.
The hydrocarbon oil raw material inlet 5 of the invention is arranged at the upper part of the moving bed reactor 1, in particular above the gas distribution plate 9, and is communicated with the feeding zone 9. In one embodiment, the hydrocarbon oil feedstock inlet 5 of the present invention is disposed in a radial direction of the moving bed reactor 1 such that the hydrocarbon oil feedstock enters the moving bed reactor 1 in a direction perpendicular to the direction of catalyst flow. In other words, the hydrocarbon oil feedstock of the present invention enters the moving bed reactor 1 in the radial direction of the moving bed reactor 1, and the catalyst enters the moving bed reactor 1 in the axial direction of the moving bed reactor 1. After the hydrocarbon oil raw material is diffused and filled in the feeding area 8, the hydrocarbon oil raw material moves downwards along the axial direction of the moving bed reactor 1 through the gas distribution plate 9 under the action of feeding driving force, and is in axial contact with the catalyst bed layer, so that the dead zone in the reactor is reduced.
In addition, the feeding direction of the hydrocarbon oil in the catalyst bed is the same as the moving direction of the catalyst, and the catalyst baffle 12 and the first valve 13 are arranged at the bottom of the catalyst bed, so that the valve port gas leakage during the hydrocarbon oil feeding and returning and the catalyst discharging is reduced, and the selectivity of the low-carbon olefin products is improved.
The hydrocarbon oil product outlet 6 is arranged at the lower part of the moving bed reactor 1 and is communicated with a hydrocarbon oil product to-be-conveyed area 14, in particular to the upper part of the hydrocarbon oil product to-be-conveyed area 14. In one embodiment, the hydrocarbon oil product outlet 6 of the present invention is disposed in the radial direction of the moving bed reactor 1 so that the hydrocarbon oil product flows out in the radial direction of the moving bed reactor 1.
The catalyst outlet 15 of the present invention is disposed at the bottom of the moving bed reactor 1 and communicates with the hydrocarbon oil product to-be-transported zone 14. In one embodiment, the catalyst outlet 15 of the present invention is disposed along the axial direction of the moving bed reactor 1 and is provided with a catalyst outlet control valve 16 for controlling the deactivated catalyst from exiting the moving bed reactor 1. In another embodiment, the front and rear ends of the catalyst outlet control valve 16 of the catalyst outlet 15 of the present invention are provided with an inert gas back-blowing structure for the bottom gas seal of the moving bed reactor 1.
In a second embodiment, the moving bed apparatus of the present invention comprises a moving bed reactor 1, a stripping distributor 2, a catalyst surge tank 3, and a catalyst regenerator 4. The moving bed reactor 1 has been described in detail in the first embodiment, and the structure of the moving bed reactor 1 in this embodiment is similar to that of the moving bed reactor in the first embodiment, and will not be described again.
In one embodiment, the catalyst buffer tank 3 of the present invention is in the shape of a cylindrical tank with a hemispherical top and a conical bottom. The catalyst regenerator 4 of the present invention is in the shape of a cylindrical pot, the top of which is hemispherical and the bottom of which is conical.
In the present invention, the stripping distributor 2 is connected to the catalyst outlet 15; the catalyst buffer tank 3 is provided with a circulating catalyst inlet 18 and a circulating catalyst outlet 20; the catalyst regenerator 4 is provided with a regenerated catalyst inlet 21 and a regenerated catalyst outlet 26, the circulating catalyst inlet 18 and the regenerated catalyst inlet 21 are respectively connected with the stripping distributor 3, and the circulating catalyst outlet 20 and the regenerated catalyst outlet 26 are respectively connected with the catalyst inlet 7. The catalyst buffer tank 3 has the functions of storing and preheating the catalyst, and aims at the strong endothermic characteristic of the catalytic cracking reaction, adjusts the internal circulation quantity of the catalyst and maintains the temperature of the catalyst bed layer to be stable. The catalyst regenerator 4 can regenerate the deactivated catalyst, and the regenerated catalyst can be recycled to the moving bed reactor 1 to continue the catalytic hydrocarbon oil raw material reaction.
In one embodiment, the bottom of the stripping distributor 2 of the present invention has a stripping gas inlet 17, and the stripping gas is, for example, nitrogen or steam, but the present invention is not limited thereto.
In one embodiment, the top of the catalyst buffer tank 3 of the present invention is provided with an exhaust port 19, the bottom catalyst outlet 20 is provided with a control valve, and the front end and the rear end of the control valve are provided with inert gas back-blowing structures for gas sealing and catalyst loosening at the bottom of the catalyst buffer tank 3.
In one embodiment, the top of the catalyst regenerator 4 of the present invention is provided with a catalyst feed inlet 22 and a regeneration tail gas discharge outlet 23, the lower end of the inside of the catalyst regenerator is provided with a catalyst baffle 24 and a rotary valve, a regeneration air inlet 25 is arranged below the catalyst baffle 24 and the rotary valve, namely, in the axial direction of the moving bed reactor 1, the regeneration air inlet 25 is arranged below the catalyst baffle 24, the bottom regenerated catalyst outlet 26 is provided with a control valve, and the front end and the rear end of the control valve are provided with an inert gas back-blowing structure for air sealing at the bottom of the catalyst regenerator.
The design of the catalyst baffle 24 and the rotary valve inside the catalyst regenerator 4 of the present invention is similar to the structure of the catalyst baffle 12 and the first valve 13 inside the moving bed reactor 1, and will not be repeated here.
The catalyst inlet 7 and the catalyst outlet 15 of the moving bed reactor 1 are respectively provided with a catalyst inlet control valve 27 and a catalyst outlet control valve 16, the circulating catalyst outlet of the catalyst buffer tank 3 is provided with a control valve, and the regenerated catalyst outlet of the catalyst regenerator 4 is provided with a control valve. The front and rear ends of the control valves are provided with an inert gas back-blowing structure, and the inert gas is one of nitrogen, carbon dioxide and argon, preferably nitrogen, but the invention is not particularly limited.
In one embodiment, the moving bed reactor 1 is located between the stripping distributor 2 and the catalyst surge tank 3 in the axial direction of the moving bed reactor 1, and the moving bed reactor 1 is located between the stripping distributor 2 and the catalyst regenerator 4.
In one embodiment, a pressure difference meter is arranged at the upper end and the lower end of a reaction zone 11, a hydrocarbon oil product to-be-conveyed zone 14, a catalyst buffer tank 3, a regenerated catalyst bed layer of a catalyst regenerator 4, a connecting pipeline of the moving bed reactor 1 and a stripping distributor 2, a connecting pipeline of the stripping distributor 2 and the catalyst buffer tank 3, a connecting pipeline of the stripping distributor 2 and the catalyst regenerator 4, a connecting pipeline of the catalyst buffer tank 3 and the moving bed reactor 1, and a connecting pipeline of the catalyst regenerator 4 and the moving bed reactor 1 in the moving bed reactor 1 of the invention, and the pressure difference value is recorded from time to time so as to monitor the inventory of the catalyst.
The device can realize the catalyst reaction-regeneration circulation, monitor the catalyst reserve of each section of units in the device at all times through the pressure difference meter in the device, and can be related with the hydrocarbon oil feeding quantity so as to ensure the stable operation of the device.
The moving bed reactor of the invention can be suitable for preparing low-carbon olefin by cracking hydrocarbon oil, and the hydrocarbon oil raw material is hydrocarbon fraction with the temperature of 30-350 ℃, such as light naphtha, heavy naphtha, straight-run diesel oil, hydrofined diesel oil and the like. The moving bed reactor can flexibly control the catalyst loading, the catalyst internal circulation and the catalyst regeneration circulation in the moving bed reaction, and can realize the flexible adjustment of cracking process conditions of different hydrocarbon oil raw materials.
The invention also provides a method for preparing low-carbon olefin by hydrocarbon oil pyrolysis, which uses the moving bed device and comprises the following steps:
catalyst enters the moving bed reactor 1 from the catalyst inlet 7, and a catalyst bed is formed in the reaction zone 11;
hydrocarbon oil raw materials enter the moving bed reactor 1 from a hydrocarbon oil raw material inlet 5, move downwards along the axial direction of the moving bed reactor 1 through a gas distribution plate 9 and contact the catalyst bed layer, so that the hydrocarbon oil raw materials are converted into low-carbon olefin;
the lower olefins and unreacted hydrocarbon oil feedstock pass through the catalyst baffle 12 and exit the hydrocarbon oil product outlet 6.
The catalyst after carbon deposition enters a hydrocarbon oil product to-be-conveyed area 14 through a catalyst baffle 12, enters a stripping distributor 2 through a catalyst outlet 15, and then enters a catalyst buffer tank 3 or a catalyst regenerator 4 for preheating or regeneration under the stripping action; after being preheated or regenerated, the carbon deposition catalyst enters the moving bed reactor 1 through the catalyst inlet 7 for recycling.
In one embodiment, the hydrocarbon oil raw material or the mixture raw material of the hydrocarbon oil raw material and the water vapor enters the moving bed reactor 1 after being preheated, the preheating temperature is 200-400 ℃, and the feeding airspeed of the hydrocarbon oil raw material is 1-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The catalyst bed temperature of the moving bed reactor 1 is 560-640 ℃, and the catalyst bed pressure () gauge pressure 0 is 0-0.1Mpa. The preheating temperature of the catalyst buffer tank 3 is 600-680 ℃, and the catalyst regeneration temperature of the catalyst regenerator 4 is 600-680 ℃. The connecting pipelines are all provided with heat preservation and heat tracing, and the temperature is 560-640 ℃.
In one embodiment of the invention, the method for preparing the low-carbon olefin by cracking the hydrocarbon oil comprises the following steps:
(1) The hydrocarbon oil raw material enters the moving bed reactor 1 from the hydrocarbon oil raw material inlet 5 after being preheated at 200-400 ℃ and is diffused and filled in the feeding area 8. Under the action of the pushing force of the feeding, the hydrocarbon oil raw material moves downwards along the axial direction of the moving bed reactor 1 through the gas distribution plate 9 and contacts with a catalyst bed layer at 560-640 ℃ in the reaction zone 11 to convert the hydrocarbon oil raw material into low-carbon olefin, wherein the pressure control range in the reaction zone 11 is 0-0.1MPa (gauge pressure). The reaction products and unreacted hydrocarbon oil raw materials pass through the catalyst baffle 12 and are diffused to fill the zone 14 to be conveyed with hydrocarbon oil products, and the reaction products and unreacted hydrocarbon oil raw materials leave the moving bed reactor 1 from the hydrocarbon oil product outlet 6 under the action of the pushing force of the feeding.
(2) The catalyst buffer tank 3 preheats the catalyst to 600-680 ℃, and the opening of a control valve of a circulating catalyst outlet 20 at the bottom of the catalyst buffer tank 3 and a control valve 27 of a catalyst inlet at the top of the moving bed reactor 1 are controlled to ensure that the catalyst is conveyed into the moving bed reactor 1 along a connecting pipeline of the catalyst buffer tank 3 and the moving bed reactor 1, wherein the pipeline heat tracing temperature is 560-640 ℃. The catalyst inlet 7 in the moving bed reactor 1 is directed through the gas distribution plate 9 by a first line so that the catalyst enters the moving bed reaction zone 11 in the moving bed reactor 1 directly. The catalyst is uniformly dispersed to the bottom of the moving bed reaction zone 11 through the dispersion action of the catalyst distribution plate 10 at the upper part of the moving bed reaction zone 11, and a catalyst bed layer is formed. In the moving bed reaction zone 11, the catalyst reacts in contact with the hydrocarbon oil feedstock. By controlling the opening of the first valve 13, the catalyst after carbon deposition enters the hydrocarbon oil product to-be-transported area 14 along the catalyst discharging holes 302 on the catalyst baffle 12. The catalyst after carbon deposition is collected at the bottom of the hydrocarbon oil product to-be-conveyed region 14, and the catalyst is conveyed to the stripping distributor 2 by controlling the opening degree of the catalyst outlet control valve 16. Under the stripping action of nitrogen or steam, the catalyst is returned to the catalyst buffer tank 3 from the circulating catalyst inlet 18 along the connecting pipeline of the stripping distributor 2 and the catalyst buffer tank 3, and the heat tracing temperature of the pipeline is 560-640 ℃. Excess gas in the catalyst surge tank 3 is exhausted from the catalyst surge tank exhaust port 19 at the top of the catalyst surge tank 3.
(3) Fresh catalyst enters the catalyst regenerator 4 from a catalyst feed inlet 22, the fresh catalyst or carbon deposition deactivated catalyst is activated or regenerated by contacting with regeneration air from the lower part of the catalyst regenerator 4, the regeneration air is introduced from a regeneration air inlet 25, the regeneration tail gas is discharged from a regeneration tail gas discharge port 23 at the top of the catalyst regenerator 4, and the regeneration temperature is controlled to be 600-680 ℃. The activated or regenerated catalyst leaves the catalyst regenerator 4 through a catalyst baffle 24, a rotary valve and a regenerated catalyst outlet 26 at the bottom of the catalyst regenerator 4, and is conveyed into the moving bed reactor 1 along a pipeline connecting the catalyst regenerator 4 and the moving bed reactor 1, wherein the heat tracing temperature of the pipeline is 560-640 ℃. The catalyst inlet 7 in the moving bed reactor 1 is directed through the gas distribution plate 9 by a first line so that the catalyst enters the moving bed reaction zone 11 in the moving bed reactor 1 directly. The catalyst is uniformly dispersed to the bottom of the moving bed reaction zone 11 through the dispersion action of the catalyst distribution plate 10 at the upper part of the moving bed reaction zone 11, and a catalyst bed layer is formed. In the moving bed reaction zone 11, the catalyst reacts in contact with the hydrocarbon oil feedstock. By controlling the opening of the first valve 13, the catalyst after carbon deposition enters the hydrocarbon oil product to-be-transported area 14 along the catalyst discharging holes 302 on the catalyst baffle 12. The catalyst after carbon deposition is collected at the bottom of the hydrocarbon oil product to-be-conveyed region 14, and the catalyst is conveyed to the stripping distributor 2 by controlling the opening degree of the catalyst outlet control valve 16. Wherein a catalyst outlet 15 is provided on the connecting line of the moving bed reactor 1 and the stripping distributor 2 (i.e. the bottommost point of the moving bed unit) for the discharge of catalyst. The catalyst is returned to the catalyst regenerator 4 from the catalyst inlet 21 to be regenerated along the connecting pipeline of the stripping distributor 2 and the catalyst regenerator 4 by the stripping action of nitrogen or water vapor, and the heat tracing temperature of the pipeline is 560-640 ℃.
The moving bed device for preparing low-carbon olefin by hydrocarbon oil pyrolysis has the characteristics of flexibly controlling the catalyst loading, the catalyst internal circulation and the catalyst regeneration circulation in the moving bed reaction, is suitable for the catalytic pyrolysis of hydrocarbon distillate oil with the boiling point of 30-350 ℃ such as light naphtha, heavy naphtha, straight-run diesel, hydrofined diesel and the like, and is used for producing high-yield low-carbon olefin. The following evaluation experiments of the apparatus and method of the present invention were conducted on naphtha, hydrogenated diesel, and straight-run diesel raw materials.
Composition analysis of hydrocarbon oil feedstock as shown in tables 1 and 2, the catalyst used in the following evaluation was a ZSM-5 catalyst system (SiO 2 /Al 2 O 3 =80, phosphorus loading of 1%), the cracking conditions and product distribution for the different feedstocks are shown in table 3.
TABLE 1 analysis of naphtha composition (omega%)
TABLE 2 analysis of diesel composition (omega%)
TABLE 3 cracking conditions and product distribution for different feedstocks
Table 3 among the cracking conditions and product yields for the different feedstocks, the product yields ignore catalyst fouling. As shown in Table 3, the device can better exert the catalyst performance, promote the hydrocarbon oil to produce more low-carbon olefin, has higher yield of ethylene and propylene products, especially higher yield of ethylene products, and breaks through the limitation that the conventional catalytic cracking device only produces propylene in a rich way and has extremely low ethylene yield.
Of course, the present invention is capable of other various embodiments and its several details are capable of modification and variation in light of the present invention by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (17)
1. A moving bed apparatus for producing light olefins by cracking hydrocarbon oil, the moving bed apparatus comprising a moving bed reactor, the moving bed reactor comprising:
the gas distribution plate is arranged in the moving bed reactor and is horizontally arranged in the radial direction of the moving bed reactor;
the catalyst baffle plate is arranged below the gas distribution plate in the moving bed reactor and horizontally arranged in the radial direction of the moving bed reactor, and the gas distribution plate and the catalyst baffle plate divide the moving bed reactor into a feeding zone, a reaction zone and a hydrocarbon oil product zone to be conveyed from top to bottom in sequence;
a catalyst inlet arranged at the top of the moving bed reactor and extending to the reaction zone through a first pipeline;
a hydrocarbon oil raw material inlet arranged at the upper part of the moving bed reactor;
a hydrocarbon oil product outlet arranged in a region to be transported of the hydrocarbon oil product;
the catalyst outlet is arranged at the bottom of the moving bed reactor and is positioned in the region where the hydrocarbon oil products are to be conveyed.
2. The moving bed apparatus according to claim 1, wherein the catalyst inlet is provided at a top end of the moving bed reactor, and the first line extends in an axial direction of the moving bed reactor and into the reaction zone; the hydrocarbon oil raw material inlet is arranged along the radial direction of the moving bed reactor, so that the hydrocarbon oil raw material enters the moving bed reactor in a direction perpendicular to the flowing direction of the catalyst.
3. The moving bed apparatus according to claim 1, wherein the moving bed reactor is further provided with a catalyst distribution plate disposed in the reaction zone so that the catalyst is uniformly dispersed into the reaction zone to form a catalyst bed.
4. A moving bed apparatus according to claim 3, wherein the catalyst distribution plate comprises at least one layer of arcuate panels, the at least one layer of arcuate panels being arranged in a step-wise arrangement; the ratio of the cambered surface height to the cambered surface width of at least one layer of cambered surface plate is less than or equal to 0.5, and the cambered surface width of at least one layer of cambered surface plate is more than 1.2 times of the diameter of the first pipeline.
5. The moving bed apparatus according to claim 4, wherein an arc panel adjacent to the first pipeline of the at least one layer of arc panels is a first layer of arc panel; the first layer of arc panel is an arc surface, the at least one layer of arc panel except the first layer of arc panel is an arc surface ring, and the relation between the number k of the arc surface plates in the arc surface ring and the number n of the arc panels is k=2 n-2 The method comprises the steps of carrying out a first treatment on the surface of the The arc surface plates of the next layer are uniformly distributed on two sides of the arc surface plate of the upper layer, and the arc surface extension lines of the arc surface plates of the upper layer are intersected at the arc surface midpoint of the arc surface plates of the next layer.
6. The moving bed apparatus according to claim 5, wherein the height difference between two adjacent arc plates is 1.2 times or more the height of at least one of the two adjacent arc plates, and the pitch between the arc plates on the same layer is 10 times or more the diameter of the catalyst particles.
7. Moving bed apparatus according to claim 1, wherein the catalyst baffle is provided with a plurality of catalyst blanking holes; the diameter of the catalyst blanking hole is 0.1-5 times of the diameter of the first pipeline; the catalyst discharging holes are symmetrical with the center point of the catalyst distribution plate in a center.
8. The moving bed apparatus of claim 7, wherein the moving bed reactor further comprises a first valve disposed proximate the catalyst barrier to control whether catalyst passes through the catalyst barrier by adjusting the first valve.
9. The moving bed apparatus according to claim 1, wherein the hydrocarbon oil product outlet is arranged in a radial direction of the moving bed reactor so that hydrocarbon oil product flows out in the radial direction of the moving bed reactor.
10. A moving bed apparatus according to claim 3, wherein the gas distribution plate is a metal powder metallurgical plate having a porosity of 55% or more; the catalyst baffle is a metal powder metallurgy plate, and the porosity is more than or equal to 55%; the catalyst distribution plate is a metal powder metallurgy plate, and the porosity is more than or equal to 55%.
11. The moving bed apparatus of claim 9, further comprising a stripping distributor, a catalyst surge tank, and a catalyst regenerator;
the stripping distributor is connected with the catalyst outlet;
the catalyst buffer tank is provided with a circulating catalyst inlet and a circulating catalyst outlet;
the catalyst regenerator is provided with a regenerated catalyst inlet and a regenerated catalyst outlet, the circulating catalyst inlet and the regenerated catalyst inlet are respectively connected with the stripping distributor, and the circulating catalyst outlet and the regenerated catalyst outlet are respectively connected with the catalyst inlet.
12. The moving bed apparatus according to claim 11, wherein a catalyst baffle and a regeneration air inlet are provided in the catalyst regenerator, and the regeneration air inlet is provided below the catalyst baffle in the axial direction of the moving bed reactor.
13. The moving bed apparatus according to claim 11, wherein the moving bed reactor is located between the stripping distributor and the catalyst surge tank in an axial direction of the moving bed reactor, and the moving bed reactor is located between the stripping distributor and the catalyst regenerator.
14. A process for the preparation of light olefins by hydrocarbon oil cracking, characterized in that it uses the moving bed apparatus according to any one of claims 1 to 13, comprising the steps of:
the catalyst enters the moving bed reactor from a catalyst inlet, and a catalyst bed layer is formed in a reaction zone;
hydrocarbon oil raw materials enter the moving bed reactor from a hydrocarbon oil raw material inlet, move downwards along the axial direction of the moving bed reactor through a gas distribution plate and contact the catalyst bed layer, and are converted into low-carbon olefin;
the low-carbon olefin and unreacted hydrocarbon oil raw materials pass through the catalyst baffle plate and flow out from the hydrocarbon oil product outlet.
15. The method for preparing low-carbon olefin by cracking hydrocarbon oil according to claim 14, wherein the catalyst after carbon deposition passes through a catalyst baffle plate, enters a region to be conveyed for hydrocarbon oil products, passes through a catalyst outlet, enters a stripping distributor, and then enters a catalyst buffer tank and/or a catalyst regenerator for preheating and/or regeneration under the stripping action; after being preheated or regenerated, the carbon deposition catalyst enters the moving bed reactor through the catalyst inlet and is recycled.
16. The method for preparing low-carbon olefin by cracking hydrocarbon oil according to claim 14, wherein the hydrocarbon oil raw material is hydrocarbon fraction with boiling point of 30-350 ℃; the hydrocarbon oil raw material enters the moving bed reactor after being preheated, the preheating temperature is 200-400 ℃, and the feeding airspeed of the hydrocarbon oil raw material is 1-10h -1 The method comprises the steps of carrying out a first treatment on the surface of the The temperature of the catalyst bed layer of the moving bed reactor is 560-640 ℃, and the pressure of the catalyst bed layer is 0-0.1MPa.
17. The method for preparing light olefins by hydrocarbon oil cracking according to claim 15, wherein the preheating temperature of the catalyst buffer tank is 600-680 ℃, and the catalyst regeneration temperature of the catalyst regenerator is 600-680 ℃.
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| CN101029250A (en) * | 2007-04-11 | 2007-09-05 | 中国石油大学(北京) | Method and apparatus for producing low-carbon olefine by catalyzing and cracking light-hydrocarbon material |
| CN103073377A (en) * | 2011-10-25 | 2013-05-01 | 中国石油化工股份有限公司 | Method for preparation of light olefins through catalytic conversion by oxygen-containing compound |
| CN105585407A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing light olefin from small molecular hydrocarbon mixture |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101029250A (en) * | 2007-04-11 | 2007-09-05 | 中国石油大学(北京) | Method and apparatus for producing low-carbon olefine by catalyzing and cracking light-hydrocarbon material |
| CN103073377A (en) * | 2011-10-25 | 2013-05-01 | 中国石油化工股份有限公司 | Method for preparation of light olefins through catalytic conversion by oxygen-containing compound |
| CN105585407A (en) * | 2014-10-20 | 2016-05-18 | 中国石油化工股份有限公司 | Method for preparing light olefin from small molecular hydrocarbon mixture |
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