CN111715153A - Alkane dehydrogenation circulating fluidized bed reaction device - Google Patents
Alkane dehydrogenation circulating fluidized bed reaction device Download PDFInfo
- Publication number
- CN111715153A CN111715153A CN201910201890.5A CN201910201890A CN111715153A CN 111715153 A CN111715153 A CN 111715153A CN 201910201890 A CN201910201890 A CN 201910201890A CN 111715153 A CN111715153 A CN 111715153A
- Authority
- CN
- China
- Prior art keywords
- reactor
- catalyst
- central axis
- phase section
- primary cyclone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 47
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 45
- 150000001335 aliphatic alkanes Chemical class 0.000 title claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 156
- 230000002093 peripheral effect Effects 0.000 claims abstract description 4
- 230000000630 rising effect Effects 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 2
- 239000007924 injection Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 15
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 238000005299 abrasion Methods 0.000 abstract description 3
- 239000012071 phase Substances 0.000 description 66
- 238000011069 regeneration method Methods 0.000 description 47
- 230000008929 regeneration Effects 0.000 description 41
- 239000007789 gas Substances 0.000 description 36
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 10
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 10
- 239000001294 propane Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000007872 degassing Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 6
- 238000005243 fluidization Methods 0.000 description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 6
- 239000001282 iso-butane Substances 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000012492 regenerant Substances 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000003546 flue gas Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008676 import Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910019923 CrOx Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- JTJMJGYZQZDUJJ-UHFFFAOYSA-N phencyclidine Chemical class C1CCCCN1C1(C=2C=CC=CC=2)CCCCC1 JTJMJGYZQZDUJJ-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/24—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles according to "fluidised-bed" technique
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/18—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with fluidised particles
- B01J8/1872—Details of the fluidised bed reactor
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
Abstract
The alkane dehydrogenation circulating fluidized bed reaction device comprises a reactor and a reactor settling section, wherein the reactor settling section is positioned at the upper part of the reactor, a reaction raw material inlet is formed in the reactor, a catalyst distributor is arranged in the reactor, a catalyst is sprayed into the reactor along the direction from the peripheral wall of the reactor to a central axis through the catalyst distributor, and the reaction raw material inlet is positioned below the catalyst distributor. The alkane dehydrogenation reaction is carried out in the reaction device, which is beneficial to the full contact of oil gas and catalyst, thereby promoting the dehydrogenation reaction. In addition, the conveying separation height in the settling section is low, and the abrasion and the running loss of the catalyst are effectively reduced.
Description
Technical Field
The application relates to an alkane dehydrogenation reaction device, more specifically relates to an alkane dehydrogenation circulating fluidized bed reaction device, and belongs to the field of petrochemical industry.
Background
Propylene and butylene are important chemical raw materials, and propane and butane are dehydrogenated to generate the propylene and the butylene, so that the selectivity of olefin is high, and hydrogen can be generated as a byproduct.
Propane and butane dehydrogenation have well-established technologies in use, and typically Oleflex from UOP and Catofin from ABB Lummus. The former adopts a load type Pt catalyst and a moving bed reaction regeneration system, and can realize continuous reaction and catalyst regeneration; the latter adopts supported CrOx catalyst and fixed bed reactor, and the single reactor can only be operated intermittently, and the whole device needs five reactors connected in parallel for continuous operation.
Alkane dehydrogenation has the following characteristics: the strong endothermic reaction needs to supply a large amount of heat for the reaction in time; the conversion rate is balanced by thermodynamics, and the conversion rate is reduced when the pressure is high; the catalyst is coked and deactivated, and needs to be regenerated in time. These characteristics determine that the circulating fluidized bed is an ideal alkane dehydrogenation reactor because the circulating fluidized bed can realize continuous reaction regeneration, the high-temperature regenerant can directly supply heat for the reaction in time, and the pressure drop of the fluidized bed is smaller under the condition of the same linear velocity. However, circulating fluidized bed dehydrogenation technology must solve the problem from both the catalyst and the reactor to achieve a real technological breakthrough.
The reaction device is especially provided for improving the efficiency of alkane dehydrogenation reaction.
Disclosure of Invention
An object of the present application is to provide an alkane dehydrogenation circulating fluidized bed reaction apparatus, in which alkane dehydrogenation reaction is performed, which facilitates sufficient contact between oil gas and a catalyst, thereby promoting dehydrogenation reaction.
Another object of the present application is to provide a circulating fluidized bed reactor for alkane dehydrogenation, which can greatly reduce the height of the transportation and separation in the settling section, and effectively reduce the abrasion and loss of the catalyst.
It is another object of the present invention to provide a circulating fluidized bed reactor for alkane dehydrogenation, which facilitates the catalyst to flow upward along the center of the reactor and downward along the sidewall of the reactor, thereby facilitating the reduction of the axial temperature gradient in the reactor.
The utility model provides a circulating fluidized bed reaction unit of alkane dehydrogenation, including reactor and reactor settling section, reactor settling section is linked together with the reactor, is equipped with the reaction raw materials import on the reactor, wherein, is equipped with the catalyst distributor in the reactor, makes the catalyst spout into the reactor along the reactor perisporium to the direction of center pin through the catalyst distributor in, the reaction raw materials import is located the below of catalyst distributor.
Drawings
FIG. 1 circulating fluidized bed reactor for alkane dehydrogenation of the present application
FIG. 2 is a schematic view of the structure of one embodiment of the catalyst distributor
FIG. 3 is a cross-sectional view of another embodiment of a catalyst distributor
FIG. 4 schematic diagram of a reactor settling section of a reactor apparatus of the present application
FIG. 5 is a schematic view of the structure of the cover and cyclone in the settling section of FIG. 4
Detailed Description
For better understanding of the inventive content of the present application, the technical solutions of the present application will be clearly and completely described below with reference to the specific embodiments, examples and drawings of the present application, and the following embodiments are used for illustrating the present application and are not intended to limit the scope of the present application.
The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. All percentages, ratios, proportions, or parts are by weight unless otherwise specified.
Dense-phase section: the section has larger bed layer diameter, lower gas velocity and higher catalyst fluidization density, and is beneficial to the contact and reaction of gas phase and solid phase.
A dilute phase section: the diameter of the bed layer at the section is smaller, the gas velocity is higher, and the fluidization density of the catalyst is lower. The purpose is as follows: the linear velocity is increased, so that oil gas quickly leaves the reactor, and secondary reaction of olefin is reduced; the catalyst has low density, and is also beneficial to reducing secondary reaction, especially the generation of coke; catalyst transport requirements.
The "peripheral wall" of the reactor in the present application refers to the wall of the reactor which is parallel to the central axis of the reactor.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present application. The preferred embodiments and materials described herein are intended to be exemplary only.
In one aspect, the application provides an alkane dehydrogenation circulating fluidized bed reaction device, which comprises a reactor and a reactor settling section, wherein the reactor settling section is located at the upper part of the reactor, a reaction raw material inlet is formed in the reactor, a catalyst distributor is arranged in the reactor, a catalyst is sprayed into the reactor along the direction from the peripheral wall of the reactor to a central shaft through the catalyst distributor, and the reaction raw material inlet is located below the catalyst distributor.
The catalyst distributor of the present application can be all possible configurations to achieve the above-described catalyst injection approach.
In some embodiments, the catalyst distributor is an annular tube, and the annular tube is provided with an opening for spraying the catalyst.
Generally, a circular pipe is a closed ring-shaped structure surrounded by a pipe with a circular cross section.
In some embodiments, more than two openings are provided on the annular tube, and the openings on the annular tube are located on the side wall close to the central axis of the annular tube and are evenly distributed.
In some embodiments, the side wall near the central axis of the annular tube is provided with through openings around the central axis.
A circle of through openings are formed in the side wall, closest to the central shaft, of the annular pipe, and the distances between the upper edge and the lower edge of each opening can be equal. It is also possible to vary, for example, in a circle of openings, the distance between the upper and lower edges of one section of opening is relatively large, and the distance between the upper and lower edges of the other section of opening is relatively small. The "upper" and "lower" edges are used herein to refer to the relative positions of the central axis of the annular tube and the opening in the reactor with the centerline axis parallel.
In some embodiments, the opening for ejecting the catalyst is provided on the wall of the annular tube on the side of the plane, with respect to the plane of the side wall of the annular tube closest to the central axis, and the opening is directed toward the central axis of the annular tube. When the annular tube is installed in the reactor, the opening is located above the above-mentioned plane, so that the catalyst is ejected in a direction obliquely upward toward the central axis of the reactor.
In certain embodiments, when the annular tube is provided with a plurality of openings, the openings are generally circular in shape.
In certain embodiments, at least two nozzles are provided on the side of the annular tube near the central axis for ejecting catalyst therethrough.
The annular pipe is provided with a plurality of nozzles uniformly close to the side wall of the central shaft, and the opening direction for spraying the catalyst is vertical to the central shaft of the annular pipe or the opening direction is inclined upwards. In this manner, the catalyst may be injected into the reactor through the nozzle perpendicularly toward the central axis, or obliquely upward toward the central axis.
Through the catalyst distributor, the high-temperature regenerated catalyst is sprayed to the center from the side surface of the reactor through the catalyst distribution ring pipe, so that the catalyst can be effectively prevented from entering a ring core structure with thick middle thin side walls near the blanking section of the reactor. That is, the catalyst concentration in the middle of the reactor increases near the catalyst inlet in the reactor. The catalytic dehydrogenation method is beneficial to improving the contact efficiency of oil gas near the catalyst inlet in the reactor and the catalyst, so that the catalytic dehydrogenation reaction of alkane is promoted.
In addition, through the catalyst distributor of the present application, the high-temperature catalyst sprayed toward the center of the reactor flows upward along the center of the reactor and then downward along the walls of the reactor by the lift medium. The temperature gradient in the axial direction is significantly reduced for the reaction temperature in the entire reactor, i.e. the temperature variation in the reactor is small. The side reaction of alkane dehydrogenation reaction caused by local high temperature is reduced, and the alkane catalytic dehydrogenation reaction is further improved, namely the conversion rate and the selectivity of alkane dehydrogenation are improved.
The reactor of the present application includes a dense phase section and a dilute phase section, the dilute phase section being located above the dense phase section.
In certain embodiments, the catalyst distributor is located between 1/6 and 5/6, preferably between 1/2 and 2/3, of the height of the dense phase section of the reactor, based on the bottom of the reactor.
Generally, the catalyst fluidization concentration is high below the catalyst inlet and decreases during the ascent. In the application, the catalyst distributor is positioned at a distance of 1/6-5/6 dense-phase section height from the bottom of the reactor, and high-temperature catalyst is continuously injected in the process that the catalyst below the catalyst distributor ascends along the axial direction, so that the fluidization density cannot be reduced due to the introduction of the catalyst in the process that the catalyst ascends. Therefore, the catalyst and the oil gas are fully contacted in the dense-phase section, thereby promoting the catalytic dehydrogenation of the alkane. Otherwise, if the catalyst distributor is arranged at the bottom of the reactor in order to increase the contact time for the catalyst and the oil gas to flow upwards simultaneously, the fluidization concentration of the catalyst is gradually reduced in the rising process, and the phenomenon of insufficient contact between the oil gas and the catalyst at the upper part of the dense-phase section can occur.
In this application, the dense phase section of the reaction is a constant diameter tank. The dilute phase section is preferably a pipeline with equal diameter, and can also have unequal diameter.
The reaction apparatus of the present application does not contain only the components defined in the present application, and other components and structures of the reaction apparatus may adopt the structures disclosed in the prior art.
On the other hand, the reactor settling section of the reactor is positioned above the reactor, the outlet of the reactor is positioned in the settler, and a primary cyclone separator, a primary cyclone riser and a cover body are arranged in the settling section; the upper part of the cover body is in a circular truncated cone shape, the lower bottom surface of the circular truncated cone is the lower part of the cover body, and the lower part of the cover body is in a cylindrical structure; the area of the opening at the lowermost end of the cover body is larger than the area of the outlet of the reactor; the outer circumference of the upper bottom surface of the circular table is connected with the periphery of the primary cyclone gas rising pipe, or the outer circumference of the upper bottom surface of the circular table is connected with the periphery above the inlet of the primary cyclone separator.
Preferably, the lower part of the cover body is of a cylindrical structure.
The cross sections of the lower part cylindrical structure of the cover body, which are perpendicular to the axial direction, can be equal or unequal. That is, the lower portion of the cover may be a cylinder whose diameter is gradually reduced from top to bottom, or may be a cylinder whose diameter is gradually increased from top to bottom. Preferably, the lower portion of the housing is cylindrical in configuration.
The primary separator is any one structure disclosed in the prior art, and generally comprises a primary separator body and a blanking leg, wherein the blanking leg is positioned below the body.
In one embodiment, the outlet of the feed leg of the primary cyclone is lower than the outlet of the reactor.
In one embodiment, an angle θ between a truncated cone generatrix of the truncated cone-shaped portion of the cover body and the lower bottom surface is larger than an angle of repose of the catalyst particles. Thus, the catalyst particles falling on the conical surface can be ensured to slide freely.
In some embodiments, the area of the lowermost end opening of the shroud is equal to or greater than the area of the dilute phase transport pipe outlet. Preferably, the area of the opening at the lowermost end of the cover body is 1.5-5 times, more preferably 2-3 times of the area of the outlet of the reactor.
In the settling section of this application, outside the cover body, still be equipped with the cyclone. More than two cyclones may be provided. Or more than two primary cyclone separators and more than two secondary cyclone separators are arranged. The cyclone separator arranged outside the cover body is communicated with a gas collection chamber in the settler through a gas rising pipe.
In some embodiments, the outlet of the primary cyclone is not connected to the inlet of the primary cyclone.
In some embodiments, the outlet of the primary cyclone gas rising pipe is connected with the inlet of the primary cyclone separator in a socket-and-spigot manner, and a gap is formed between the pipe walls of the primary cyclone gas rising pipe and the inlet of the primary cyclone separator, so that oil gas in the settler can enter the cyclone separator.
In this application, the top end of the hood in the settling section is relatively far from the reactor outlet. In some cases, the top of the hood is spaced from the reactor outlet by a distance of about one cyclone height. In addition, a cylindrical portion is provided below the circular truncated cone. The oil gas discharged from the outlet of the reactor, a part of the oil gas flows into the settler from the edge of the lower opening of the cover body; the other part of the oil gas enters the cover body and directly enters the upper part of the settler through the inlet of the primary separator. Thus, compared with the condition that oil gas completely enters the settler and flows upwards, the oil gas flows into the cyclone separator from the upper direction and the lower direction of the settler, so that the apparent gas velocity is greatly reduced, the amount of catalyst carried by the upward flow of the oil gas is reduced, and the conveying separation height (TDH) is reduced.
In certain embodiments, the lowermost end of the hood is below the reactor outlet in the settling section. I.e. the plane of the lowermost end of the hood is lower than the plane of the reactor outlet. The oil gas discharged from the outlet of the reactor can enter the cover body, and can also directly enter the settler outside the cover body.
In certain embodiments, the settling section comprises a dense phase section and a dilute phase section, and the lowermost end of the hood is higher than the interface between the dilute phase section and the dense phase section, i.e., the lowermost end of the hood is located within the dilute phase section of the settler.
In certain embodiments, the inlet of the primary separator is not connected to the reactor outlet.
In some embodiments, the draft tube outlet of the primary separator is at the same level as the primary cyclone inlet, or the draft tube outlet of the primary separator is higher than the primary cyclone inlet.
On the other hand, the alkane dehydrogenation circulating fluidized bed reaction-regeneration device comprises a reaction device and a regeneration device, wherein the reaction device and the regeneration device are communicated with each other through a catalyst regeneration inclined pipe and a catalyst waiting inclined pipe;
the regeneration device comprises a regenerator and a regeneration settler, the regeneration settler is positioned above the regenerator, the regenerator comprises a regeneration dense-phase section and a regeneration dilute-phase section, and the regeneration dilute-phase section extends into the regeneration settler.
The height of the catalyst in the annular space between the dilute phase section conveying pipe and the wall of the settler can be controlled by increasing the height of the reactor dilute phase section conveying pipe. This height can be used, on the one hand, to adjust the driving force of the catalyst circulation and, on the other hand, to adjust the degassing and stripping effect of the catalyst.
The larger the proportion of the height of the regeneration dilute phase section to the height of the regeneration settler is, the larger the driving force of the regeneration catalysis in the regeneration settler is, and the better the degassing and gas stripping effects are. Therefore, the amount of additionally introduced stripping nitrogen when the regenerated catalyst enters the reactor can be reduced, the degassing and stripping effects are better, the stripping demand is reduced, the cost is saved, and the dehydrogenation reaction is more favorable.
The reactor here is also provided with a catalyst distributor as described above.
Compared with the prior art, the application has the advantages that:
1) the catalyst enters the reactor from the side of the reactor, and the fluidization density of the catalyst below the entry point is high and cannot fall along with the rise of the axial position of the reactor, so that the full contact between oil gas and the catalyst is facilitated, and the dehydrogenation reaction is promoted.
2) The catalyst entering the reactor is sprayed from the side to the center through the distribution ring pipe, so that the catalyst can be effectively prevented from entering the position near the blanking section of the reactor to form a ring-core structure with a thick middle thin side wall, and the contact efficiency of oil gas near the blanking section of the catalyst and the catalyst can be improved.
3) The catalyst distribution pipe is favorable for promoting the catalyst to flow upwards along the center of the reactor and downwards along the wall of the reactor, thereby being favorable for reducing the axial temperature gradient in the reactor.
4) The height of the catalyst in the annular space between the dilute phase conveying pipe and the wall of the settler can be controlled by increasing the heights of the dilute phase conveying pipes of the reactor and the regenerator. This height can be used, on the one hand, to adjust the driving force of the catalyst circulation and, on the other hand, to adjust the degassing and stripping effect of the catalyst. The higher the height, the greater the driving force, and the better the degassing and air stripping effects. Particularly, the better the natural degassing effect of the regenerant, the less the consumption of stripping nitrogen, and the better the degassing and stripping effects, the more beneficial to the dehydrogenation reaction.
5) In this application reaction unit, under the circumstances that does not change tolerance, settler diameter, reduced the catalytic agent amount that oil gas upflow carried in the settler to reduce substantially and carry the high TDH of separation. The concentration of the catalyst before the oil gas enters the cyclone separator is reduced, and the abrasion and the running loss of the catalyst are effectively reduced.
The following further description is made with reference to the specific drawings and specific examples:
example 1
As shown in the attached fig. 1 and fig. 2, the reaction device for alkane catalytic dehydrogenation provided by the present application is used in combination with a catalyst regeneration device. These two units may be used separately, in combination with other prior art reaction units or catalyst regeneration units, respectively.
The circulating fluidized bed alkane catalytic dehydrogenation reaction-regeneration device of the present example, the reaction device and the regeneration device were arranged in parallel.
The reaction device for catalytic dehydrogenation of alkane comprises a reactor and a reaction settler 3, wherein the reactor settler 3 is positioned at the upper part of the reactor, and the reactor comprises a catalyst distributor 2, a dense phase section 1 and a dilute phase section 13. Dense phase section 1 and dilute phase section 13 are both of equal diameter structure, and dilute phase section 13 extends into reaction settler 3. The catalyst distributor 2 is positioned between 1/6-5/6, preferably 1/2-2/3, of the height of the dense-phase section 1 of the reactor by taking the bottom of the reactor as a reference, and the catalyst distributor 2 is arranged above an inlet of the alkane dehydrogenation raw material.
Several layers of grids 10 are provided in the dense phase section 1 of the reactor.
Referring to fig. 2, the catalyst distributor 2 is an annular tube having a plurality of openings uniformly formed in the side wall thereof near the central axis. Alternatively, the opening for ejecting the catalyst is provided on the wall of the annular tube on the side of the plane, with reference to the plane of the side wall of the annular tube closest to the central axis, and the direction of the opening is toward the central axis of the annular tube, as shown in fig. 1, that is, in this case, the opening for ejecting the catalyst is located above the plane, so that the catalyst is ejected in a direction obliquely upward toward the central axis of the reactor.
Referring to fig. 3, the catalyst distributor 2 is a ring-shaped pipe, and through openings are provided in a side wall of the ring-shaped pipe, which is close to a central axis of the ring-shaped pipe, and a side wall of the ring-shaped pipe, which surrounds the central axis by one turn. The upper and lower edges of the opening are equally spaced.
The regenerator comprises a regenerator and a regenerator settling section 5, the regenerator comprises a regeneration dense-phase section 4 and a regeneration dilute-phase section 15, the regeneration dense-phase section 4 and the regeneration dilute-phase section 15 are both in an equal-diameter structure, and the regeneration dilute-phase section 15 extends into the regenerator settling section 5.
One end of the catalyst regeneration inclined tube 12 is connected with the regeneration settler, the other end is connected with the dense phase section 2 of the reactor, one end of the catalyst to-be-regenerated inclined tube 11 is connected with the reaction settler 3, and the other end is connected with the regeneration dense phase section 4. In dense phase section 1, catalyst regeneration chute 12 passes through the reactor wall into the reactor and is connected to catalyst distributor 2, or catalyst regeneration chute 12 is integral with catalyst distributor 2. In the regeneration settling section 5 of the regeneration device, because the height of the dilute phase section of the regenerator is higher, the height of the catalyst in the annular gap between the dilute phase section and the wall of the regeneration settling device is higher, and a larger driving force is given to the regenerated catalyst in the regeneration settling device, so that the regenerated catalyst can enter the catalyst distributor through the catalyst regeneration inclined tube. Due to this greater driving force for regenerating the catalyst, the amount of lift medium (e.g. nitrogen) fed to the reactor is reduced and, consequently, the degassing of the catalyst in the settler is also greatly improved.
The specific process flow comprises the following steps: the alkane catalytic dehydrogenation raw material 18 enters the reactor through the lower part of the dense-phase section 1 of the reactor, the internal oil gas and the catalyst flow upwards in parallel flow in the reactor, the raw material reacts in the dense-phase section 1 of the reactor, then enters the settling section 3 of the reactor through the dilute-phase section 13 and is rapidly separated by the aid of the cyclone separator, and the oil gas 17 leaves the reactor and enters a subsequent separation system. The settled spent catalyst is stripped by stripping medium 14 (such as steam) and then enters the dense phase section 4 of the regenerator through spent inclined tube 11. The bottom of the dense phase section 4 of the regenerator is injected with air and fuel 9 to burn, and simultaneously, the coke on the surface of the spent catalyst is burnt. The regenerated flue gas and the catalyst flow upwards in parallel like the reactor and enter the settling section 5 of the regenerator through the dilute phase section 15 for gas-solid separation, and the flue gas 7 leaves the regenerator and is discharged after energy recovery, washing and dust removal. The settled regenerated catalyst is stripped by stripping medium 14 (such as nitrogen) and then passed through the catalyst distributor from the side of the reactor via the regeneration chute 12 into the dense phase section 2 of the reaction.
The reaction settler of the reaction device in this embodiment may be of any structure disclosed in the prior art, and may also be as shown in fig. 4. The reactor comprises a dense phase section 1 and a dilute phase section 13, the dilute phase section 13 extending into the settler 3.
The settling section 3 comprises a parachute cap cyclone fast subassembly comprising a primary cyclone separator 6 and a shroud 19. As shown in fig. 5, the primary separator 6 comprises a cylinder 61, an inverted cone 64 and a blanking leg 65 from top to bottom, an inlet 62 of the primary separator 6 is arranged at the upper part of the cylinder 61, and the air flow enters the primary separator 6 from the inlet 62 along the tangential direction. The top of the primary cyclone separator 6 is provided with a gas lift pipe 63 which is communicated with the primary cyclone separator 6, and the oil gas or the flue gas entering the primary cyclone separator 6 is discharged through the gas lift pipe 63. The cover 19 comprises two parts, the upper part is in the shape of a circular truncated cone, the lower part is in the shape of a cylinder, and the cover can be integrally formed. The upper end (i.e. the upper bottom surface of the circular truncated cone) edge of the cover body 19 is connected with the periphery of the gas rising pipe 63, and the primary cyclone separator 6 is arranged in the cover body. The lower end face of the cover 19 is lower than the dilute phase section 13 outlet, and the lower end face of the cover 19 is located in the dilute phase section of the settler.
The included angle between the generatrix of the truncated cone-shaped upper part of the cover body 19 and the lower bottom surface is larger than the repose angle of the catalyst particles. That is, the size of the included angle of the truncated cone is dependent on the angle of repose of the catalyst particles used, and the catalyst can be ensured to flow downwards.
The cross-sectional area of the opening at the lower end of the cover body 19 is larger than that of the outlet of the dilute phase conveying section 13
In this embodiment, the center lines of the cylindrical body 61, the inverted cone 64, the cover 19, and the reactor 2 of the primary cyclone 6 coincide with each other. The outlet of the dipleg is remote from the outlet of the dilute phase section 13, i.e. the outlet of the dipleg cannot be remote from the outlet of the dilute phase section 13, otherwise the catalyst of the coarse cyclone 6 is not favoured for discharge from the dipleg by being subjected to an upward flow of gas from the dilute phase section 13.
In this embodiment, the inlet 62 of the primary cyclone 6 is not connected to the outlet of the dilute-phase feed pipe 5.
In the settling section 3, a cyclone separator 8 and a gas collection chamber 20 are arranged in the space outside the cover body 19. In this embodiment, two sets of cyclone separators are provided, each set of cyclone separator includes a primary cyclone separator 81 and a secondary cyclone separator 82, and the secondary cyclone separator 82 is communicated with the plenum chamber 20 through a riser. The inlet of the primary cyclone 81 is at the same level as the inlet 62 of the primary cyclone 6, or the inlet of the primary cyclone 81 is slightly lower than the inlet 62 of the primary cyclone 6.
The following is a reaction carried out by using the alkane catalytic dehydrogenation reaction-regeneration apparatus provided in example 1 of the present application, and the specific reaction process and reaction result are shown in experimental examples 2-5, in experimental example 1, no catalyst feeding loop is used.
The catalyst ADHO-1 used in the experimental examples 1-5 is an alkane dehydrogenation catalyst in the patent ZL201110123675.1 of the inventor, and the carrier of the catalyst is alumina, and the catalyst also comprises zinc oxide, tungsten oxide and sodium oxide. The mass ratio of the zinc oxide to the tungsten oxide is about 8.4, and the content of the sodium oxide is proper.
Experimental example 1: dehydrogenation of propane to propylene
Raw materials: 99.9 wt% propane
Catalyst: environment-friendly metal oxide catalyst ADHO-1(ZL 201110123675.1)
Average temperature of bed layer: at 600 ℃.
Structural form of the reaction-regeneration system: the regenerated catalyst enters the reactor from the side of the reactor at a location 1/2 located at the height of the dense phase section of the reactor, based on the bottom of the reactor. The regeneration inclined tube is stopped at the opening on the side surface of the reactor.
Experimental example 2: dehydrogenation of propane to propylene
Raw materials: 99.9 wt% propane
Catalyst: environment-friendly metal oxide catalyst ADHO-1(ZL 201110123675.1)
Average temperature of bed layer: at 600 ℃.
Structural form of the reaction-regeneration system: the regenerated catalyst enters the reactor from the side of the reactor at a location 1/2 located at the height of the dense phase section of the reactor, based on the bottom of the reactor. The regeneration inclined pipe is connected with a catalyst distribution pipe with a plurality of openings on the side surface of a circular ring, and the positions of the openings on the catalyst distribution ring pipe are shown in figure 1.
Experimental example 3: dehydrogenation of propane to propylene
Raw materials: 99.9 wt% propane
Catalyst: environment-friendly metal oxide catalyst ADHO-1(ZL 201110123675.1)
Average temperature of bed layer: at 600 ℃.
Structural form of the reaction-regeneration system: the regenerated catalyst enters the reactor from the side of the reactor at a location 2/3 located at the height of the dense phase section of the reactor, based on the bottom of the reactor. The regeneration inclined pipe is connected with a catalyst distribution pipe with a plurality of openings on the side surface of a circular ring, and the positions of the openings on the catalyst distribution ring pipe are shown in figure 1.
TABLE 1 Experimental examples 1-3 propane dehydrogenation product distribution and propylene Selectivity, wt.%
Experimental example 4: preparation of isobutene by isobutane dehydrogenation
Raw materials: 99.9 wt% isobutane
Catalyst: environment-friendly metal oxide catalyst ADHO-1(ZL 201110123675.1)
Average temperature of bed layer: 580 deg.C.
The structure form of the anti-repeating system is as follows: the regenerant enters the reactor from the side of the reactor at a location 1/2 at the height of the dense phase section of the reactor, based on the bottom of the reactor. The regeneration inclined pipe is connected with a catalyst distribution pipe with a plurality of openings on the side surface of a circular ring, and the positions of the openings on the catalyst distribution ring pipe are shown in figure 1.
Experimental example 5: preparation of isobutene by isobutane dehydrogenation
Raw materials: 99.9 wt% isobutane
Catalyst: environment-friendly metal oxide catalyst ADHO-1(ZL 201110123675.1)
Average temperature of bed layer: 580 deg.C.
The structure form of the anti-repeating system is as follows: the regenerant enters the reactor from the side of the reactor at a location 2/3 at the height of the dense phase section of the reactor, based on the bottom of the reactor. The regeneration inclined pipe is connected with a catalyst distribution pipe with a plurality of openings on the side surface of a circular ring, and the positions of the openings on the catalyst distribution ring pipe are shown in figure 1.
TABLE 2 Experimental examples 4-5 Isobutane dehydrogenation product distribution and isobutene Selectivity, wt%
The present application is described in detail for the purpose of enabling those skilled in the art to understand the content of the present application and to implement the same, and the scope of the present application should not be limited thereby.
Claims (10)
1. The alkane dehydrogenation circulating fluidized bed reactor includes reactor and reactor settling section, the reactor settling section is communicated with the reactor, and the reactor is provided with reaction material inlet, in which a catalyst distributor is set in the reactor, the catalyst is sprayed into the reactor along the direction from peripheral wall of the reactor to central shaft by means of the catalyst distributor, and the reaction material inlet is positioned under the catalyst distributor.
2. The reactor according to claim 1, wherein the catalyst distributor is a ring-shaped tube having a central axis parallel to the central axis of the reactor and having an opening for ejecting the catalyst toward the central axis of the ring-shaped tube,
preferably, the central axis of the annular tube coincides with the central axis of the reactor.
3. The reactor apparatus as claimed in claim 2, wherein the opening in the annular tube is located in the side wall near the central axis of the annular tube;
preferably, the openings for catalyst injection are provided in the side wall of the annular tube at the shortest distance from the central axis.
4. The reactor according to claim 2 or 3, wherein the side wall of the annular tube which is close to the central axis is provided with through openings on the side wall which surrounds the central axis for one circle; or
More than two openings are arranged on the side wall close to the central axis of the annular pipe along the circumferential direction and are uniformly distributed.
5. The reactor according to claim 2 or 3, wherein the openings for ejecting the catalyst are provided in the wall of the annular tube on the side of the plane of the side wall of the annular tube closest to the central axis, with the direction of the openings facing the central axis of the annular tube.
6. The reactor according to claim 1, wherein the catalyst distributor is an annular tube, the central axis of the annular tube is parallel to the axis of the reactor, and at least two nozzles are arranged on the side of the annular tube close to the central axis for ejecting the catalyst through the nozzles;
preferably, a plurality of nozzles are uniformly arranged on the side wall of the annular pipe close to the central axis, and the opening direction of the nozzles is vertical to the central axis of the annular pipe or the opening direction of the nozzles is inclined upwards.
7. The reactor apparatus of any one of claims 1-6 wherein the reactor comprises a dense phase section and a dilute phase section, the dilute phase section being located above the dense phase section,
the catalyst distributor is positioned between 1/6-5/6 of the height of the dense-phase section of the reactor by taking the bottom of the reactor as a reference;
preferably, the catalyst distributor is located between 1/2 and 2/3 of the height of the dense phase section of the reactor.
8. The reactor apparatus according to any one of claims 1 to 7, wherein a primary cyclone separator, a primary cyclone riser and a hood are provided in the settling section of the reactor; the upper part of the cover body is in a circular truncated cone shape, the lower bottom surface of the circular truncated cone is the lower part of the cover body, and the lower part of the cover body is in a cylindrical structure; the area of the opening at the lowermost end of the cover body is larger than the area of the outlet of the reactor; the outer circumference of the upper bottom surface of the circular table is connected with the periphery of the primary cyclone gas rising pipe, or the outer circumference of the upper bottom surface of the circular table is connected with the periphery above the inlet of the primary cyclone separator;
preferably, the lower part of the cover body is of a cylindrical structure.
9. The reactor according to claim 8, wherein the primary cyclone comprises a primary cyclone body and a blanking leg, the blanking leg is positioned below the body, and the edge of the upper bottom surface of the truncated cone-shaped part of the cover body is connected with the periphery of the primary cyclone above the inlet;
preferably, the top of the primary cyclone separator body is provided with a gas lift pipe and is communicated with the primary cyclone separator body, and the edge of the upper bottom surface of the truncated cone-shaped part of the cover body is connected with the periphery of the gas lift pipe of the primary cyclone separator.
10. The reactor apparatus of claim 9 wherein the lowermost end of the hood is below the reactor outlet in the settling section;
preferably, the settling section comprises a dense phase section and a dilute phase section, the lowermost end of the hood being located within the dilute phase section of the settler.
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910201890.5A CN111715153B (en) | 2019-03-18 | 2019-03-18 | Alkane dehydrogenation circulating fluidized bed reaction device |
| EP20773112.6A EP3939697B1 (en) | 2019-03-18 | 2020-02-10 | Alkane catalytic dehydrogenation reaction device comprising an annular catalyst distributor |
| ES20773112T ES2955289T3 (en) | 2019-03-18 | 2020-02-10 | Alkane catalytic dehydrogenation reaction device comprising an annular catalytic distributor |
| US17/440,000 US20220168699A1 (en) | 2019-03-18 | 2020-02-10 | Alkane catalytic dehydrogenation reaction device and catalyst regeneration device |
| PCT/CN2020/074584 WO2020186937A1 (en) | 2019-03-18 | 2020-02-10 | Alkane catalytic dehydrogenation reaction device and catalyst regeneration device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910201890.5A CN111715153B (en) | 2019-03-18 | 2019-03-18 | Alkane dehydrogenation circulating fluidized bed reaction device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111715153A true CN111715153A (en) | 2020-09-29 |
| CN111715153B CN111715153B (en) | 2022-08-05 |
Family
ID=72562978
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910201890.5A Active CN111715153B (en) | 2019-03-18 | 2019-03-18 | Alkane dehydrogenation circulating fluidized bed reaction device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111715153B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1528432A (en) * | 1976-05-07 | 1978-10-11 | Texaco Development Corp | Fluidized cracking catalyst regeneration process and apparatus |
| US20080220965A1 (en) * | 2007-03-09 | 2008-09-11 | Chris Santner | Bathtub-type spent catalyst distributor for effective counter-current regeneration in fluid catalytic cracking units |
| CN102294205A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Reactor for producing low carbon olefin by using methanol or dimethyl ether |
| CN202497866U (en) * | 2011-10-14 | 2012-10-24 | 李小燕 | Powder catalyst distributor of fluidized bed |
| CN203408694U (en) * | 2013-07-10 | 2014-01-29 | 刘英聚 | Fluidized bed powder catalyst distributor |
| CN204469679U (en) * | 2015-01-28 | 2015-07-15 | 中国石化工程建设有限公司 | A kind of reaction system of organic oxygen compound catalytic cracking aromatic hydrocarbons |
| CN104826559A (en) * | 2015-05-05 | 2015-08-12 | 中国石油大学(北京) | Methanol-to-olefin reaction equipment |
| CN106890602A (en) * | 2017-03-25 | 2017-06-27 | 青岛京润石化设计研究院有限公司 | A kind of gas-solid fluidized bed reactor gas-solid preseparator |
-
2019
- 2019-03-18 CN CN201910201890.5A patent/CN111715153B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1528432A (en) * | 1976-05-07 | 1978-10-11 | Texaco Development Corp | Fluidized cracking catalyst regeneration process and apparatus |
| US20080220965A1 (en) * | 2007-03-09 | 2008-09-11 | Chris Santner | Bathtub-type spent catalyst distributor for effective counter-current regeneration in fluid catalytic cracking units |
| CN102294205A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | Reactor for producing low carbon olefin by using methanol or dimethyl ether |
| CN202497866U (en) * | 2011-10-14 | 2012-10-24 | 李小燕 | Powder catalyst distributor of fluidized bed |
| CN203408694U (en) * | 2013-07-10 | 2014-01-29 | 刘英聚 | Fluidized bed powder catalyst distributor |
| CN204469679U (en) * | 2015-01-28 | 2015-07-15 | 中国石化工程建设有限公司 | A kind of reaction system of organic oxygen compound catalytic cracking aromatic hydrocarbons |
| CN104826559A (en) * | 2015-05-05 | 2015-08-12 | 中国石油大学(北京) | Methanol-to-olefin reaction equipment |
| CN106890602A (en) * | 2017-03-25 | 2017-06-27 | 青岛京润石化设计研究院有限公司 | A kind of gas-solid fluidized bed reactor gas-solid preseparator |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111715153B (en) | 2022-08-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103540345B (en) | Catalytic cracking method | |
| CN108753356B (en) | Multistage countercurrent catalytic cracking/cracking system and method | |
| CN105985209A (en) | Method of producing aromatic hydrocarbon through catalytic conversion of organic oxides | |
| CN103540346B (en) | A kind of Desending catalytic cracking device | |
| WO2010074891A2 (en) | Apparatus for regenerating catalyst | |
| US20090107092A1 (en) | Stripping apparatus | |
| CN111715153B (en) | Alkane dehydrogenation circulating fluidized bed reaction device | |
| US20090107884A1 (en) | Stripping apparatus and process | |
| CN216630754U (en) | Fluidized bed reactor | |
| US7914610B2 (en) | Stripping process | |
| EP3939697B1 (en) | Alkane catalytic dehydrogenation reaction device comprising an annular catalyst distributor | |
| EP3854772B1 (en) | Method for catalytic cracking of naphtha | |
| CN113926396B (en) | Heavy oil catalytic conversion reactor and method for preparing propylene by heavy oil catalytic cracking | |
| CN112708447B (en) | Riser reactor capable of reducing back mixing of side wall area | |
| CN113366089B (en) | Process for converting naphtha-containing feedstock to lower olefins and aromatics | |
| CN111715154B (en) | Circulating fluidized bed reaction device | |
| CN109107615B (en) | Regeneration method and regeneration device for alkane dehydrogenation catalyst | |
| EP1456325A1 (en) | Process to regenerate fcc spent catalyst | |
| CN108079912B (en) | Reaction device and reaction method for catalytic dehydrogenation of alkane | |
| US5286281A (en) | Solids-gas separation apparatus and method | |
| CN115253934B (en) | Propane catalytic dehydrogenation fluidized bed reaction-regeneration coupling device and propane catalytic dehydrogenation process method | |
| CN111715306B (en) | Alkane dehydrogenation catalyst regenerating unit | |
| CN113457584B (en) | Reactor for strengthening feed oil mixing | |
| RU2762038C9 (en) | Separation system of elevator reactor | |
| CN216864088U (en) | Clean fuel production riser reactor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231122 Address after: 214522 No.1, wanfugang Road, Jingjiang Economic Development Zone, Taizhou City, Jiangsu Province Patentee after: Jiangsu Bosong Energy Technology Co.,Ltd. Patentee after: HANYI SHENFEI NEW MATERIAL Co.,Ltd. Patentee after: QINGDAO SHENFEI CHEMICAL TECHNOLOGY Co.,Ltd. Patentee after: CHINA University OF PETROLEUM (EAST CHINA) Address before: 214522 No.1, wanfugang Road, Jingjiang Economic Development Zone, Taizhou City, Jiangsu Province Patentee before: JIANGSU BOSONG CHEMICAL TECHNOLOGY Co.,Ltd. Patentee before: HANYI SHENFEI NEW MATERIAL Co.,Ltd. Patentee before: QINGDAO SHENFEI CHEMICAL TECHNOLOGY Co.,Ltd. Patentee before: CHINA University OF PETROLEUM (EAST CHINA) |