CN116407874B - Simulated moving bed adsorption separation system, flushing equipment and method - Google Patents
Simulated moving bed adsorption separation system, flushing equipment and method Download PDFInfo
- Publication number
- CN116407874B CN116407874B CN202111637502.1A CN202111637502A CN116407874B CN 116407874 B CN116407874 B CN 116407874B CN 202111637502 A CN202111637502 A CN 202111637502A CN 116407874 B CN116407874 B CN 116407874B
- Authority
- CN
- China
- Prior art keywords
- flushing
- pipeline
- fluid
- mixing chamber
- inlet
- 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.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1814—Recycling of the fraction to be distributed
- B01D15/1821—Simulated moving beds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
- B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
- B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
- B01D15/1814—Recycling of the fraction to be distributed
- B01D15/1821—Simulated moving beds
- B01D15/1828—Simulated moving beds characterised by process features
- B01D15/1835—Flushing
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Liquids With Adsorbents In General (AREA)
Abstract
本申请涉及模拟移动床吸附分离系统、冲洗设备以及方法，该冲洗设备包括流体分配器，以及循环管路。在模拟移动床吸附分离工艺应用中，使用本申请的吸附分离系统可以减少吸附塔内的物料扰动，不影响吸附塔内的区域流量，提高吸附分离性能，且可以灵活调整冲洗流量的比例；并且可以提高目标产品的纯度与收率，并降低解吸剂/原料比。The present application relates to a simulated moving bed adsorption separation system, a flushing device and a method, wherein the flushing device includes a fluid distributor and a circulation pipeline. In the application of the simulated moving bed adsorption separation process, the use of the adsorption separation system of the present application can reduce the material disturbance in the adsorption tower, does not affect the regional flow in the adsorption tower, improves the adsorption separation performance, and can flexibly adjust the proportion of the flushing flow; and can improve the purity and yield of the target product, and reduce the desorbent/raw material ratio.
Description
Technical Field
The invention relates to the field of simulated moving beds, in particular to a simulated moving bed adsorption separation system, a feed flushing device for the simulated moving bed adsorption separation system and an adsorption separation method.
Background
Simulated moving beds are commonly used to separate components having relatively close relative volatilities but different structural characteristics, common separation components being para-xylene and other mixed xylenes, n-isoparaffins of similar carbon numbers, and the like. In a simulated moving bed, the material flows countercurrent to the adsorbent and periodically changes the position of the incoming and outgoing material, a simulated moving bed process is described in detail in WO2013013493A1 and CN102895800a, among others.
In a typical simulated moving bed process, it generally comprises two feeds (feed F and desorbent D), and two discharges (draw E and raffinate R), wherein the draw is the material enriched in the target product, the raffinate is the remaining material after separation of the target product, and each of the materials periodically changes its position into and out of the adsorption column to effect simulated movement of the adsorbent relative to the bed of material. In a complete simulated moving bed process, the number of the adsorption towers can be 1-2, and materials in the adsorption towers are connected end to end and do self-circulation flow. The material inlet and outlet of the adsorption tower can be controlled by a rotary valve or a program control valve.
In the operation process of the simulated moving bed, in different stepping periods, raffinate R, raw material F, extract E and desorbent D respectively pass through the same bed pipeline, so as to avoid pollution of the residual materials in the pipeline to the materials passing through the pipeline, change the concentration of feed components, disturb the concentration distribution of the components in the bed, lead to the reduction of the purity and yield of a target product, and need to wash the bed pipeline after the materials flow through the bed pipeline.
CN1174750a discloses a flushing device in a simulated moving bed adsorption apparatus, which is characterized in that a flushing valve is arranged on a distribution pipeline of each bed layer, the flushing valve is connected with a circulation pipeline, material pipeline flushing is carried out by using internal reflux liquid to flow through a built-in flushing pipeline, a common section fluid in a specific area is extracted in one part of operation period and discharged to an external collector, and a fluid in the external collector is extracted in another part of operation period, pipeline flushing is carried out, and the fluid is discharged to another common section of an adsorption tower. The entire flushing process requires that the volume of flushing material be greater than the sum of the line volume of the bed and the volume within the fluid distributor.
However, the pipeline flushing method used in the simulated moving bed adsorption separation system at present has the following problems that need to be improved:
(1) Pipeline flushing is carried out by using materials outside the tower, and after the materials enter the adsorption tower, the regional flow in the adsorption tower is affected;
(2) The used flushing materials are inconsistent with the compositions of the materials in the bed layer of the adsorption tower, so that the disturbance of the concentration of the components in the adsorption tower is increased;
(3) The materials such as the extraction liquid, the desorbent and the like are used for pipeline flushing, so that the output of the extraction liquid is reduced, and the circulation quantity of the materials and the desorbent is increased.
Disclosure of Invention
The invention aims to provide a simulated moving bed adsorption separation system, a flushing method and a separation method, wherein the system and the method can flush a material inlet and outlet pipeline by using materials consistent with the components in a fluid in a simulated moving bed adsorption tower on the premise of not influencing the flow rate of the simulated moving bed adsorption tower, the flushing flow rate ratio can be flexibly adjusted, the number of control valves is reduced, and the material inlet and outlet pipeline and the flushing process thereof are simplified.
In one aspect, the present application provides a feed flushing apparatus for a simulated moving bed comprising:
a fluid distributor, wherein the fluid distributor is disposed inside a simulated moving bed, the fluid distributor comprising:
An upper surface support having a channel for passage of fluid,
A lower surface fluid distribution member having a channel for passage of fluid,
A partition extending horizontally across a cross-sectional area of the fluid dispenser, the partition dividing an interior fluid dispenser chamber defined by an upper surface support and a lower surface fluid distribution member into an upper compartment and a lower compartment, the upper compartment being a fluid collection chamber and the lower compartment being a fluid distribution chamber;
A mixing chamber disposed within the fluid dispenser, an upper layer of the mixing chamber being in fluid communication with the fluid collection chamber and a lower layer of the mixing chamber being in fluid communication with the fluid dispensing chamber such that external fluid entering the fluid collection chamber enters the fluid dispensing chamber after passing through the mixing chamber and exits the fluid dispenser through the lower surface fluid distribution member;
A circulation line, the circulation line comprising:
the material inlet and outlet pipeline is connected with the upper layer of the mixing chamber;
a flushing line connected to a lower layer of the mixing chamber;
And the flushing pump is communicated with the material inlet and outlet pipeline and the flushing pipeline.
In one embodiment, a first control valve is provided between the connection port of the material inlet and outlet line and the upper layer of the mixing chamber and the flushing pump, and a second control valve is provided between the connection port of the flushing line and the lower layer of the mixing chamber and the flushing pump.
In one embodiment, a flow controller is also provided in the circulation line.
In one embodiment, a part of the flushing pipeline is sleeved inside the material inlet and outlet pipeline.
In one embodiment, the flushing line is juxtaposed with the in-out material line.
In one embodiment, the size of the flush line is no greater than the size of the in-out line.
In one embodiment, the material feeding and discharging pipeline is further provided with:
a raw material feed port communicated with the raw material feed pipeline,
A desorbent feed inlet in communication with the desorbent feed line,
An extract outlet communicated with the extract outlet pipeline, and
And a raffinate outlet communicated with the raffinate outlet pipeline.
In a second aspect, the present application provides a simulated moving bed adsorptive separation system comprising an adsorption column comprising a plurality of column sections, each column section comprising a fluid distributor and an adsorbent bed;
Wherein, inside the adsorption tower, the fluid distributor and the adsorbent bed layer of each tower section are alternately arranged;
Wherein the fluid distributor of each tower section comprises:
An upper surface support having a channel for passage of fluid,
A lower surface fluid distribution member having a channel for passage of fluid,
A partition extending horizontally across a cross-sectional area of the fluid dispenser, the partition dividing an interior fluid dispenser chamber defined by an upper surface support and a lower surface fluid distribution member into an upper compartment and a lower compartment, the upper compartment being a fluid collection chamber and the lower compartment being a fluid distribution chamber;
A mixing chamber disposed within the fluid dispenser, an upper layer of the mixing chamber being in fluid communication with the fluid collection chamber and a lower layer of the mixing chamber being in fluid communication with the fluid dispensing chamber such that external fluid entering the fluid collection chamber enters the fluid dispensing chamber after passing through the mixing chamber and exits the fluid dispenser through the lower surface fluid distribution member;
wherein, each tower section's fluid distributor still is connected with the circulation pipeline, the circulation pipeline includes:
the material inlet and outlet pipeline is connected with the upper layer of the mixing chamber;
a flushing line connected to a lower layer of the mixing chamber;
The flushing pump is communicated with the material inlet and outlet pipeline and the flushing pipeline;
wherein, still be provided with on the business turn over material pipeline:
a raw material feed port communicated with the raw material feed pipeline,
A desorbent feed inlet in communication with the desorbent feed line,
An extract outlet communicated with the extract outlet pipeline, and
And a raffinate outlet communicated with the raffinate outlet pipeline.
In one embodiment, a first control valve is arranged between the connection port of the material inlet and outlet pipeline and the upper layer of the mixing chamber and the flushing pump, and a second control valve is arranged between the connection port of the flushing pipeline and the lower layer of the mixing chamber and the flushing pump;
and a flow controller is also arranged in the circulating pipeline.
In one embodiment, a part of the flushing pipeline is sleeved inside the material inlet and outlet pipeline.
In one embodiment, the flushing line is juxtaposed with the in-out material line.
In one embodiment, the size of the flush line is no greater than the size of the in-out line.
In a third aspect, the present application provides a line flushing method of a simulated moving bed adsorptive separation system, which line flushing method is performed in the simulated moving bed adsorptive separation system of the present application,
The method comprises the following steps:
in the flushing step, the first control valve, the second control valve and the flushing pump are started, the material is led out from the upper layer of the mixing chamber of the fluid dispenser through the port of the material inlet and outlet pipeline, the material inlet and outlet pipeline is flushed, and the flushed material is led into the lower layer of the mixing chamber of the fluid dispenser through the flushing pipeline, or
In the flushing step, the first control valve, the second control valve and the flushing pump are started, materials are led out from the lower layer of the mixing chamber of the fluid distributor through the ports of the flushing pipeline, the material inlet and outlet pipeline is flushed, and the flushed materials are led into the upper layer of the mixing chamber of the fluid distributor.
In one embodiment, the total volume of material flowing through the flush line in the flush step is greater than the sum of the in and out material line volume, the flush line volume, and the fluid distributor volume.
In one embodiment, the first control valve is in an open state for n times the flushing step time, 0.2 n 1.0.
In one embodiment, the flow rate of the material in the flushing line is 1-3 m/s.
In a fourth aspect, the application is a method for performing adsorption separation using a simulated moving bed adsorption separation system, said method being performed in the simulated moving bed adsorption separation system described above,
The method comprises the following steps:
1) In a first step, feeding the feed in the fluid distributors of the first tower sections, feeding the desorbent in the fluid distributors of the second tower sections, discharging the effluent in the fluid distributors of the third tower sections, and discharging the raffinate in the fluid distributors of the fourth tower sections, and performing a flushing procedure in the fluid distributors of the fifth tower sections,
The flushing process comprises the following steps:
Starting the first control valve, the second control valve and the flushing pump, leading out materials from the upper layer of the mixing chamber of the fluid distributor through the ports of the material inlet and outlet pipelines, flushing the material inlet and outlet pipelines, and leading the flushed materials into the lower layer of the mixing chamber of the fluid distributor through the flushing pipelines, or
Starting a first control valve, a second control valve and a flushing pump, leading out materials from the lower layer of a mixing chamber of the fluid distributor through a port of a flushing pipeline, flushing the material inlet and outlet pipeline, and leading the flushed materials into the upper layer of the mixing chamber of the fluid distributor;
2) In the next step, changing the positions of the sections of the column into which the raw material and the desorbent are fed and the positions of the sections of the column from which the extracted liquid and the raffinate are discharged, and changing the positions of the sections of the column into which the flushing process is performed;
3) Repeating the step 2) until all steps are completed.
In the application of the simulated moving bed adsorption separation process, the adsorption separation system can reduce material disturbance in the adsorption tower, does not influence regional flow in the adsorption tower, improves adsorption separation performance, can flexibly adjust the ratio of flushing flow, can improve the purity and yield of a target product, and reduces the desorbent/raw material ratio.
Drawings
FIG. 1 shows a schematic diagram of a simulated moving bed adsorption column;
fig. 2 shows a schematic view of a flushing device and a flushing mode;
FIG. 3 shows a schematic view of a flushing device and another flushing mode;
FIGS. 4A and 4B show the relationship of the flush line to the in-out material line in the mixing chamber of the fluid dispenser;
fig. 5 shows a schematic diagram of two simulated moving bed adsorption columns connected in series.
Detailed Description
The application is further described in detail below by means of the figures and examples. The features and advantages of the present application will become more apparent from the description.
The word "exemplary" is used herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments. Although various aspects of the embodiments are illustrated in the accompanying drawings, the drawings are not necessarily drawn to scale unless specifically indicated.
In addition, the technical features described below in the different embodiments of the present application may be combined with each other as long as they do not collide with each other.
Fig. 1 shows a simulated moving bed adsorptive separation system comprising an adsorption column 1 comprising a plurality of column sections 200 within said adsorption column 1, each column section 200 comprising a fluid distributor 2 and an adsorbent bed 3. Various materials such as feedstock F, desorbent D, extract E and raffinate R can be fed and discharged during different steps in the fluid distributor 2 of different column sections 200, with each material undergoing adsorption-desorption distribution in the adsorbent bed 3.
In the simulated moving bed adsorption separation system of the present application, a plurality of adsorption towers 1 may be included, and these adsorption towers 1 may be arranged in series or in parallel. For example, 1 to 2 adsorption towers 1 arranged in series may be included.
The fluid distributor 2 of each tower section 200 is connected with a material inlet and outlet pipeline 4 and extends out of the adsorption tower, a raffinate R export pipeline 5 is sequentially arranged on the material inlet and outlet pipeline 4 outside the adsorption tower and used for exporting raffinate R, a raw material F import pipeline 6 is used for importing raw material F, a desorbent D import pipeline 7 is used for importing desorbent D, and a extract E export pipeline 8 is used for exporting extract E. Generally, in an adsorption column, the region between raffinate injection and raffinate withdrawal is referred to as the desorption zone, the region between raffinate withdrawal and feed injection is referred to as the purification zone, the region between feed injection and raffinate withdrawal is referred to as the adsorption zone, and the region between raffinate withdrawal and desorbent injection is referred to as the buffer zone. In one embodiment, the simulated moving bed system may have two adsorption columns, 24 beds, 4-7 beds in the desorption zone, 7-10 beds in the purification zone, 4-7 beds in the adsorption zone, and 2-4 beds in the buffer zone.
In the simulated moving bed process, four strands of material in and out can periodically change the positions of the material in and out of the adsorption tower, so that the material pipeline needs to be washed before the material in and out of the bed pipeline is changed. In order to flush the pipeline clean enough, the on-off valves of the four material inlet and outlet pipelines of raffinate R, raw material F, desorbent D and extract E need to be close to the total material inlet and outlet pipeline as much as possible, so that the volume of the residual material is minimized.
In the above simulated moving bed adsorptive separation system, as shown in fig. 1, in each column section, a fluid distributor 2 is disposed above the adsorbent bed 3. Each column section is arranged in turn so that the fluid distributor 2 and the adsorbent bed 3 are arranged alternately. A bottom collector 210 is further provided at the bottom of the adsorption column for collecting the collected streams from the upper beds thereof and for supporting the adsorbent beds thereon. The stream collected by the bottom collector 210 may also be delivered to the top of the adsorption column by a pump (not shown). The bottom collector is not connected to the circulation line.
The fluid dispenser 2 is described in detail below in connection with fig. 2-4.
The fluid dispenser 2 comprises:
An upper surface support 101 having a channel for fluid passage,
A lower surface fluid distribution member 102 having a channel for fluid passage,
A partition 110 extending horizontally across the cross-sectional area of the fluid dispenser, the partition dividing the fluid dispenser interior chamber, defined by the upper surface support and the lower surface fluid distribution member, into an upper compartment, the fluid collection chamber 16, and a lower compartment, the fluid distribution chamber 17;
A mixing chamber 120 disposed within the fluid dispenser, the upper layer 14 of the mixing chamber being in fluid communication with the fluid collection chamber 16, the lower layer 15 of the mixing chamber being in fluid communication with the fluid distribution chamber 17 such that external fluid entering the fluid collection chamber enters the fluid distribution chamber 17 through the mixing chamber and exits the fluid dispenser through the lower surface fluid distribution member 102.
The upper surface support 101 and the lower surface fluid distribution 102 of the fluid dispenser 2 have channels for fluid to pass through.
The function of the upper surface support 101 is to support the adsorbent bed 3 above the fluid distributor, blocking solid adsorbent particles in the adsorbent bed 3 above the fluid distributor from entering the fluid distributor 2, while allowing fluid to flow into the fluid distributor 2. The component may be generally composed of an upper part and a lower part, or may be composed of a plurality of parts. The upper portion of the component employs a special type of grid known as a "shaped wire screen", but is not limited to this construction and may be constructed of materials such as various wire screens, grids, porous screen panels, honeycomb materials, and the like, alone or in combination. The lower part of the component can be provided with a supporting structure consisting of a series of supporting bars which are staggered transversely and longitudinally, the supporting structure can also consist of a forming supporting plate with holes, and can also be a combination of a plurality of supporting components.
The lower surface distribution member 102 can be similar in structure to the upper portion of the upper surface support member 101, and is a means for improving and/or maintaining a uniform distribution of fluid velocity, and can be formed from, for example, porous screen panels, forming wire mesh, grids, honeycomb materials, corrugated sheets, and combinations thereof. The upper portion of the upper surface support 101 and the lower surface distribution 102 of the fluid dispenser may typically be a johnson mesh.
The upper surface support 101 and the lower surface fluid distribution member 102 together define an interior chamber of the fluid dispenser 2 of the present application. A partition 110 is provided in the fluid dispenser 2, which partitions the internal chamber of the fluid dispenser into an upper compartment, which is a fluid collection chamber 16, and a lower compartment, which is a fluid distribution chamber 17. The upper surface support 101, lower surface fluid distribution 102, and baffle 110 are substantially parallel to each other at reasonable intervals and are substantially perpendicular to the vertical major axis imaginary line of the vessel. The separator 110 is typically made of a flat plate without holes.
The fluid dispenser 2 is further provided with a mixing chamber 120 inside, and the outer peripheral wall of the mixing chamber 120 is provided with through holes, so that the upper layer 14 of the mixing chamber 120 is in fluid communication with the fluid collecting chamber 16, and the lower layer 15 of the mixing chamber is in fluid communication with the fluid distributing chamber 17, so that the external fluid entering the fluid collecting chamber 16 enters the fluid distributing chamber 17 after passing through the mixing chamber 120, and is discharged from the fluid dispenser 2 through the lower surface fluid distributing member 102. The mixing chamber 120 is located within the interior of the interior chamber defined by the upper surface support 101 and the lower surface fluid distribution member 102 of the fluid dispenser 2 of the present application. The upper end of the mixing chamber 120 is flush with the upper surface support 101, the lower end is flush with the lower surface fluid distribution member 102, and the partition plate 110 is provided with a through hole for the mixing chamber 120 to be sleeved therein, such that the partition plate 110 surrounds the outer periphery of the mixing chamber 120 at the through hole. The space above the partition 110 in the mixing chamber 120 is referred to as the upper layer 14 of the mixing chamber 120 and the space below the partition 110 in the mixing chamber 120 is referred to as the lower layer 15 of the mixing chamber 120.
Material from the upper adsorbent bed enters the fluid collection chamber 16 via the upper surface support 101 and then enters the fluid mixing chamber 120 where it is thoroughly mixed with material, flows to the fluid distribution chamber 17 and exits the fluid distributor 2 via the lower surface fluid distribution member 102.
The fluid dispenser 2 is also externally connected with a circulation line comprising:
A material inlet and outlet pipeline 4, wherein the material inlet and outlet pipeline 4 is connected with the upper layer 14 of the mixing chamber 120;
A flushing line 9, said flushing line 9 being connected to the lower layer 15 of said mixing chamber 120;
a flushing pump 12, wherein the flushing pump 12 is communicated with the material inlet and outlet pipeline 4 and the flushing pipeline 9.
Raffinate R is led out of line 5, feedstock F is led in line 6, desorbent D is led in line 7, and extract E is led out of line 8 via feed-in and feed-out line 4 into or out of the respective materials during the different steps. Thus, an external material circulation flushing path is formed by the material inlet and outlet line 4, the flushing pump 12 and the flushing line 9, which can be used for flushing the material inlet and outlet line 4 during flushing.
In one embodiment, a first control valve 10 is provided between the connection port of the material inlet and outlet line 4 to the upper layer of the mixing chamber 120 and the flushing pump 12. The valve 10 serves as a buffer to avoid damage to the rinse pump when the rinse pump is started up for high pressure streams in the adsorption column. In one embodiment, a second control valve 11 is arranged between the flushing line 9 and the connection port of the lower layer of the mixing chamber 120 and the flushing pump 12. When flushing is required, the flushing pump 12 and the first and second control valves 10 and 11 are opened. In general, it is desirable that the two components of the flush inlet stream and flush outlet stream differ as much as possible, and that the connection port of the flush line 9 to the lower layer of the mixing chamber 120 and the connection port of the in-out line to the upper layer of the mixing chamber 120 be as far as possible. A flow controller 13 is also provided in the circulation line for flow control. The position of the flow controller 13 in the circulation line can be varied as desired, typically at a position downstream of the flushing pump.
As described above, in the simulated moving bed process, four inlet and outlet materials periodically change the positions of the inlet and outlet adsorption towers, so that the raw material pipeline needs to be flushed before the inlet and outlet materials in the bed pipeline are changed.
The application relates to a pipeline flushing method of a simulated moving bed adsorption separation system, which is carried out in the simulated moving bed adsorption separation system, and the flushing mode comprises two modes:
in a first way, the first control valve 10, the second control valve 11 and the flushing pump 12 are opened, material is led out from the upper layer of the mixing chamber 120 of the fluid dispenser through the port of the material inlet and outlet line 4, the material inlet and outlet line 4 is flushed, and the flushed material is led into the lower layer of the mixing chamber 120 of the fluid dispenser through the flushing line 9.
In the second way, the first control valve 10, the second control valve 11 and the flushing pump 12 are opened, material is led out from the lower layer of the mixing chamber 120 of the fluid dispenser through the port of the flushing line 9, the material inlet and outlet line 4 is flushed, and the flushed material is led into the upper layer of the mixing chamber 120 of the fluid dispenser.
In one embodiment, the flushing flow rate is controlled, as well as the duration of the flushing steps, in which the total volume of material flowing through the flushing line 9 is greater than the sum of the in-out material line volume, the flushing line volume and the fluid distributor volume.
In one embodiment, the first control valve is in an open state for n times the flushing step time, 0.2 n 1.0.
In one embodiment, the flow rate of the material in the flushing line is 1-3 m/s.
The invention simplifies the flushing process, directly leads out a stream of material flow from the fluid distributor, and after flushing the material inlet and outlet pipelines through the flushing pipeline and the flushing pump, the stream of material flow is led back to the fluid distributor. The method can wash the material inlet and outlet pipelines by using the materials consistent with the fluid components in the tower on the premise of not influencing the regional flow of the simulated moving bed adsorption tower, the washing flow ratio can be flexibly adjusted, the number of control valves is reduced, and the material inlet and outlet pipelines and the washing process thereof are simplified.
Fig. 4A and 4B show the position of the flushing line in relation to the material inlet and outlet line in the mixing chamber of the fluid distributor. As shown in fig. 4A, a part of the flushing pipeline 9 is sleeved inside the material inlet and outlet pipeline 4. As shown in fig. 4B, the flushing line 9 is arranged in parallel with the material inlet and outlet line 4. In general, it is desirable that the two components of the flush inlet stream and flush outlet stream differ as much as possible, and that the connection port of the flush line 9 to the lower layer of the mixing chamber 120 and the connection port of the in-out line to the upper layer of the mixing chamber 120 be as far as possible. Thus, in one embodiment, the flushing line 9 is located in the lower part of the lower layer 15 of the mixing chamber 120 at the outlet end of the lower layer 15 of the mixing chamber 120. In one embodiment, the material inlet and outlet line 4 is located in the upper portion of the upper layer 14 of the mixing chamber 120 at the outlet end of the upper layer 14 of the mixing chamber 120.
In one embodiment, the size of the flushing line 9 is not larger than the size of the in-out material line 4.
Thus, the present application relates to a feed flushing device for a simulated moving bed comprising:
A fluid distributor 2, wherein the fluid distributor is arranged in the simulated moving bed, and an upper surface supporting piece 101 and a lower surface fluid distribution piece 102 of the fluid distributor 2 are provided with channels for fluid to pass through, wherein a partition plate 110 is arranged in the fluid distributor 2 and divides the fluid distributor into an upper compartment and a lower compartment, the upper compartment is a fluid collection chamber 16, and the lower compartment is a fluid distribution chamber 17;
the material inlet and outlet pipeline 4 is connected with the upper layer 14 of the mixing chamber, and is communicated with the flushing pump 12;
A flushing line 9, said flushing line 9 being connected to the lower layer 15 of said mixing chamber, said flushing line 9 being in communication with said flushing pump 12.
The above-described line flushing method can be realized by means of this feed flushing device.
The application also relates to a method for carrying out adsorption separation by using the simulated moving bed adsorption separation system, which is carried out in the simulated moving bed adsorption separation system,
The method comprises the following steps:
1) In a first step, feeding the feed in the fluid distributors of the first tower sections, feeding the desorbent in the fluid distributors of the second tower sections, discharging the effluent in the fluid distributors of the third tower sections, and discharging the raffinate in the fluid distributors of the fourth tower sections, and performing a flushing procedure in the fluid distributors of the fifth tower sections,
The flushing process comprises the following steps:
Starting the first control valve, the second control valve and the flushing pump, leading out materials from the upper layer of the mixing chamber of the fluid distributor through the ports of the material inlet and outlet pipelines, flushing the material inlet and outlet pipelines, and leading the flushed materials into the lower layer of the mixing chamber of the fluid distributor through the flushing pipelines, or
Starting a first control valve, a second control valve and a flushing pump, leading out materials from the lower layer of a mixing chamber of the fluid distributor through a port of a flushing pipeline, flushing the material inlet and outlet pipeline, and leading the flushed materials into the upper layer of the mixing chamber of the fluid distributor;
2) In the next step, changing the positions of the sections of the column into which the raw material and the desorbent are fed and the positions of the sections of the column from which the extracted liquid and the raffinate are discharged, and changing the positions of the sections of the column into which the flushing process is performed;
3) Repeating the step 2) until all steps are completed.
In the present application, the column section fed with the raw material is referred to as a first column section, the column section fed with the desorbent is referred to as a second column section, the column section discharged with the extracted liquid is referred to as a third column section, the column section discharged with the raffinate is referred to as a fourth column section, and the column section subjected to the flushing process is referred to as a fifth column section. It should be noted that the locations of these tower sections in the adsorption tower are not fixed and will vary as adsorption progresses.
For example, in the system of only 1 adsorption column shown in fig. 1, the adsorption column has 12 column sections, each column section including one adsorbent bed and a fluid distributor, and thus the adsorption column has 12 beds of adsorbent and 12 fluid distributors, one possible adsorption separation column zone division is, but not limited to, 3 beds of adsorption zone, 4 beds of purification zone, 3 beds of desorption zone, and 2 beds of buffer zone according to the zone division experience of the whole adsorption column. The bottom of the adsorption tower is provided with a bottom collector, which is not externally connected with a circulating pipeline.
An exemplary procedure is to open only desorbent D feed line at column 1, only extract E discharge line at column 4, only feed line for feed F at column 8, only discharge line for raffinate R at column 11, and open flush line valves and flush pumps at the remaining column sections to provide a flow composition in the feed and discharge lines consistent with the flow composition in that column section at step 1.
When step2, the feeding line of desorbent D of the 1 st tower section is closed, the feeding line of desorbent D of the 2 nd tower section is opened, the discharging line of the liquid E of the 4 th tower section is closed, the discharging line of the liquid E of the 5 th tower section is opened, the feeding line of raw material F of the 8 th tower section is closed, the feeding line of raw material F of the 9 th tower section is opened, the discharging line of raffinate R of the 11 th tower section is closed, the discharging line of raffinate R of the 12 th tower section is opened, and the rest tower sections are opened with a flushing pipeline valve and a flushing pump, so that the composition of the material flow in the total inlet and outlet material pipeline is consistent with the composition of the material flow in the tower section.
When step 3, 2 nd tower section desorbent D feed line is closed, 3 rd tower section desorbent D feed line is opened, 5th tower section extract E discharge line is closed, 6 th tower section extract E discharge line is opened, 9 th tower section raw material F feed line is closed, 10 th tower section raw material F feed line is opened, 12 th tower section raffinate R discharge line is closed, 1 st tower section raffinate R discharge line is opened, and the rest tower sections are opened to flush pipeline valves and flushing pumps, so that the material flow composition in the material inlet and outlet pipeline is consistent with the material flow composition in the tower section.
According to this rule, every step, the material in and out positions are replaced sequentially for the next tower section, as shown in table 1. Table 1 is merely exemplary and one skilled in the art can modify the four passes in and out of desorbent D, draw E, feed F, raffinate R, and the location, number, and order of the sections of the column to be flushed, etc., as desired.
After 1 cycle and 12 steps, the next cycle starts.
According to the requirements of the simulated moving bed process, four material inlet and outlet flows of desorbent D, extract E, raw material F and raffinate R are changed to the material inlet and outlet position of the next tower section after each step. Table 1 shows that in one embodiment, in 12 steps, each tower section in each step cycle is fed and discharged, 8 tower sections are not needed to be fed and discharged, a flushing pipeline valve and a flushing pump are all opened for pipeline flushing, and the material composition in the rest flushing pipelines is the same as the material composition of the tower section in the adsorption tower except for four pipelines fed and discharged. Different material inlet and outlet modes can be selected according to the needs.
Depending on the operating conditions, two flushing modes of fig. 2 and 3 can be selected, wherein fig. 2 is that materials are led out from the upper layer of the fluid mixing chamber, and after flushing the material inlet and outlet pipelines, the materials enter the lower layer of the fluid mixing chamber. Fig. 3 shows the flow of material from the lower layer of the fluid mixing chamber, flushing the feed and discharge lines, and then into the upper layer of the fluid mixing chamber. In fig. 2 and 3, arrows indicate the flow direction of the material, and double-headed arrows indicate that the material can flow in both directions between the upper and lower layers of the mixing chamber of the fluid dispenser and the fluid collection chamber and the fluid dispensing chamber.
If the step time is 80s, the flushing time of the next tower section pipeline of the tower section where the desorbent D is located is set to be 80s, the flushing time of the next tower section pipeline of the tower section where the extract E is located is set to be 80s, the flushing pumps are not started when the other tower sections are set to be 0-40 s, and the flushing pumps are started for 40-80 s.
The volume of the pipeline to be flushed is calculated according to 0.04m 3, the flow rate of the flushing pump is calculated according to 20m 3/h, and if the pipeline is flushed for 80 seconds in one step time, the flushing volume reaches 0.44m 3, and the flushing linear speed is 1.1m/s. If the flushing time is 40s, the flushing volume is 0.22m 3, which is much larger than the line volume. Therefore, the flushing pump can complete flushing and replacement of materials in the material inlet and outlet pipelines under a small flow. At the same time, to ensure that the flow pattern of the fluid in the pipeline is close to the plug flow, the flow rate of the flushing pump can be further improved, which is beneficial to improving the flushing efficiency.
The valve is specifically operated in such a way that a flushing pump and a valve of the next tower section of the tower section where the desorbent D is positioned are closed, a feeding pipeline of the desorbent D is opened, a feeding pipeline of the original desorbent feeding tower section is closed, and the flushing pump and the valve are opened. And closing a flushing pump and a valve of the next tower section of the tower section where the extraction liquid E is positioned, opening an extraction liquid E discharging pipeline, closing an E discharging pipeline of the original extraction liquid discharging tower section, and opening the flushing pump and the valve. And closing a flushing pump and a valve of the next tower section of the tower section where the raw material F is positioned, opening a raw material F feeding pipeline, closing the F feeding pipeline of the original raw material feeding tower section, and opening the flushing pump and the valve. And closing a flushing pump and a valve of the next tower section of the tower section where the raffinate R is positioned, opening a raffinate R discharging pipeline, closing an R discharging pipeline of the original raffinate tower section, and opening the flushing pump and the valve.
Table 1 different steps of each tower section feeding and discharging materials
It should be noted that "the material in and out of each tower section" actually refers to the material in and out of the fluid distributor of each tower section. In table 1, D represents feeding a desorbent into the column section, C represents performing a flushing process in the column section, E represents drawing out a draw in the column section, F represents feeding a raw material into the column section, and R represents drawing out a raffinate in the column section. The tower sections are numbered in a top-to-bottom order.
The adsorption system of the invention connects four material inlet and outlet and one circulating flushing material in the simulated moving bed in the same pipeline, and when the material inlet and outlet are needed, the flushing pipeline flushing pump is stopped. When the tower section does not need to pass in and out materials, the flushing pipeline flushing pump is turned on. After a stream of material is drawn from the fluid mixing chamber of the tower section through the flushing pump and the material inlet and outlet line, it is returned to the fluid mixing chamber of the tower section. The method can simplify the material inlet and outlet pipelines and the flushing process, reduce material disturbance in the adsorption tower, improve the separation performance of the adsorption tower, improve the yield and reduce the energy consumption of the device.
The simulated moving bed adsorption separation system and the method provided by the invention can be applied to separation of C8 aromatic hydrocarbon isomers and separation of normal and isoparaffins. When the simulated moving bed adsorption separation system is used for separating components such as C8 aromatic isomers and normal isoparaffins, each bed layer is divided into four strands of materials which are fed and discharged and one strand of flushing material, so that the number of control valves on a bed layer pipeline is further reduced, and the flushing process operation is simplified.
Example 1
Para-xylene PX is separated from mixed xylenes using a simulated moving bed process. The simulated moving bed adsorption system is shown in fig. 5 and comprises 2 adsorption towers, wherein the two adsorption towers are connected in series, each adsorption tower comprises 12 tower sections, 6 tower sections in an adsorption zone, 5 tower sections in a desorption zone, 10 tower sections in a purification zone and 3 tower sections in a buffer zone, each tower section comprises a fluid distributor and an adsorbent bed layer, and the fluid distributor is positioned on the adsorbent bed layer. Each adsorption tower has a structure as shown in fig. 1, and a bottom collector is arranged at the bottom of each adsorption tower.
The positions of the raw material F, the desorbent D, the extract E and the raffinate R are marked in fig. 1 (the inlet line 6 for the raw material F, the inlet line 7 for the desorbent D, the outlet line 8 for the extract E and the outlet line 6 for the raffinate R are connected to valves, not shown in fig. 1, which are only opened at most one during a step for feeding or discharging one material in each column section), the line flushing method shown in fig. 2 is used, in which material is led from the upper layer of the mixing chamber of the fluid distributor via the ports of the material inlet and outlet lines, the material inlet and outlet lines are flushed and the flushed material is led via the flushing lines to the lower layer of the mixing chamber of the fluid distributor.
The operating temperature of example 1 was 177 ℃, the operating pressure was 0.88MPa, the feed was mixed xylenes, wherein the para-xylene was 22.18 mass%, the ortho-xylene was 20.44 mass%, the meta-xylene was 51.67 mass%, the ethylbenzene was 4.94 mass%, a small amount of toluene was 0.53 mass% and a small amount of non-aromatic hydrocarbons was 0.22 mass%, the desorbant was para-diethylbenzene, the purity was 99.27 mass%, the extract was para-xylene and para-diethylbenzene, and the raffinate was para-diethylbenzene, the remaining C8 aromatic hydrocarbons other than para-xylene, toluene and non-aromatic hydrocarbons.
The whole adsorption separation system comprises 24 tower sections, each tower section comprises 1 material inlet and outlet pipeline (for 4 materials of feeding and discharging) and one flushing pipeline, 24 flushing pumps are required in total, and the flow of each flushing pump is controlled by a flow controller.
One step time was 80s and one cycle period was 32min.
The working procedure of this embodiment is:
In the first step, desorbent D feed line 7 of column segment ① is opened (i.e., the corresponding valve is opened, the same applies below), draw E discharge line 8 of column segment ⑥ is opened, and column segment Is opened by the feed line 6 of the raw material F, and the tower sectionThe raffinate R discharge line 5 was opened, the remaining column sections were all opened with a flushing pump 12 and valves 10 and 11 and the valves of desorbent D feed line 7, draw E discharge line 8, feed F feed line 6 and raffinate R discharge line 5 were closed, the flushing times being 80s.
In the second step, the flushing pump of column section ② is turned off, the desorbent D feed line 7 of column section 2 is opened, the flushing pump 12 and valves 10 and 11 of column section ① are opened and the valves of desorbent D feed line 7, draw-off liquid E feed line 8, feed-off liquid F feed line 6 and raffinate R feed line 5 are closed, the flushing pump 12 of column section ⑦ is turned off, the draw-off liquid E feed line 8 of column section ⑦ is discharged open, the flushing pump 12 and valves 10 and 11 of column section ⑥ are opened and the valves of desorbent D feed line 7, draw-off liquid E feed line 8, feed-off liquid F feed line 6 and raffinate R feed line 5 are closed, and the column sectionIs turned off, tower sectionIs opened by the feed line 6 of the raw material F, and the tower sectionValves 10 and 11 open and close the valves of desorbent D feed line 7, draw E discharge line 8, feed F feed line 6 and raffinate R discharge line 5, column sectionsIs turned off, tower sectionIs opened, the raffinate R discharge line 5 is opened, and the tower sectionValves 10 and 11 open and close the valves of desorbent D feed line 7, draw E discharge line 8, feed F feed line 6 and raffinate R discharge line 5;
the tower sections are numbered in the order from top to bottom.
And the like, carrying out the switching operation of the material inlet and outlet pipelines of each tower section and the flushing pump in each stepping time.
The results of the parameters of para-xylene purity, yield and catalyst-to-oil ratio D/F in the extract E are shown in Table 2.
Example 2
The procedure of example 1 was followed using the line flush scheme shown in FIG. 3, with material being drawn from the lower layer of the mixing chamber of the fluid dispenser through the ports of the flush line, flushing the material in and out line, and directing the flushed material to the upper layer of the mixing chamber of the fluid dispenser.
The results of the parameters of para-xylene purity, yield and catalyst-to-oil ratio D/F in the extract E are shown in Table 2.
Example 3
With the operation of example 1, the flushing time of the next section line of the section where the raw material F, desorbent D, extract E and raffinate R are located was set to 80s, the flushing pumps were not turned on for the other sections set to 0 to 40s, and the flushing pumps were turned on for 40 to 80 s.
Example 4
With the operation of example 2, the flushing time of the next section line of the section where the raw material F, desorbent D, extract E and raffinate R are located was set to 80s, the flushing pumps were not turned on for the other sections set to 0 to 40s, and the flushing pumps were turned on for 40 to 80 s.
Comparative example 1
The simulated moving bed system of this comparative example comprises 2 adsorption columns each having 12 adsorbent beds (24 beds in total) and 13 grids (top, bottom and 11 intermediate bed grids), feed F, desorbent D, raffinate R, extract E and four flushing streams of C1, C2, C3, C4, 6 beds in the desorption zone, 5 beds in the desorption zone, 10 beds in the purification zone, 3 beds in the buffer zone, operating temperature 177 ℃, operating pressure 0.88MPa, feed mixed xylenes, wherein the feed is 22.18 mass% para-xylene, 20.44 mass% ortho-xylene, 51.67 mass% meta-xylene, 4.94 mass% ethylbenzene, a small amount of toluene 0.53 mass% and a small amount of non-aromatic 0.22 mass%, the desorbent is para-diethylbenzene, and the purity is 99.27 mass%. The second bed upstream of the draw-off point is injected using a desorbent as a primary flush stream C1, a draw-off E as a secondary flush stream C2, a third flush stream C3, a fourth flush stream C4, and a fourth flush stream C4. The bed had a step time of 80s and a cycle time of 32min.
The comparative results of the parameters such as purity, yield and D/F ratio (desorber/raw material ratio) of the paraxylene product separated by the adsorption separation process are shown in the following table 2.
Table 2 comparison of para-xylene product purity, yield and D/F ratio of examples and comparative examples
| Purity of the product | Product yield | D/F ratio | |
| Example 1 | 99.87% | 99.1% | 1.1 |
| Example 2 | 99.85% | 98.0% | 1.1 |
| Example 3 | 99.83% | 97.5% | 1.1 |
| Example 4 | 99.80% | 97.3% | 1.1 |
| Comparative example 1 | 99.72% | 95.0% | 1.3 |
As can be seen from the comparison of the data of the examples and the comparative examples in Table 2, the pipeline flushing method provided by the invention can effectively improve the product purity and the product yield, improve the separation performance of the adsorption tower, remarkably reduce the D/F (desorbent/raw material) ratio and reduce the consumption of the desorbent.
In the description of the present application, it should be noted that the directions or positional relationships indicated by the terms "upper", "lower", "inner", "outer", "front", "rear", "left", "right", etc. are directions or positional relationships based on the operation state of the present application are merely for convenience of describing the present application and simplifying the description, and do not indicate or imply that the devices or elements to be referred to must have a specific orientation, be configured and operated in a specific orientation, and thus should not be construed as limiting the present application.
In the description of the present application, it should be noted that the terms "mounted," "connected," and "connected" are to be construed broadly, unless otherwise specifically defined and limited. The specific meaning of the above terms in the present application will be understood in specific cases by those of ordinary skill in the art.
The application has been described above in connection with preferred embodiments, which are, however, exemplary only and for illustrative purposes. On this basis, the application can be subjected to various substitutions and improvements, and all fall within the protection scope of the application.
Claims (17)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111637502.1A CN116407874B (en) | 2021-12-29 | 2021-12-29 | Simulated moving bed adsorption separation system, flushing equipment and method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111637502.1A CN116407874B (en) | 2021-12-29 | 2021-12-29 | Simulated moving bed adsorption separation system, flushing equipment and method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN116407874A CN116407874A (en) | 2023-07-11 |
| CN116407874B true CN116407874B (en) | 2025-07-08 |
Family
ID=87058009
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111637502.1A Active CN116407874B (en) | 2021-12-29 | 2021-12-29 | Simulated moving bed adsorption separation system, flushing equipment and method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116407874B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5972224A (en) * | 1997-12-22 | 1999-10-26 | Hotier; Gerard | Process and device for improving the purity of a product in a simulated fluid bed |
| CN105521622A (en) * | 2014-09-30 | 2016-04-27 | 中国石油化工股份有限公司 | Simulated moving bed adsorption tower external pipeline leaching device and application thereof in adsorptive separation |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2750886B1 (en) * | 1996-07-11 | 1998-09-25 | Inst Francais Du Petrole | RINSING DEVICE IN A SIMULATED MOBILE BED ADSORPTION UNIT AND ITS USE |
| FR2782656B1 (en) * | 1998-09-02 | 2000-09-29 | Inst Francais Du Petrole | FLUID DISPENSER-MIXER-EXTRACTOR AND RELATED METHOD |
| FR2904776B1 (en) * | 2006-08-08 | 2009-01-23 | Inst Francais Du Petrole | METHOD AND DEVICE FOR SEPARATING A MOBILE BED SIMUL WITH A REDUCED NUMBER OF VALVES |
| CN102451647B (en) * | 2010-10-21 | 2014-04-30 | 中国石油化工股份有限公司 | Fluid distribution equipment |
-
2021
- 2021-12-29 CN CN202111637502.1A patent/CN116407874B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5972224A (en) * | 1997-12-22 | 1999-10-26 | Hotier; Gerard | Process and device for improving the purity of a product in a simulated fluid bed |
| CN105521622A (en) * | 2014-09-30 | 2016-04-27 | 中国石油化工股份有限公司 | Simulated moving bed adsorption tower external pipeline leaching device and application thereof in adsorptive separation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN116407874A (en) | 2023-07-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4709381B2 (en) | Fluid distribution and recovery system and method | |
| CN102895800B (en) | Moving-bed adsorption separation method and equipment | |
| CN102895799B (en) | The moving-bed adsorption separation method that control valve quantity reduces and equipment | |
| US6110364A (en) | Device for improving the purity of a product in a simulated fluid bed | |
| CN101636210B (en) | Method and device for separation into simulated mobile bed with reduced valve number and duct volume | |
| CN101143274B (en) | Process and device for simulated moving bed seperation with a reduced number of valves | |
| JP5015374B2 (en) | Apparatus and methods for collecting, dispensing, mixing, redistributing and discharging fluids | |
| CN104513125B (en) | A method for adsorbing and separating C8 aromatics with liquid-phase simulated moving bed | |
| CN106267931A (en) | A kind of efficient back-flushing filtering device and there is the multi-bed filter of this device | |
| CN104511184B (en) | A kind of adsorbing separation C8The pipeline flushing method of aromatic hydrocarbons simulation used moving bed | |
| CN104815458A (en) | Separator-plates alternative extraction tower and extraction method | |
| CN116407874B (en) | Simulated moving bed adsorption separation system, flushing equipment and method | |
| CN101636209B (en) | Method and apparatus for simulated moving bed separation with reduced number of large diameter valves and reduced pipeline volume | |
| RU2009124518A (en) | NEW FLOW DISTRIBUTION AND COLLECTION SYSTEM IN A MULTI-STAGE COLUMN CONTAINING A SPRAYER | |
| CN103285779A (en) | Fluid mixed distribution equipment | |
| TW201325684A (en) | Process and apparatus for para-xylene production using multiple adsorptive separation units and multiple adsorptive bed feed points | |
| RU2556668C1 (en) | System and method of recovering products using simulated moving bed adsorption | |
| US6146537A (en) | Process and device for improving the purity of a product in a simulated moving bed that comprises forced fluid recirculation | |
| CN208975753U (en) | A fluid mixing and distribution equipment | |
| CN102451647A (en) | Fluid distribution equipment | |
| CN114345257A (en) | Trapping device, system and method for preventing salt deposition of refining device | |
| CN216629758U (en) | Liquid phase simulated moving bed adsorption separation system | |
| CN110613953B (en) | Simulated moving bed separation method and apparatus with reduced number of beds and bypass fluid flow | |
| TW202333838A (en) | Simulated moving bed separation device and method with extended jet breaker | |
| CN116135278A (en) | Liquid phase simulated moving bed adsorption separation system and application thereof, and method for extracting meta-xylene by mixed xylene adsorption separation |
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 |