CN110180469A - A kind of reaction control method catalyzing and synthesizing vinyl chloride with gas permeable member optimization mercury-free - Google Patents
A kind of reaction control method catalyzing and synthesizing vinyl chloride with gas permeable member optimization mercury-free Download PDFInfo
- Publication number
- CN110180469A CN110180469A CN201910418534.9A CN201910418534A CN110180469A CN 110180469 A CN110180469 A CN 110180469A CN 201910418534 A CN201910418534 A CN 201910418534A CN 110180469 A CN110180469 A CN 110180469A
- Authority
- CN
- China
- Prior art keywords
- permeable member
- gas permeable
- gas
- mercury
- free
- 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 20
- 238000000034 method Methods 0.000 title claims abstract description 17
- 238000005457 optimization Methods 0.000 title claims abstract description 14
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 title claims description 12
- 230000002194 synthesizing effect Effects 0.000 title claims description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 39
- -1 chloroethene alkene Chemical class 0.000 claims abstract description 12
- 238000009826 distribution Methods 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims description 98
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 10
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000012495 reaction gas Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
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
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/0292—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds with stationary packing material in the bed, e.g. bricks, wire rings, baffles
-
- 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
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides a kind of control methods that chloroethene alkene reaction is catalyzed and synthesized with gas permeable member optimization mercury-free, by the way that elongated rod shape gas permeable member is arranged at tube of convertor center, after so that unstripped gas is entered the shell and tube converter by top, by a certain percentage, part enters annular space catalyst bed, part enters gas permeable member, unstripped gas into gas permeable member is flowed from above to below along gas permeable member axial direction, it is spread outward in the ventilative hole that radial direction passes through gas permeable member simultaneously, into annular space catalyst bed, thus improve contact path of the unstripped gas with catalyst, keep catalyst bed reaction uniform, improve the converter axial Temperature Distribution with tubulation internal catalyst bed layer by introversion and extroversion radial direction from top to bottom；It can be conducive to improve converter heat exchanger tube effective use area, reduce temperature runaway phenomenon, extend catalyst service life, reduce reformer bed layer resistance, improve the utility of production of catalyst and device.
Description
Technical field
The present invention relates to mercury-frees to catalyze and synthesize vinyl chloride field more particularly to a kind of gas permeable member optimization mercury-free catalysis conjunction
At the control method of chloroethene alkene reaction.
Background technique
Domestic acetylene method technique generallys use the mercury chloride of load on the activated carbon as catalyst, reacts anti-in fixed bed
It answers in device and carries out.Since mercury chloride has stronger volatility, mercury has high toxicity again, therefore is caused using mercuric chleride catalyst
Serious mercury is lost and mercury pollution.For the requirement for adapting to environmental protection, acetylene and hydrogen chloride synthesis vinyl chloride thereof must use mercury-free
Catalyst.
During catalyst without mercury synthesis vinyl chloride thereof, for high activity catalyst without mercury, since activity is higher, reaction
Speed is fast, reaction heat point is concentrated, and concentrates on top after entering converter and reacts, if shifting thermal effect is bad, will lead to
React hot spot bed hot-spot nearby, will cause catalyst without mercury when serious and be damaged, influence catalyst without mercury activity and
Service life, to influence normal production.
Summary of the invention
The present invention provides a kind of control methods that chloroethene alkene reaction is catalyzed and synthesized with gas permeable member optimization mercury-free, in tubulation
Interior setting gas permeable member after unstripped gas enters the shell and tube converter by top, by a certain percentage, partially enters annular space and is catalyzed
Agent bed, partially enter the gas permeable member, the unstripped gas into gas permeable member along the gas permeable member axial direction from
Upper and lower flowing, while passing through the air hole of the gas permeable member to external diffusion in radial direction, into annular space catalyst bed,
Improve contact path of the unstripped gas with catalyst, keep catalyst bed reaction uniform, improve converter cata bed from upper and
Lower axial direction and tubulation internal catalyst bed layer radial Temperature Distribution from inside to outside；Temperature runaway phenomenon is advantageously reduced, catalyst is extended
Service life reduces reformer bed layer resistance, improves the utility of production of catalyst and device.
The technical scheme is that realized by following measures:
A kind of control method catalyzing and synthesizing chloroethene alkene reaction with gas permeable member optimization mercury-free, comprising the following steps:
Step 1: gas permeable member being removably mounted to center in every tubulation of shell and tube converter, the shell and tube turns
Change in device tubulation and the gas permeable member annular space and is filled with catalyst without mercury below gas permeable member；
Step 2: after unstripped gas enters the shell and tube converter by top, by a certain percentage, partially entering annular space and be catalyzed
Agent bed, partially enter the gas permeable member, the unstripped gas into gas permeable member along the gas permeable member axial direction from
Upper and lower flowing, while being spread from inside to outside in the air hole that radial direction passes through the gas permeable member, into annular space catalyst
Bed；
Step 3: unstripped gas reacts in the annular space catalyst bed, catalyzes and synthesizes vinyl chloride gas, the chloroethene
Alkene gas after the outflow of each tubulation lower part, is discharged from top to bottom by shell and tube converter bottom pooled portion.
Further, the gas permeable member is screen casing, bourdon tube or various other irregular gas permeable members.
Further, in the step 2, the unstripped gas into the gas permeable member accounts for the 10% of unstripped gas total volumetric flow rate
~80%.
Further, in the step 2, the gas permeable member is led to for the purpose of the balanced distribution of bed temperature from top to bottom
Percent opening from the top down is overregulated to control reaction gas and pass through point from the top down that gas permeable member enters catalyst bed
With ratio.
Further, the gas permeable member is apart from the shell and tube tube of convertor 50~180cm of bottom, to guarantee raw material
The conversion ratio of gas.
Further, the gas permeable member is made of high temperature resistant, corrosion-resistant, the indeformable material of radial direction.
The beneficial effects of the present invention are: with gas permeable member optimization mercury-free, to catalyze and synthesize vinyl chloride anti-the present invention provides a kind of
The control method answered, gas permeable member is arranged in center in tubulation, after unstripped gas enters the shell and tube converter by top, by one
Certainty ratio partially enters annular space catalyst bed, partially enters the gas permeable member, the unstripped gas edge into gas permeable member
The gas permeable member axial direction flows from above to below, while passing through the air hole of the gas permeable member to extending out in radial direction
It dissipates, into annular space catalyst bed, first is that improving contact path of the unstripped gas with catalyst；Second is that keeping entire catalyst bed anti-
Converter cata bed axial temperature point radial from inside to outside with tubulation internal catalyst bed layer from top to bottom uniformly should be improved
Cloth；Third is that reducing temperature runaway phenomenon, extend catalyst service life；Fourth is that reducing reformer bed layer resistance；Fifth is that improving catalyst
With the utility of production of device；Gas permeable member ensure that raw material apart from the shell and tube tube of convertor 50~180cm of bottom simultaneously
The conversion ratio of gas.
Detailed description of the invention
In order to illustrate more clearly of technical solution of the present invention, attached drawing needed in embodiment will be made below
Simply introduce, it should be apparent that, the accompanying drawings in the following description is only some embodiments of the present invention, general for this field
For logical technical staff, without creative efforts, it is also possible to obtain other drawings based on these drawings.
Fig. 1 be the present invention it is a kind of with gas permeable member optimize mercury-free catalyze and synthesize the converter structure of vinyl chloride reaction controlling with
Operation schematic diagram；
Wherein: 1. gas permeable members；2. tubulation；3. catalyst bed.
Specific embodiment
In the description of the present invention, it is to be understood that, term " on ", "lower", "front", "rear", "left", "right", " perpendicular
Directly ", the orientation or positional relationship of the instructions such as "horizontal", "inner", "outside" is to be based on the orientation or positional relationship shown in the drawings, and is only
For the convenience of describing the present invention and simplifying the description, rather than the device or element of indication or suggestion meaning must have specific side
Position is constructed and operated in a specific orientation, therefore is not considered as limiting the invention.
The present invention is described in detail below with reference to the accompanying drawings and embodiments.
A kind of control method catalyzing and synthesizing chloroethene alkene reaction with gas permeable member optimization mercury-free, comprising the following steps:
Step 1, gas permeable member 1 is removably mounted to center in the every tubulation 2 of shell and tube converter, the shell and tube
Catalyst without mercury is filled in tube of convertor 2 and 1 annular space of gas permeable member and below gas permeable member；
Step 2, after unstripped gas enters the shell and tube converter by top, by a certain percentage, partially enter annular space and be catalyzed
Agent bed 3 partially enters the gas permeable member 1, and the unstripped gas into gas permeable member 1 is along the 1 axial direction side of gas permeable member
It spreads to flowing from above to below, while in the air hole that radial direction passes through the gas permeable member 1, is urged into annular space from inside to outside
Agent bed 3；
Step 3, unstripped gas reacts in the annular space catalyst bed 3, catalyzes and synthesizes vinyl chloride gas, the chloroethene
Alkene gas after the outflow of each tubulation lower part, is discharged from top to bottom by shell and tube converter bottom pooled portion.
Specifically, the gas permeable member 1 is screen casing, bourdon tube or various other irregular gas permeable members.
Specifically, in the step 2, the 10%- of unstripped gas total volumetric flow rate is accounted for into the unstripped gas of the gas permeable member 1
80%.
Specifically, in the step 2, the gas permeable member 1 is passed through for the purpose of the balanced distribution of bed temperature from top to bottom
Percent opening from the top down is adjusted to control the ratio that reaction gas enters gas permeable member 1 from the top down.
Specifically, the gas permeable member 1 is apart from the shell and tube tube of convertor 50~180cm of bottom, to guarantee raw material
The conversion ratio of gas.
Specifically, the gas permeable member 1 is made of high temperature resistant, corrosion-resistant, the indeformable material of radial direction.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (6)
1. a kind of control method for catalyzing and synthesizing chloroethene alkene reaction with gas permeable member optimization mercury-free, it is characterised in that: including following
Step:
Step 1: gas permeable member is removably mounted to center in every tubulation of shell and tube converter, the shell and tube converter
Catalyst without mercury is filled in tubulation and the gas permeable member annular space and below gas permeable member；
Step 2: after unstripped gas enters the shell and tube converter by top, by a certain percentage, partially entering annular space catalyst bed
Layer, partially enters the gas permeable member, the unstripped gas into gas permeable member along the gas permeable member axial direction from upper and
Lower flowing, while being spread from inside to outside in the air hole that radial direction passes through the gas permeable member, into annular space catalyst bed；
Step 3: unstripped gas reacts in the annular space catalyst bed, catalyzes and synthesizes vinyl chloride gas, the vinyl chloride gas
Body after the outflow of each tubulation lower part, is discharged from top to bottom by shell and tube converter bottom pooled portion.
2. a kind of control method that chloroethene alkene reaction is catalyzed and synthesized with gas permeable member optimization mercury-free as described in claim 1,
Be characterized in that: the gas permeable member is screen casing, bourdon tube or various other irregular gas permeable members.
3. a kind of control method that chloroethene alkene reaction is catalyzed and synthesized with gas permeable member optimization mercury-free as described in claim 1,
Be characterized in that: in the step 2, the unstripped gas into the gas permeable member accounts for the 10%~80% of unstripped gas total volumetric flow rate.
4. a kind of control method that chloroethene alkene reaction is catalyzed and synthesized with gas permeable member optimization mercury-free as described in claim 1,
Be characterized in that: in the step 2, the gas permeable member for the purpose of the balanced distribution of bed temperature from top to bottom, by adjust from
Upper downward percent opening enters the allocation proportion from the top down of catalyst bed to control reaction gas across gas permeable member.
5. a kind of control method that chloroethene alkene reaction is catalyzed and synthesized with gas permeable member optimization mercury-free as described in claim 1,
It is characterized in that, the gas permeable member is apart from the shell and tube tube of convertor 50~180cm of bottom, to guarantee the conversion of unstripped gas
Rate.
6. a kind of temprature control method that vinyl chloride is catalyzed and synthesized with gas permeable member optimization mercury-free as described in claim 1,
It is characterized in that, the gas permeable member is made of high temperature resistant, corrosion-resistant, the indeformable material of radial direction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910418534.9A CN110180469B (en) | 2019-05-20 | 2019-05-20 | Reaction control method for optimizing mercury-free catalytic synthesis of chloroethylene by using air-permeable member |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910418534.9A CN110180469B (en) | 2019-05-20 | 2019-05-20 | Reaction control method for optimizing mercury-free catalytic synthesis of chloroethylene by using air-permeable member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110180469A true CN110180469A (en) | 2019-08-30 |
| CN110180469B CN110180469B (en) | 2022-04-12 |
Family
ID=67716819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910418534.9A Expired - Fee Related CN110180469B (en) | 2019-05-20 | 2019-05-20 | Reaction control method for optimizing mercury-free catalytic synthesis of chloroethylene by using air-permeable member |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110180469B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113160900A (en) * | 2021-05-24 | 2021-07-23 | 北京化工大学 | Method for obtaining optimized path of Ag-based catalyst synthesized in high flux based on ant colony algorithm |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2499385Y (en) * | 2001-08-24 | 2002-07-10 | 中国石油天然气股份有限公司 | Radial reactor for preparing synthesis gas by partial oxidation |
| CN2782679Y (en) * | 2005-04-21 | 2006-05-24 | 中国石油天然气股份有限公司 | Axial-radial two-dimensional flow reactor for preparing dimethyl ether by converting synthesis gas |
| CN1900036A (en) * | 2006-07-07 | 2007-01-24 | 清华大学 | Fluidized bed reactor for preparing vinyl chloride by hydrogen chloride and acetylene reaction and method |
| CN201144199Y (en) * | 2007-10-12 | 2008-11-05 | 上海工程化学设计院有限公司 | Converter for chloroethylene synthesis |
| CN201410382Y (en) * | 2009-06-05 | 2010-02-24 | 中国石油天然气股份有限公司 | Adiabatic fixed bed reactor without temperature gradient |
| EP2607301A1 (en) * | 2011-12-20 | 2013-06-26 | Karl-Heinz Tetzlaff | Method and device for reforming natural gas |
| CN205833125U (en) * | 2016-07-26 | 2016-12-28 | 天脊煤化工集团股份有限公司 | A kind of cold shock mixing arrangement for fixed bed adiabatic reactor |
-
2019
- 2019-05-20 CN CN201910418534.9A patent/CN110180469B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2499385Y (en) * | 2001-08-24 | 2002-07-10 | 中国石油天然气股份有限公司 | Radial reactor for preparing synthesis gas by partial oxidation |
| CN2782679Y (en) * | 2005-04-21 | 2006-05-24 | 中国石油天然气股份有限公司 | Axial-radial two-dimensional flow reactor for preparing dimethyl ether by converting synthesis gas |
| CN1900036A (en) * | 2006-07-07 | 2007-01-24 | 清华大学 | Fluidized bed reactor for preparing vinyl chloride by hydrogen chloride and acetylene reaction and method |
| CN201144199Y (en) * | 2007-10-12 | 2008-11-05 | 上海工程化学设计院有限公司 | Converter for chloroethylene synthesis |
| CN201410382Y (en) * | 2009-06-05 | 2010-02-24 | 中国石油天然气股份有限公司 | Adiabatic fixed bed reactor without temperature gradient |
| EP2607301A1 (en) * | 2011-12-20 | 2013-06-26 | Karl-Heinz Tetzlaff | Method and device for reforming natural gas |
| CN205833125U (en) * | 2016-07-26 | 2016-12-28 | 天脊煤化工集团股份有限公司 | A kind of cold shock mixing arrangement for fixed bed adiabatic reactor |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113160900A (en) * | 2021-05-24 | 2021-07-23 | 北京化工大学 | Method for obtaining optimized path of Ag-based catalyst synthesized in high flux based on ant colony algorithm |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110180469B (en) | 2022-04-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100460311C (en) | Hydrogen producing device and fuel cell system with the same | |
| CN110180469A (en) | A kind of reaction control method catalyzing and synthesizing vinyl chloride with gas permeable member optimization mercury-free | |
| CN101554585B (en) | Dual-function knitted catalytic gauze used for nitric acid manufacture | |
| CN205529059U (en) | Catalysis hydrogen device that disappears | |
| CN106391036A (en) | Solid solution catalyst for acetic acid self-heating hydrogen production by reforming and preparation method | |
| CN204412216U (en) | A kind of Axial and radial gas solid reactor | |
| CN113578345B (en) | Platinum-based composite catalyst and method for preparing propylene and synthesis gas by carbon dioxide oxidation propane hydrodehydrogenation | |
| CN206519139U (en) | A kind of heat exchange converter | |
| CN110193326A (en) | A kind of gas permeable member catalyzing and synthesizing vinyl chloride optimization reaction controlling for mercury-free | |
| CN202729790U (en) | Two-section heating type byproduct steam or hot water three-in-one hydrochloric acid synthesis furnace | |
| CN202113842U (en) | Novel fixed bed reactor for vinyl acetate synthesis | |
| CN108499492B (en) | Three-bed five-section detachable ammonia synthesis reactor and reduction method of catalyst | |
| CN202729789U (en) | Two-section heating type byproduct steam or hot water four-in-one hydrochloric acid synthesis furnace | |
| CN211302999U (en) | Air permeable member for optimized reaction control of mercury-free catalytic synthesis of chloroethylene | |
| CN205925652U (en) | DMO reactor | |
| CN202474103U (en) | Fuel cell gas deflector structure | |
| JPH06296854A (en) | Reactor and its manufacture | |
| CN211471327U (en) | Improved methanol washing tower equipment capable of absorbing purified gas | |
| CN104338419B (en) | A kind of hydrogen chloride combined absorbing tower | |
| CN215991736U (en) | Vehicle-mounted mainboard heat dissipation structure | |
| CN209205252U (en) | A kind of system that mercury-free catalysis preparing chloroethylene quickly adjusts converter temperature | |
| CN111729619A (en) | Multistage combined type conversion device and conversion process | |
| CN207371505U (en) | A kind of even depressed structure of reactor and even balloon | |
| CN219174216U (en) | Hydrogen purification device | |
| CN219663652U (en) | Dynamic and static combined gas distributor for hydrochlorination |
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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220412 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |