CN107138101A - A kind of system of acetylene and formaldehyde deep reaction - Google Patents
A kind of system of acetylene and formaldehyde deep reaction Download PDFInfo
- Publication number
- CN107138101A CN107138101A CN201710497535.8A CN201710497535A CN107138101A CN 107138101 A CN107138101 A CN 107138101A CN 201710497535 A CN201710497535 A CN 201710497535A CN 107138101 A CN107138101 A CN 107138101A
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- alkynes aldehyde
- aldehyde reaction
- acetylene
- alkynes
- 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.)
- Pending
Links
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
- B01J8/08—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles
- B01J8/10—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with moving particles moved by stirrers or by rotary drums or rotary receptacles or endless belts
-
- 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
- B01J8/001—Controlling catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
- C07C29/38—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones
- C07C29/42—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal by reaction with aldehydes or ketones with compounds containing triple carbon-to-carbon bonds, e.g. with metal-alkynes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to the system of a kind of acetylene and formaldehyde deep reaction, including the first alkynes aldehyde reaction kettle being sequentially connected, the second alkynes aldehyde reaction kettle, the 3rd alkynes aldehyde reaction kettle, filtration system feed pump, filtration system, recovery system, the first alkynes aldehyde reaction kettle connects formaldehyde, catalyst, raw material acetylene and acetylene tail gas house steward by the pipeline that feeds and discharge respectively, and the second alkynes aldehyde reaction kettle is respectively connected raw material acetylene, filtration system feed pump, filtration system, recovery system and acetylene tail gas house steward with the 3rd alkynes aldehyde reaction kettle by the pipeline that feeds and discharge.The present invention is three-level alkynes aldehyde reaction technological process, and each kettle reaction depth is different, and concentration of formaldehyde is gradually reduced in reaction product, reaction temperature is controlled with pressure by gradient, catalyst online recycling regenerates discharges online with supplement, by-product polymerizing thing, it is adaptable to continuous alkynes aldehyde reaction:The industrialized production of 1,4 butynediols.
Description
Technical field
The invention belongs to Isosorbide-5-Nitrae-butynediols production field, more particularly to a kind of acetylene is with formaldehyde deep reaction
System.
Background technology
The unique method of industrial production butynediols is Reppe methods, also referred to as acetylene-formaldehyde process, and this method is in 1940s
Start industrialization.The method is using the acetylene copper complex of bismuth-containing as catalyst, and bismuth-containing acetylene copper complex is adsorbed on silica-gel carrier,
Acetylene and formalin reaction generation butynediols, and release heat.
Current domestic industry application is up to:One-step method has been reacted in reactor of the separate unit with candle filter
Into including formaldehyde, acetylene and catalyst granules in its reactor, catalyst granules passes through the candle filter inside reactor
Separated, catalyst granules can be piled into filter cake, it is necessary to by each mistake that periodically recoils on the filter in filter process
Filter removes the filter cake, to avoid completely plugged reactor.It is not high to there is formaldehyde transformation efficiency in such process system(After reaction
Concentration of formaldehyde is 8-10%), byproduct of reaction(Carbene)It can not remove, catalyst month is changed per 2-3 once and instead in reactor
Answer kettle and can just must carry out offline, inside reactor candle filter often safeguard and reactor can just must carry out offline, second
The problems such as alkynes and butynediols product are wasted.
The content of the invention
Present invention seek to address that drawbacks described above is there is provided the system of acetylene and formaldehyde deep reaction, it is that three-level alkynes aldehyde is anti-
Technological process is answered, each kettle reaction depth is different, and concentration of formaldehyde is gradually reduced in reaction product, and reaction temperature presses gradient with pressure
It is controlled, the regeneration of catalyst online recycling and supplement, by-product polymerizing thing are discharged online, it is adaptable to continuous alkynes aldehyde reaction:1,
The industrialized production of 4- butynediols.
In order to overcome defect present in background technology, the technical solution adopted for the present invention to solve the technical problems is:
The system of a kind of acetylene and formaldehyde deep reaction, including the first alkynes aldehyde reaction kettle, the second alkynes aldehyde that are sequentially connected by pipeline are anti-
Kettle and the 3rd alkynes aldehyde reaction kettle are answered, the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle are folder
Nested structure, and the discharging opening of the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle is sequentially connected filtering
System feeding pump, filtration system and recovery system, the recovery system by connected respectively by pipeline the first alkynes aldehyde reaction kettle,
The charging aperture of second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle.
In the preferred embodiment of the present invention, the first alkynes aldehyde reaction kettle connects first respectively by feeding hole pipeline
Aldehyde, catalyst, raw material acetylene, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle connect raw material by feeding hole pipeline
Acetylene, the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle top are all connected with acetylene tail gas house steward.
In the preferred embodiment of the present invention, the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle, the 3rd alkynes aldehyde reaction
The top end of kettle is equipped with deeply to its internal agitator, and propeller-blade is 1-5 layers, preferably 3 layers.
In the preferred embodiment of the present invention, filtration system is by the pipeline coupled reaction clear liquid that discharges, and reaction is clear
Liquid is connected at the charging aperture of the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle by pipeline.
In the preferred embodiment of the present invention, recovery system also connects polymer collection device by the pipeline that discharges.
In the preferred embodiment of the present invention, the catalyst is copper bismuth class.
The beneficial effects of the invention are as follows:The present invention is three-level alkynes aldehyde reaction technological process, and each kettle reaction depth is different, instead
Concentration of formaldehyde in product is answered gradually to reduce, reaction temperature is controlled with pressure by gradient, the regeneration of catalyst online recycling is with mending
Fill, by-product polymerizing thing is discharged online, it is adaptable to continuous alkynes aldehyde reaction:The industrialized production of 1,4- butynediols.
Brief description of the drawings
The present invention is further described with reference to the accompanying drawings and examples.
Fig. 1 is the structural representation of the present invention.
Embodiment
Presently preferred embodiments of the present invention is described in detail below in conjunction with the accompanying drawings, so that advantages and features of the invention energy
It is easier to be readily appreciated by one skilled in the art, apparent is clearly defined so as to be made to protection scope of the present invention.
The system of a kind of acetylene as shown in Figure 1 and formaldehyde deep reaction, including the first alkynes aldehyde being sequentially connected by pipeline
Reactor 1, the second alkynes aldehyde reaction kettle 2 and the 3rd alkynes aldehyde reaction kettle 3, the first alkynes aldehyde reaction kettle 1, the second alkynes aldehyde reaction kettle 2
It is jacket structured with the 3rd alkynes aldehyde reaction kettle 3, and the first alkynes aldehyde reaction kettle 1, the second alkynes aldehyde reaction kettle 2 and the 3rd alkynes aldehyde reaction
The discharging opening of kettle 3 is sequentially connected filtration system feed pump 4, filtration system 5 and recovery system 6, and the recovery system 6 passes through logical
Cross the charging aperture that pipeline connects the first alkynes aldehyde reaction kettle 1, the second alkynes aldehyde reaction kettle 2 and the 3rd alkynes aldehyde reaction kettle 3 respectively;First alkynes
Aldehyde reaction kettle 1 connects formaldehyde, catalyst, raw material acetylene, the second alkynes aldehyde reaction kettle 2 and the 3rd alkynes aldehyde by feeding hole pipeline respectively
Reactor 3 connects raw material acetylene by feeding hole pipeline;Catalyst in above-mentioned is copper bismuth class, for example:Catalyst is powder
Shape, particle diameter is in 10-30 m, and bulk density is 0.9 kg/L, specific surface area (45 ± 15) m/g, and it is lO to have 40% in size distribution
Um, 60% is l0~35um, and its chemical composition is copper 35%, bismuth 3~4% (mass fraction), using magnesium silicate as carrier;First alkynes
Aldehyde reaction kettle 1, the second alkynes aldehyde reaction kettle 2, the top of the 3rd alkynes aldehyde reaction kettle 3 also connect acetylene tail by gas phase discharging pipeline
Gas house steward.
First alkynes aldehyde reaction kettle 1, the second alkynes aldehyde reaction kettle 2, the top end of the 3rd alkynes aldehyde reaction kettle 3 are equipped with deeply to it
Internal agitator 7, is easy to be sufficiently mixed uniform, and the blade of agitator 7 is 1-5 layers, preferably 3 layers, to ensure stepwise reaction efficiency.
Filtration system 5 is by the pipeline coupled reaction clear liquid that discharges, and reaction clear liquid is connected to the first alkynes aldehyde by pipeline
At the charging aperture of reactor, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle;Recovery system 6 passes through the pipeline connection polymerization that discharges
Thing collection device.
Embodiment:
35%-45% formalins, 98%-99% acetylene gas enter the first alkynes aldehyde reaction kettle 1 together with copper bismuth catalyst, in stirring
Device 7(3 layers of blade)Being thoroughly mixed under carry out alkynes aldehyde reaction, control pressure is in 100-106kpa (g), and control temperature exists
90-92 DEG C, control concentration of formaldehyde material in 4%-5.5%, the first alkynes aldehyde reaction kettle 1 enters the second alkynes aldehyde reaction kettle 2 through overflow,
Under acetylene gas and the effect of copper bismuth catalyst, agitated device 7(3 layers of blade)Being thoroughly mixed under carry out alkynes aldehyde reaction,
Control pressure is in 92-98kpa (g), and control temperature is at 96-100 DEG C, and control concentration of formaldehyde is in 2%-3.5%, the second alkynes aldehyde reaction kettle
Material enters the 3rd alkynes aldehyde reaction kettle 3 through overflow in 2, under acetylene gas and the effect of copper bismuth catalyst, agitated device 7(3 layers of oar
Leaf)Being thoroughly mixed under carry out alkynes aldehyde reaction, control pressure in 82-90kpa (g), control temperature at 100-104 DEG C,
Concentration of formaldehyde is controlled in 0.5%-1.5%, the bottoms material of the 3rd alkynes aldehyde reaction kettle 3, through filtering the feeding filtration system of system feeding pump 4
5, through filtering reaction clear liquid(Product:The 1,4- butynediols aqueous solution)Rear system is delivered to, catalyst and polymer containing copper bismuth
(Carbene)Mixed solution enter recovery system 6, through solvent dissolve with centrifuge(Not in this patent scope)Recovery contains copper
System continues to participate in alkynes aldehyde reaction, the discharge polymer of recovery system 6 before the catalyst of bismuth is returned to(Carbene), realize catalysis
The recovery of agent.
Embodiments of the invention are the foregoing is only, are not intended to limit the scope of the invention, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright specification and accompanying drawing content are made, or directly or indirectly it is used in other related skills
Art field, is included within the scope of the present invention.
Claims (6)
1. the system of a kind of acetylene and formaldehyde deep reaction, it is characterised in that:Including the first alkynes aldehyde being sequentially connected by pipeline
Reactor, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle, the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle and the 3rd
Alkynes aldehyde reaction kettle is jacket structured, and the discharging of the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle
Mouth is sequentially connected filtration system feed pump, filtration system and recovery system, and the recovery system by being connected respectively by pipeline
Connect the charging aperture of the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle.
2. the system of acetylene and formaldehyde deep reaction according to claim 1, it is characterised in that:The first alkynes aldehyde reaction kettle
Connect formaldehyde, catalyst, raw material acetylene, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction kettle respectively by feeding hole pipeline
Raw material acetylene, the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle and the 3rd alkynes aldehyde reaction are connected by feeding hole pipeline
Kettle top is all connected with acetylene tail gas house steward.
3. the system of acetylene and formaldehyde deep reaction according to claim 1, it is characterised in that:The first alkynes aldehyde reaction
Kettle, the second alkynes aldehyde reaction kettle, the top end of the 3rd alkynes aldehyde reaction kettle are equipped with deeply to its internal agitator, propeller-blade
For 1-5 layers.
4. the system of acetylene and formaldehyde deep reaction according to claim 1, it is characterised in that:The filtration system is by going out
Expects pipe line coupled reaction clear liquid, and reaction clear liquid by pipeline be connected to the first alkynes aldehyde reaction kettle, the second alkynes aldehyde reaction kettle and
At the charging aperture of 3rd alkynes aldehyde reaction kettle.
5. the system of acetylene and formaldehyde deep reaction according to claim 1, it is characterised in that:The recovery system also passes through
Discharge pipeline connection polymer collection device.
6. the system of acetylene and formaldehyde deep reaction according to claim 2, it is characterised in that:The catalyst is copper bismuth
Class.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710497535.8A CN107138101A (en) | 2017-06-27 | 2017-06-27 | A kind of system of acetylene and formaldehyde deep reaction |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201710497535.8A CN107138101A (en) | 2017-06-27 | 2017-06-27 | A kind of system of acetylene and formaldehyde deep reaction |
Publications (1)
Publication Number | Publication Date |
---|---|
CN107138101A true CN107138101A (en) | 2017-09-08 |
Family
ID=59784402
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201710497535.8A Pending CN107138101A (en) | 2017-06-27 | 2017-06-27 | A kind of system of acetylene and formaldehyde deep reaction |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN107138101A (en) |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1470498A (en) * | 2003-07-04 | 2004-01-28 | 石光强 | Method for continuous hydrogenation preparation of 4-amino diphenylamine |
CN101337894A (en) * | 2008-08-08 | 2009-01-07 | 德纳(南京)化工有限公司 | Process for preparation of meta-benzene dimethanamine by continuous hydrogenation reaction in stirring vessel |
JP2013136538A (en) * | 2011-12-28 | 2013-07-11 | Hitachi Zosen Corp | Methanation reaction device |
CN103274991A (en) * | 2013-06-11 | 2013-09-04 | 衡水凯亚化工有限公司 | Method and device for producing 2, 2, 6, 6-Tetramethyl-4-piperidinol through continuous catalytic hydrogenation |
CN103570557A (en) * | 2013-11-08 | 2014-02-12 | 山东沾化天九化工有限公司 | Method and device for producing 3,4-dichloroaniline through continuous kettle type reaction |
CN204702680U (en) * | 2015-04-29 | 2015-10-14 | 内蒙古东源科技有限公司 | A kind of alkynes aldehyde method produces the BYD two reactor system of BDO |
CN204727802U (en) * | 2014-11-20 | 2015-10-28 | 上海迅凯化工科技有限公司 | Prepare the system of polymethoxy dimethyl ether |
CN206838031U (en) * | 2017-06-27 | 2018-01-05 | 查都(上海)科技有限公司 | A kind of system of acetylene and formaldehyde deep reaction |
-
2017
- 2017-06-27 CN CN201710497535.8A patent/CN107138101A/en active Pending
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1470498A (en) * | 2003-07-04 | 2004-01-28 | 石光强 | Method for continuous hydrogenation preparation of 4-amino diphenylamine |
CN101337894A (en) * | 2008-08-08 | 2009-01-07 | 德纳(南京)化工有限公司 | Process for preparation of meta-benzene dimethanamine by continuous hydrogenation reaction in stirring vessel |
JP2013136538A (en) * | 2011-12-28 | 2013-07-11 | Hitachi Zosen Corp | Methanation reaction device |
CN103274991A (en) * | 2013-06-11 | 2013-09-04 | 衡水凯亚化工有限公司 | Method and device for producing 2, 2, 6, 6-Tetramethyl-4-piperidinol through continuous catalytic hydrogenation |
CN103570557A (en) * | 2013-11-08 | 2014-02-12 | 山东沾化天九化工有限公司 | Method and device for producing 3,4-dichloroaniline through continuous kettle type reaction |
CN204727802U (en) * | 2014-11-20 | 2015-10-28 | 上海迅凯化工科技有限公司 | Prepare the system of polymethoxy dimethyl ether |
CN204702680U (en) * | 2015-04-29 | 2015-10-14 | 内蒙古东源科技有限公司 | A kind of alkynes aldehyde method produces the BYD two reactor system of BDO |
CN206838031U (en) * | 2017-06-27 | 2018-01-05 | 查都(上海)科技有限公司 | A kind of system of acetylene and formaldehyde deep reaction |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104689637B (en) | The method of equipment for separating liquid from solid and production hopcalite agent | |
WO2014000501A1 (en) | Combined filtering process for recycling precious metal from fischer-tropsch synthetic product | |
CN107640780A (en) | A kind of preparation method of high-purity hydrogen aluminum oxide | |
CN108264935A (en) | A kind of floating bed hydrogenation system for handling heavy oil | |
CN102649920B (en) | Device and method for continuously preparing biodiesel under intermediate-temperature and medium-pressure condition | |
CN114572969A (en) | Microfluidic reaction system and method for preparing reduced graphene oxide | |
CN102861572A (en) | Catalyst for preparing cyclohexene, preparation method of catalyst, preparation method of cyclohexene and preparation device of cyclohexene | |
CN106397673A (en) | Method and apparatus for continuous kettle type hydrogenation of petroleum resin | |
CN205099601U (en) | System for hydrogenation device and production hydrogen peroxide | |
CN108585045A (en) | The recovery method of the homogeneous molybdenum complex catalyst of epoxidation of propylene | |
CN206838031U (en) | A kind of system of acetylene and formaldehyde deep reaction | |
CN103769076A (en) | Method for preparing olefin-removal catalyst by taking clay as raw materials | |
CN107138101A (en) | A kind of system of acetylene and formaldehyde deep reaction | |
CN103055543A (en) | Large-channel vertical-flow membrane device for recycling superfine solid catalyst and process | |
CN103922930B (en) | Method for preparing n-propyl acetate by using multi-acid intercalated hydrotalcite catalyst | |
CN103570557A (en) | Method and device for producing 3,4-dichloroaniline through continuous kettle type reaction | |
CN106629594A (en) | High-performance magnesium hydride invertible hydrogen manufacturing system and hydrogen manufacturing method | |
CN102350291A (en) | Reactor for gas phase modified nano-powder body | |
CN112827215B (en) | Cyclone extraction method and device for C5 petroleum resin polymerization liquid | |
CN214183129U (en) | Equipment for preparing composite silicon adsorbent by using chlorosilane residual liquid and chitosan | |
CN104557810A (en) | Method for producing furfuraldehyde from pentose solution by adopting impinging stream reactor | |
CN209393158U (en) | Bubbling bed reactor, methyl methacrylate production equipment | |
CN105948294B (en) | A kind of waste acid resource treatment process blocking method based on nano combined carrier | |
CN1325607C (en) | Filter device for reaction system of petroleum catalytic cracking experiment apparatus | |
CN109179405A (en) | A method of carbonized resin is prepared using waste ion-exchang resin |
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 | ||
CB02 | Change of applicant information |
Address after: 570000 No. a5002-323, A1 area, Fuxing City, 32 Binhai Avenue, Longhua District, Haikou City, Hainan Province Applicant after: Chadu (Hainan) Technology Co.,Ltd. Address before: 541, floor 5a, building B, 155 Fute West 1st Road, Shanghai pilot Free Trade Zone, Pudong New Area, Shanghai, China Applicant before: CHADU (SHANGHAI) TECHNOLOGY Co.,Ltd. |
|
CB02 | Change of applicant information | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20170908 |
|
WD01 | Invention patent application deemed withdrawn after publication |