CN103305848A - Method for preparing etching liquid by purifying and regenerating high-concentration ammonia nitrogen waste liquor - Google Patents
Method for preparing etching liquid by purifying and regenerating high-concentration ammonia nitrogen waste liquor Download PDFInfo
- Publication number
- CN103305848A CN103305848A CN2013102556756A CN201310255675A CN103305848A CN 103305848 A CN103305848 A CN 103305848A CN 2013102556756 A CN2013102556756 A CN 2013102556756A CN 201310255675 A CN201310255675 A CN 201310255675A CN 103305848 A CN103305848 A CN 103305848A
- Authority
- CN
- China
- Prior art keywords
- ammonia nitrogen
- nitrogen waste
- waste liquid
- purifying
- waste liquor
- 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
Abstract
The invention discloses a method for preparing etching liquid by purifying and regenerating high-concentration ammonia nitrogen waste liquor. The method comprises the following steps of: carrying out purifying and impurity-removing on ammonia nitrogen waste liquor; removing heavy metal cation Cu<2+> and Sn<2+> by adding S<2-> in the ammonia nitrogen waste liquor; adjusting a pH value of the ammonia nitrogen waste liquor to 9.5-10.5 by ammonia water or liquid ammonia after purifying and removing impurities; adding auxiliary agent to the obtained ammonia nitrogen waste liquor to obtain the regenerated etching liquid, wherein the auxiliary agent is urea or thiourea. The method for preparing etching liquid by purifying and regenerating high-concentration ammonia nitrogen waste liquor disclosed by the invention can be used for carrying out resource utilization and harmless treatment on the copper-containing etching liquid in the circuit board industry. Moreover, the method is low in energy consumption, capable of creating benefits for the society and capable of reducing burden for the environment.
Description
Technical field
The present invention relates to circuit card etching waste liquor treatment process, particularly a kind of ammonia nitrogen in high density effluent purifying regeneration prepares the method for etching solution.
Background technology
As the basis of electronic industry, information industry and household electrical appliance, over nearly 20 years, the PCB(printed circuit board of China) industry keeps the annual growth rate of 10-12% to advance always.China PCB enterprise has exceeded family more than 5000 at present, and annual production reaches more than 1.5 hundred million square metres.And the wiring board industry uses a large amount of a large amount of cuprics of etching solution corrosion removal copper coin generation to contain the ammonia nitrogen etching waste liquor, because contain the copper of high density, has therefore expedited the emergence of enterprise and the technology of large quantities of recovery copper.But all enterprises and technology really rarely have the people to go research nearly all with extraction of copper in the target alignment waste liquid for the treatment technology of having carried the ammonia nitrogen in high density waste liquid that is left behind the copper.Current way is to adopt the method for evaporative crystallization to process remaining ammonia nitrogen in high density waste liquid in the industry, and this most original method possesses several characteristics: high energy consumption, the ammonium chloride of output contains heavy metal, does not possess economic worth fully.Namely typical secondary pollution, in other words seriously be to enlarge secondary pollution technique.Because do not possess economic worth, so so-called evaporative crystallization technique is a treatment process on the symbolic meaning.But country is to the increasingly attention of environmental protection, and the discharging indices restriction of waste liquid and waste water especially also is tending towards rigorous to restriction, the law of government, the rules of ammonia nitrogen.Therefore, solve etching waste liquor and put forward this difficult problem of a large amount of ammonia nitrogen in high density waste liquids that produce behind the copper, realize that the new technology that a kind of less energy-consumption, zero release, cleaner production gain again is significant, be enterprise or government, environmental administration, employer's organization and publicly all can welcome and safeguard.
Now carry in the industry copper enterprise take the electronic circuit board etching waste liquor as raw material, the processing of copper-containing etching waste solution is had the several different methods such as electrolysis, redox and neutralization precipitation.Though electrolysis can propose metallic copper, facility investment is large, the life-span is short, in fact namely not energy-conservation also not environmental protection, also can't process ammonia nitrogen equally.Therefore, mostly be at present chemical precipitation method or acidization and extract copper sulfate or basic copper chloride, these methods are carried the many harmful elements that also increased waste water behind the copper, be difficult to process, do not reach the discharge index requirement, process the technique of high dense ammonia nitrogen waste water for the evaporative crystallization that adopts in the present industry, be actually high energy consumption, expensive, and the ammonium chloride that crystallizes out is not because purity problem almost has market.Can say that also being one enlarges secondary pollution technique.
Chinese patent CN1367147A discloses high-concentration ammonia nitrogen waste water treatment method, at first in waste water, add alkaline Composite agent unslaked lime and calcium peroxide, aeration is 1 hour behind the stirring reaction, add again sodium hydroxide and Sodium peroxoborate, aeration is 1 hour behind the stirring reaction, add again aluminium salt or Ferric Salt Flocculants, stirred rear aeration 0.5-1 hour, at last sedimentation under the effect that adds polymeric flocculant, separation.But the main drawback that this technique exists is that each step reagent adds the afterreaction aeration, causes a large amount of ammonia nitrogen gas to fly away in air, cures the symptoms, not the disease, still contaminate environment.
Chinese patent CN1778707A discloses a kind of high-concentration ammonia nitrogenous wastewater treatment technology, especially a kind of method of utilizing trade waste to process high-concentration ammonia nitrogenous wastewater, has following technical process: with the waste residue that contains nitrite anions or the waste liquid that produces in the Chemical Manufacture, join in the waste water that contains ammonia nitrogen, drip again the pH value to 3 of sulphuric acid soln conditioned reaction solution～5, be warming up to 50～60 ℃, kept above-mentioned pH value and thermotonus 1.5～2.5 hours.High-concentration ammonia nitrogen waste water treatment method of the present invention is processed the nitrite nitrogen in waste water or the waste residue when can utilize the ammonia nitrogen of trade waste in making waste water to obtain processing simultaneously.But this treatment process is still cured the symptoms, not the disease, and still contaminate environment can not get resource regeneration.
At present, also there is the ammonia nitrogen in high density waste liquid to prepare the technology of ammonium chloride product.Waste printed circuit board etching liquid (also claiming the PCB etching waste liquor) comprises acid copper-containing etching waste solution and alkaline copper-containing etching waste solution, behind the copper sulfate or basic copper chloride product by the production of printed circuit board copper-containing etching waste solution, remaining ammonia nitrogen in high density waste liquid adopts evaporative crystallization technique to prepare ammonium chloride, this process energy consumption is high, and the purity of ammonia chloride of making is low.
China Patent No. 200710030322.0, name are called " a kind of method of ammonia nitrogen from printed circuit board waste liquid recycling " and disclose: a kind of method of ammonia nitrogen from printed circuit board waste liquid recycling; Produce the crystalline mother solution that contains high strength ammonium-chloride that produces in the processes such as basic copper chloride, Α crystal type basic copper chloride, cupric sulfate pentahydrate to utilizing circuitboard etching waste liquid, first any in mechanically compress evaporation, multiple-effect evaporation technique with thermo compression or two kinds of combinations are carried out evaporation concentration, crystallization to reclaim most ammonium chloride, transfer pH to carry out ammonia still process to reclaim ammoniacal liquor or ammonium sulfate again; The tin stripper ammonia neutralization is reclaimed the ammonia nitrogen waste water that tin mud produces, and directly the mode of ammonia still process is processed behind the employing adjusting PH; Remaining sewage enters Sewage treatment systems and further processes.This technology energy consumption is high, and sewage production, still contaminate environment are arranged.
Summary of the invention
Technical problem to be solved: the present invention is directed to the prior art deficiency, the method that a kind of ammonia nitrogen in high density effluent purifying regeneration prepares etching solution is proposed, be a kind of circuit-board industry copper-containing etching waste solution recycling and harmless treatment, be fit to circuit card etching waste liquor in enormous quantities is processed the ammonia nitrogen in high density spent solution regeneration recycle of rear production.
The technical scheme that the present invention solve the technical problem employing comprises the steps:
(1), to the removal of impurities of purifying of the ammonia nitrogen waste liquid of concentration 50 ~ 300g/L: use S
2-Add removal heavy metal positively charged ion Cu in the ammonia nitrogen waste liquid
2+And Sn
2+S
2-Add-on is the 4-5 kg/ton;
Above-mentioned after the purification removal of impurities, SO in the ammonia nitrogen waste liquid
4 2-Content is greater than 10 grams per liters or S
2-Content is used BaCl during greater than 100PPm again
2Add in the ammonia nitrogen waste liquid and remove SO
4 2-And S
2-Harmful anion, BaCl
2Add-on is the 20-80 kg/ton;
(2), the ammonia nitrogen waste liquid after step (1) purification removal of impurities, adjust ammonia nitrogen waste liquor PH value between 9.5 ~ 10.5 with ammoniacal liquor or liquefied ammonia;
(3), add auxiliary agent in step (2) the gained ammonia nitrogen waste liquid, auxiliary agent is urea or thiocarbamide, and promoter addition obtains the etching solution of regenerating between 10PPm ~ 3000PPm.
Beneficial effect of the present invention is as follows:
1, the fully different existing evaporative crystallizations of the present invention are processed ammonia nitrogen in high density waste liquid method, the present invention only uses the chemical process purifying waste, being prepared into the PCB etching waste liquor, having solved an ammonia nitrogen in high density liquid waste disposal difficult problem, is recycling utilization truly.
2, the present invention compares with ammonia distillation process, less energy-consumption, and processing cost is low.
3, no matter the present invention is the electronics etching waste liquor before a kind of product of every extraction or extracts filtrate after producing, all passed through purification removal of impurities utilization, what extract for the last time is the ammonium chloride finished product, and filtrate is actual to be that ammonium chloride mother liquor is used to the new etching solution of regenerating, drip and all utilize, three-waste free discharge.Regeneration of the present invention does not form secondary pollution.
4, the present invention beyond doubt can be for the electronic circuit board industry reduces cost, additional income, and decontamination, thus realize the recycling economy zero release.Extensively promote the present invention, be producer's create beneficial result, be the social creativity benefit, be the environment Reduction of Students' Study Load.If calculate by present 1.5 hundred million square metres PCB output, then the annual etching waste liquor that produces reaches nearly 3,000,000 tons, be equivalent to 300,000 tons of ammonia nitrogens and generate, and present steaming ammonium technique can't be avoided the discharging of ammonia nitrogen fully, also will drop into 300,000 tons of ammonia nitrogens and produce so many etching solutions.The present invention can produce 42 yuan of hundred million markets, can bring appreciable economic and social benefit.Can reduce for country by 300,000 tons ammonia nitrogen discharging simultaneously, also be that country saves a large amount of energy.
5, the present invention's etching solution of regenerating is best in quality: parameter 150G/L cupric ion, 190G/L chlorion, pH=8.6, temperature=50 degree centigrade, pressure=2.0 kg/cm.Etch-rate=50 micron/minute, etching factor are about 2.0.This quality is equal to prepares etching solution for the first time.
Description of drawings
Fig. 1 the inventive method process flow sheet.
Embodiment
The present invention comprises acid copper-containing etching waste solution and alkaline copper-containing etching waste solution to waste printed circuit board etching liquid (also claiming the PCB etching waste liquor), behind the copper sulfate or basic copper chloride product by the production of printed circuit board copper-containing etching waste solution, remaining ammonia nitrogen in high density waste liquid carries out purifying regeneration and prepares etching solution.
The copper sulfate that the printed circuit board copper-containing etching waste solution is produced or the ammonia nitrogen in high density waste liquid technique of basic copper chloride product and production are prior aries, are not described further.
The present invention is the method that a kind of ammonia nitrogen in high density effluent purifying regeneration is prepared etching solution, it is characterized in that method steps is as follows:
(1), to the removal of impurities of purifying of the ammonia nitrogen waste liquid of concentration 50 ~ 300g/L: use S
2-Add removal heavy metal positively charged ion Cu in the ammonia nitrogen waste liquid
2+And Sn
2+S
2-Add-on is the 4-5 kg/ton;
Above-mentioned after the purification removal of impurities, SO in the ammonia nitrogen waste liquid
4 2-Content is greater than 10 grams per liters or S
2-Content is used BaCl during greater than 100PPm again
2Add in the ammonia nitrogen waste liquid and remove SO
4 2-And S
2-Harmful anion, BaCl
2Add-on is the 20-80 kg/ton;
(2), the ammonia nitrogen waste liquid after step (1) purification removal of impurities, adjust ammonia nitrogen waste liquor PH value between 9.5 ~ 10.5 with ammoniacal liquor or liquefied ammonia;
(3), add auxiliary agent in step (2) the gained ammonia nitrogen waste liquid, auxiliary agent is urea or thiocarbamide, and promoter addition obtains the etching solution of regenerating between 10PPm ~ 3000PPm.
Embodiment 1
(1), be the removal of impurities of purifying of the ammonia nitrogen waste liquid of 50 ~ 300g/L to 500 kilograms, concentration: use S
2-Add removal heavy metal positively charged ion Cu in the ammonia nitrogen waste liquid
2+And Sn
2+S
2-2 kilograms;
Above-mentioned after the purification removal of impurities, through test, SO in the ammonia nitrogen waste liquid
4 2-Content is 11 grams per liters, 11 kilograms of BaCl
2Add in the ammonia nitrogen waste liquid and remove SO
4 2-Harmful anion.BaCl
2SO in adding and the ammonia nitrogen waste liquid
4 2-Harmful anion forms insoluble barium sulfate precipitate, refilters separation;
(2), the ammonia nitrogen waste liquid is after step (1) purification removal of impurities, with ammoniacal liquor or liquefied ammonia adjustment ammonia nitrogen waste liquor PH=9.5;
(3), 1.5 kilograms of auxiliary agent urea in step (2) the gained ammonia nitrogen waste liquid, obtain the etching solution of regenerating.
Embodiment 2
(1), be the removal of impurities of purifying of the ammonia nitrogen waste liquid of 50 ~ 300g/L to 1000 kilograms, concentration: use S
2-Add removal heavy metal positively charged ion Cu in the ammonia nitrogen waste liquid
2+And Sn
2+S
2-5 kilograms of add-ons;
Above-mentioned after the purification removal of impurities, S in the ammonia nitrogen waste liquid
2-Content is 150PPm, uses BaCl again
2Add in the ammonia nitrogen waste liquid and remove S
2-Harmful anion, BaCl
2Add-on is 20 kilograms.BaCl
2S in adding and the ammonia nitrogen waste liquid
2-Harmful anion forms insoluble barium sulphide precipitation, refilters separation;
(2), the ammonia nitrogen waste liquid is after step (1) purification removal of impurities, with ammoniacal liquor or liquefied ammonia adjustment ammonia nitrogen waste liquor PH=10;
(3), add 3 kilograms of auxiliary agent ureas in step (2) the gained ammonia nitrogen waste liquid, obtain the etching solution of regenerating.
Embodiment 3
(1), to 2000 kilograms, concentration be 50 ~ 300g/L the removal of impurities of purifying of ammonia nitrogen waste liquid: use S
2-Add removal heavy metal positively charged ion Cu in the ammonia nitrogen waste liquid
2+And Sn
2+S
2-Add-on is 9 kilograms;
(2), the ammonia nitrogen waste liquid is after step (1) purification removal of impurities, with ammoniacal liquor or liquefied ammonia adjustment ammonia nitrogen waste liquor PH=10;
(3), add auxiliary agent urea in step (2) the gained ammonia nitrogen waste liquid, add 0.02 kilogram of thiocarbamide, obtain the etching solution of regenerating.
Regeneration efficiency of the present invention and steaming ammonium Energy Efficiency Ratio are used 1964.2 tons in ammonia nitrogen water, containing ammonium chloride 290766.1 kg; Ammonium chloride is by 800 yuan/tons; The regeneration etching solution is by 1.1 yuan/kg of wholesale price.
Annotate: 1. above calculating, consumable material has at a low price and is higher-priced by the high price calculation consumption; 2. production marketing has calculating by the low level valency of low level valency and high-order valency to take in.
Claims (1)
1. an ammonia nitrogen in high density effluent purifying is regenerated and is prepared the method for etching solution, it is characterized in that method steps is as follows:
(1), to the removal of impurities of purifying of the ammonia nitrogen waste liquid of concentration 50 ~ 300g/L: use S
2-Add removal heavy metal positively charged ion Cu in the ammonia nitrogen waste liquid
2+And Sn
2+S
2-Add-on is the 4-5 kg/ton;
Above-mentioned after the purification removal of impurities, SO in the ammonia nitrogen waste liquid
4 2-Content is greater than 10 grams per liters or S
2-Content is used BaCl during greater than 100PPm again
2Add in the ammonia nitrogen waste liquid and remove SO
4 2-And S
2-Harmful anion, BaCl
2Add-on is the 20-80 kg/ton;
(2), the ammonia nitrogen waste liquid after step (1) purification removal of impurities, adjust ammonia nitrogen waste liquor PH value between 9.5 ~ 10.5 with ammoniacal liquor or liquefied ammonia;
(3), add auxiliary agent in step (2) the gained ammonia nitrogen waste liquid, auxiliary agent is urea or thiocarbamide, and promoter addition obtains the etching solution of regenerating between 10PPm ~ 3000PPm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255675.6A CN103305848B (en) | 2013-06-25 | 2013-06-25 | Method for preparing etching liquid by purifying and regenerating high-concentration ammonia nitrogen waste liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310255675.6A CN103305848B (en) | 2013-06-25 | 2013-06-25 | Method for preparing etching liquid by purifying and regenerating high-concentration ammonia nitrogen waste liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103305848A true CN103305848A (en) | 2013-09-18 |
| CN103305848B CN103305848B (en) | 2015-05-27 |
Family
ID=49131557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310255675.6A Active CN103305848B (en) | 2013-06-25 | 2013-06-25 | Method for preparing etching liquid by purifying and regenerating high-concentration ammonia nitrogen waste liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103305848B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150083669A1 (en) * | 2013-09-24 | 2015-03-26 | Baker Hughes Incorporated | Reduction or removal of sulfates from water |
| CN107740105A (en) * | 2017-11-09 | 2018-02-27 | 佛山市华希盛化工有限公司 | A kind of alkaline etching liquid and preparation method thereof |
| CN109095642A (en) * | 2018-08-30 | 2018-12-28 | 惠州大亚湾亿田环保技术有限公司 | A kind of alkalinity erosion copper waste liquid environmental protection recovery process of zero-emission |
| CN109778192A (en) * | 2019-01-18 | 2019-05-21 | 成都虹华环保科技股份有限公司 | A kind of regenerating alkaline etching liquid additive and regenerated liquid regeneration method |
| CN112121618A (en) * | 2020-08-13 | 2020-12-25 | 广东臻鼎环境科技有限公司 | Device and method for improving liquid ammonia absorption efficiency |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4083758A (en) * | 1976-09-27 | 1978-04-11 | Criterion | Process for regenerating and for recovering metallic copper from chloride-containing etching solutions |
| JPH11140673A (en) * | 1997-11-10 | 1999-05-25 | Mec Kk | Method of regenerating waste liquid of copper etching solution |
| CN102345128A (en) * | 2011-09-30 | 2012-02-08 | 重庆浩康医药化工集团有限公司 | Recycling process of etching solution of circuit board |
-
2013
- 2013-06-25 CN CN201310255675.6A patent/CN103305848B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4083758A (en) * | 1976-09-27 | 1978-04-11 | Criterion | Process for regenerating and for recovering metallic copper from chloride-containing etching solutions |
| JPH11140673A (en) * | 1997-11-10 | 1999-05-25 | Mec Kk | Method of regenerating waste liquid of copper etching solution |
| CN102345128A (en) * | 2011-09-30 | 2012-02-08 | 重庆浩康医药化工集团有限公司 | Recycling process of etching solution of circuit board |
Non-Patent Citations (2)
| Title |
|---|
| 崔晓飞等: "含铜蚀刻废液的回收与利用", 《安全与环境工程》 * |
| 蒋玉思等: "碱性蚀刻废液的萃取电积再生", 《再生资源与循环经济》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150083669A1 (en) * | 2013-09-24 | 2015-03-26 | Baker Hughes Incorporated | Reduction or removal of sulfates from water |
| US9643865B2 (en) * | 2013-09-24 | 2017-05-09 | Baker Hughes Incorporated | Reduction or removal of sulfates from water |
| CN107740105A (en) * | 2017-11-09 | 2018-02-27 | 佛山市华希盛化工有限公司 | A kind of alkaline etching liquid and preparation method thereof |
| CN109095642A (en) * | 2018-08-30 | 2018-12-28 | 惠州大亚湾亿田环保技术有限公司 | A kind of alkalinity erosion copper waste liquid environmental protection recovery process of zero-emission |
| CN109778192A (en) * | 2019-01-18 | 2019-05-21 | 成都虹华环保科技股份有限公司 | A kind of regenerating alkaline etching liquid additive and regenerated liquid regeneration method |
| CN112121618A (en) * | 2020-08-13 | 2020-12-25 | 广东臻鼎环境科技有限公司 | Device and method for improving liquid ammonia absorption efficiency |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103305848B (en) | 2015-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102107978B (en) | Method for resource utilization and innocent treatment of etching waste liquid containing copper in circuit board industry | |
| CN103305848B (en) | Method for preparing etching liquid by purifying and regenerating high-concentration ammonia nitrogen waste liquor | |
| CN101161596B (en) | A method for resource processing non-ferro metals processing wastewater containing ammonia and sulfate radical | |
| CN103466870A (en) | Material recovery method of wastewater containing high-concentration ammonia-nitrogen and heavy metal ions and treatment system | |
| CN101948133B (en) | Method for co-producing sodium stannate and stannic oxide by solder removing liquid | |
| CN102775197B (en) | Method for preparing fertilizer-grade ammonium nitrate concentrated solution by use of mother liquid after immersion tin of tin-stripping waste liquid of circuit board | |
| CN103276208B (en) | A kind of method of decompose tunstite | |
| CN104591435B (en) | A kind of processing method of industrial wastewater | |
| CN103436885A (en) | Method for recycling tin removal waste liquor | |
| CN109678196B (en) | Method for fully recycling anions and cations in microetching waste liquid | |
| CN109516631A (en) | A kind of processing method of fluorine-containing ammonia nitrogen waste water | |
| CN102583819B (en) | Method for processing waste water generated by extracting copper oxide from acidic corrosion waste fluid | |
| CN103819026A (en) | Resource utilization method of high-concentration ammonia nitrogen waste liquid | |
| CN105460972A (en) | Recycling method of circuit board solder stripping waste liquid | |
| CN102190326A (en) | Methods for recovering copper from copper-containing waste liquor | |
| CN103086558A (en) | Treatment method of copper chloride hydroxide production wastewater | |
| CN210528685U (en) | Flowing water treatment line for tin stripping waste liquid | |
| CN104860465A (en) | Double-tower catalysis thermal-coupling reflux deamination method and deamination device thereof | |
| KR101214187B1 (en) | Treatment of wastewater from electroless nickel plating process | |
| CN112626561A (en) | Method for recovering copper ions in alkaline etching solution | |
| CN102070436A (en) | Method for recovering oxalate and acid liquor from acidic etching waste liquor | |
| CN103911513B (en) | Move back the treatment process of tin waste liquid | |
| TWI486312B (en) | Process for recovering copper from copper-containing waste liquid | |
| CN100513314C (en) | High purity water-soluble cupric salt reagent production method and precipitating reagent used therefor | |
| CN114394709A (en) | Bromine removal and purification process for high-salt bromine-containing wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20170209 Address after: 516006 Guangdong Province, Huizhou city Huicheng District Jiangbei Wangjiang village kapok Road No. 208 Patentee after: Huizhou Hongyu Thai Technology Co. Ltd. Address before: The New South Road 516000 Guangdong city of Huizhou province Huicheng District No. 6 lane two Patentee before: Cai Guojun |