CN105223257A - The on-line determination method of zinc ion concentration in electroplate liquid - Google Patents
The on-line determination method of zinc ion concentration in electroplate liquid Download PDFInfo
- Publication number
- CN105223257A CN105223257A CN201410264901.1A CN201410264901A CN105223257A CN 105223257 A CN105223257 A CN 105223257A CN 201410264901 A CN201410264901 A CN 201410264901A CN 105223257 A CN105223257 A CN 105223257A
- Authority
- CN
- China
- Prior art keywords
- sample
- line
- time
- zinc
- determination
- 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 the on-line determination method of zinc ion concentration in a kind of electroplate liquid, namely this method set the associated period of online sample determination and time, on-line determination instrument from safeguarding, resetting and the precision confirmation time; Adopt compleximetry, titrant and the quantitative complexing of zinc ion; Adopting Cu ion-selective electrode and mercurous chloride electrode to cause chemical cell, for measuring the chemical potential of zinc, in titration process, obtaining the titration curve that the current potential U of zinc and titrant add volume V; Obtain the first differential curve of Δ U and Δ V, when zinc titrated to chemistry endpoints time, zinc current potential is undergone mutation, the first differential maximal value of Δ U/ Δ V is the titration end-point of zinc ion, obtains zinc ion concentration in on-line sample according to titrant concentration, consumption and sampling amount by the quantitative chemical formula of zinc and EDTA.This method can zinc ion concentration in on-line determination electroplate liquid, improves determination efficiency, is beneficial to high speed electrodeposition operation, effectively reduce zinc consumption, ensure that the quality of electroplated product.
Description
Technical field
The present invention relates to the on-line determination method of zinc ion concentration in a kind of electroplate liquid.
Background technology
Domestic and international mensuration for zinc ion concentration in electroplate liquid depends on offline inspection substantially at present, though offline inspection has higher estimating precision, but due to the hysteresis quality of measured value, the process condition of the electroplate liquid in certain sampling moment can only be represented, the change of zinc ion concentration in electroplate liquid cannot be obtained in real time, all round process process condition can not be reflected in real time, and offline inspection needs hand sampling, reduce and measure work efficiency, and bring certain error at measurment.Therefore from continuous production, especially high speed electrodeposition is produced and is set out, research and develop zinc ion concentration assay method in online electroplate liquid, energy real-time continuous ground carries out monitoring to principal ingredient in electroplate liquid and and guides electroplating technology, adjust in time, for reduction zinc consumption, improve electroplate liquid control accuracy, ensure that the aspects such as electroplated product quality have more directive significance than offline inspection.
Summary of the invention
Technical matters to be solved by this invention is to provide the on-line determination method of zinc ion concentration in a kind of electroplate liquid, this method overcomes offline inspection defect, can zinc ion concentration in on-line determination electroplate liquid, improve determination efficiency, be beneficial to high speed electrodeposition operation, effective reduction zinc consumption, ensure that the quality of electro-galvanized steel sheet.
For solving the problems of the technologies described above, in electroplate liquid of the present invention, the on-line determination method of zinc ion concentration comprises the steps:
Step one, set the online sample determination cycle, on-line sample pretreatment time, on-line sample sample time, sampling amount, the sample determination time, on-line determination instrument from maintenance time, on-line determination instrument reset time, on-line determination instrument estimating precision acknowledging time;
Step 2, adopt compleximetry, titrant is EDTA, in the ammonia buffer solution of PH=10, and the quantitative complexing of zinc ion in titrant and on-line sample, its chemical equation is:
Zn
2+＋EDTA＝ZnEDTA
Step 3, employing Cu ion-selective electrode and mercurous chloride electrode cause chemical cell, and for measuring the chemical potential of zinc, in the titration process of PH=10 acidity, zinc and titrant EDTA react and generate ZnEDTA complex compound, its current potential U
zn2+/ZnEDTAdecrease, obtain the titration curve that the current potential U of zinc and titrant EDTA adds volume V;
Step 4, according to titration curve, obtain the first differential curve of Δ U and Δ V, when zinc titrated to chemistry endpoints time, the current potential of zinc is undergone mutation, the first differential maximal value of Δ U/ Δ V is the titration end-point of zinc ion in electroplate liquid, obtains zinc ion concentration in on-line sample according to titrant concentration, the titrant consumption amount reaching titration end-point and sampling amount by the quantitative chemical formula of zinc and EDTA.
Further, described on-line sample determination period is 30 minutes, the described sample pretreatment time is 15 minutes, described on-line sample sample time is 5 minutes, the described sample determination time is 5 minutes, and the described sample pretreatment time comprises online sample preparation and pretreatment system safeguards two stages certainly, and the on-line sample processing time is 10 minutes, period samples for on-line analysis after carrying out dividing potential drop, cooling, filtration to on-line sample, and unnecessary on-line sample returns technology groove by the pipeline of pretreatment system; Pretreatment system is 5 minutes from maintenance time, and period carries out hot water back flush to pretreatment system, and the described sample pretreatment time is included in an on-line sample determination period.
Further, the Pressure Drop of sample stream is low to moderate 1Bar by dividing potential drop by described on-line sample, the temperature of sample stream is made to be reduced to less than 30 DEG C by cooling, the granularity of sample stream is made to be reduced to below 20um by cascade filtration, then enter on-line determination instrument to sample, guaranteeing filter effect by hot water back flush after sample pretreatment terminates, reduce filter service amount, carrying out pretreatment system from safeguarding.
Further, described on-line sample is included in the on-line sample processing time of sample pretreatment sample time, and on-line sample constantly flows into and flows out in sampling line, sampler, guarantees the real-time that on-line determination instrument samples.
Further, in described titrant, EDTA content is 0.15mol/L, and described sample volume is 1.00ml.
Further, within the sample determination time, add ammonia buffer solution, EDTA titration zinc ion calculate measurement result.
Further, in maintenance time, the titration cup of analyzer being cleaned of described on-line determination instrument, terminate rear first by discharging of waste liquid by clear water flushing titration cup 1 time, mensuration before measuring, pickle is adopted to rinse titration cup 1 time to remove precipitation by metallic ion thing in titration process, then clear water is adopted to rinse titration cup 2 times, each flushing process flushing waste automatic-discharging, being included in an on-line sample determination period from maintenance time of described on-line determination instrument.
Further, described on-line determination instrument carries out emptying to the titration unit of on-line determination instrument in reset time, to get rid of bubble in titration unit quantity tube, described on-line determination instrument reset time is 3 minutes, described on-line determination instrument reseting procedure automatically performs after often carrying out 9*n on-line sample determination period, and is included in an on-line sample determination period.
Further, switched by stream in described on-line determination instrument estimating precision acknowledging time, concentration known mark liquid is added online analyzer and carries out precision confirmation, described on-line determination instrument estimating precision acknowledging time is 15 minutes, described on-line determination instrument estimating precision confirms that process automatically performs after often carrying out 10*n on-line sample determination period, and takies an on-line sample determination period.
Further, sample message is automatically transferred to host computer by described on-line determination instrument after each on-line sample determination period terminates, and sample message comprises sample determination time, on-line sample, precision confirmation sample and measured value.
Because in electroplate liquid of the present invention, the on-line determination method of zinc ion concentration have employed technique scheme, namely this method set the online sample determination cycle, on-line sample pretreatment time, on-line sample sample time, sampling amount, the sample determination time, on-line determination instrument from maintenance time, on-line determination instrument reset time, on-line determination instrument from acknowledging time; Adopt compleximetry, under certain acidity, titrant EDTA and the quantitative complexing of zinc ion; Adopt Cu ion-selective electrode and mercurous chloride electrode to cause chemical cell, for measuring the chemical potential of zinc, in titration process, zinc and titrant EDTA react and generate ZnEDTA complex compound, obtain the titration curve that the current potential U of zinc and titrant EDTA adds volume V; According to titration curve, obtain the first differential curve of Δ U and Δ V, when zinc titrated to chemistry endpoints time, the current potential of zinc is undergone mutation, the first differential maximal value of Δ U/ Δ V is the titration end-point of zinc ion in electroplate liquid, obtains zinc ion concentration in on-line sample according to titrant concentration, the titrant consumption amount reaching titration end-point and sampling amount by the quantitative chemical formula of zinc and EDTA.This method overcomes offline inspection defect, can zinc ion concentration in on-line determination electroplate liquid, improves determination efficiency, is beneficial to high speed electrodeposition operation, effectively reduce zinc consumption, ensure that the quality of electroplated product.
Accompanying drawing explanation
Below in conjunction with drawings and embodiments, the present invention is described in further detail:
Fig. 1 is the schematic diagram of titration curve and first differential curve in this method.
Embodiment
In electroplate liquid of the present invention, the on-line determination method of zinc ion concentration comprises the steps:
Step one, set the online sample determination cycle, on-line sample pretreatment time, on-line sample sample time, sampling amount, the sample determination time, on-line determination instrument from maintenance time, on-line determination instrument reset time, on-line determination instrument estimating precision acknowledging time;
Step 2, adopt compleximetry, titrant is EDTA, in the ammonia buffer solution of PH=10, and the quantitative complexing of zinc ion in titrant and on-line sample, its chemical equation is:
Zn
2+＋EDTA＝ZnEDTA
Step 3, employing Cu ion-selective electrode and mercurous chloride electrode cause chemical cell, and for measuring the chemical potential of zinc, in the titration process of PH=10 acidity, zinc and titrant EDTA react and generate ZnEDTA complex compound, its current potential U
zn2+/ZnEDTAdecrease, obtain the titration curve that the current potential U of zinc and titrant EDTA adds volume V;
Step 4, as shown in Figure 1, according to titration curve 1, obtain the first differential curve 2 of Δ U and Δ V, when zinc titrated to chemistry endpoints time, the current potential of zinc is undergone mutation, the first differential maximal value A of Δ U/ Δ V is the titration end-point of zinc ion in electroplate liquid, obtains zinc ion concentration in on-line sample according to titrant concentration, the titrant consumption amount reaching titration end-point and sampling amount by the quantitative chemical formula of zinc and EDTA.
Further, described on-line sample determination period is 30 minutes, the described sample pretreatment time is 15 minutes, described on-line sample sample time is 5 minutes, the described sample determination time is 5 minutes, and the described sample pretreatment time comprises online sample preparation and pretreatment system safeguards two stages certainly, and the on-line sample processing time is 10 minutes, period samples for on-line analysis after carrying out dividing potential drop, cooling, filtration to on-line sample, and unnecessary on-line sample returns technology groove by the pipeline of pretreatment system; Pretreatment system is 5 minutes from maintenance time, and period carries out hot water back flush to pretreatment system, and the described sample pretreatment time is included in an on-line sample determination period.
Further, the Pressure Drop of sample stream is low to moderate 1Bar by dividing potential drop by described on-line sample, the temperature of sample stream is made to be reduced to less than 30 DEG C by cooling, the granularity of sample stream is made to be reduced to below 20um by cascade filtration, then enter on-line determination instrument to sample, guaranteeing filter effect by hot water back flush after sample pretreatment terminates, reduce filter service amount, carrying out pretreatment system from safeguarding.
Further, described on-line sample is included in the on-line sample processing time of sample pretreatment sample time, and on-line sample constantly flows into and flows out in sampling line, sampler, guarantees the real-time that on-line determination instrument samples.
Further, in described titrant, EDTA content is 0.15mol/L, and described sample volume is 1.00ml.
Further, within the sample determination time, add ammonia buffer solution, EDTA titration zinc ion calculate measurement result.
Further, in maintenance time, the titration cup of analyzer being cleaned of described on-line determination instrument, terminate rear first by discharging of waste liquid by clear water flushing titration cup 1 time, mensuration before measuring, pickle is adopted to rinse titration cup 1 time to remove precipitation by metallic ion thing in titration process, then clear water is adopted to rinse titration cup 2 times, each flushing process flushing waste automatic-discharging, being included in an on-line sample determination period from maintenance time of described on-line determination instrument.
Further, described on-line determination instrument carries out emptying to the titration unit of on-line determination instrument in reset time, to get rid of bubble in titration unit quantity tube, described on-line determination instrument reset time is 3 minutes, described on-line determination instrument reseting procedure automatically performs after often carrying out 9*n on-line sample determination period, and is included in an on-line sample determination period.Wherein n gets positive integer.
Further, switched by stream in described on-line determination instrument estimating precision acknowledging time, concentration known mark liquid is added online analyzer and carries out estimating precision confirmation, described on-line determination instrument estimating precision acknowledging time is 15 minutes, described on-line determination instrument estimating precision confirms that process automatically performs after often carrying out 10*n on-line sample determination period, and takies an on-line sample determination period.Wherein n gets positive integer.
Further, sample message is automatically transferred to host computer by described on-line determination instrument after each on-line sample determination period terminates, and sample message comprises sample determination time, on-line sample, precision confirmation sample and measured value.
This method can be widely used in the on-line determination of zinc ion concentration in electroplate liquid, and can be applicable to the on-line determination of other ion concentration in electroplating technology flow process, Automated condtrol and detection technique are organically combined, achieve the functions such as the full-automatic mensuration of detection system, overcome the defect that conventional offline measures, in electroplate liquid, zinc ion concentration on-line determination can reflect zinc ion concentration change in electroplate liquid in real time, improve determination efficiency, instruct electroplating technology, decrease hand sampling, detect the error brought, thus estimating precision is greatly improved, thus ensure that the quality of electroplated product, and be especially adapted to high speed electrodeposition production line.
Claims (10)
1. the on-line determination method of zinc ion concentration in electroplate liquid, is characterized in that this method comprises the steps:
Step one, set the online sample determination cycle, on-line sample pretreatment time, on-line sample sample time, sampling amount, the sample determination time, on-line determination instrument from maintenance time, on-line determination instrument reset time, on-line determination instrument estimating precision acknowledging time;
Step 2, adopt compleximetry, titrant is EDTA, in the ammonia buffer solution of PH=10, and the quantitative complexing of zinc ion in titrant and on-line sample, its chemical equation is:
Zn
2+＋EDTA＝ZnEDTA
Step 3, employing Cu ion-selective electrode and mercurous chloride electrode cause chemical cell, and for measuring the chemical potential of zinc, in the titration process of PH=10 acidity, zinc and titrant EDTA react and generate ZnEDTA complex compound, its current potential U
zn2+/ZnEDTAdecrease, obtain the titration curve that the current potential U of zinc and titrant EDTA adds volume V;
Step 4, according to titration curve, obtain the first differential curve of Δ U and Δ V, when zinc titrated to chemistry endpoints time, the current potential of zinc is undergone mutation, the first differential maximal value of Δ U/ Δ V is the titration end-point of zinc ion in electroplate liquid, obtains zinc ion concentration in on-line sample according to titrant concentration, the titrant consumption amount reaching titration end-point and sampling amount by the quantitative chemical formula of zinc and EDTA.
2. the on-line determination method of zinc ion concentration in electroplate liquid according to claim 1, it is characterized in that: described on-line sample determination period is 30 minutes, the described sample pretreatment time is 15 minutes, described on-line sample sample time is 5 minutes, the described sample determination time is 5 minutes, the described sample pretreatment time comprises online sample preparation and pretreatment system safeguards two stages certainly, the on-line sample processing time is 10 minutes, period carries out dividing potential drop to on-line sample, cooling, sample for on-line analysis after filtration, unnecessary on-line sample returns technology groove by the pipeline of pretreatment system, pretreatment system is 5 minutes from maintenance time, and period carries out hot water back flush to pretreatment system, and the described sample pretreatment time is included in an on-line sample determination period.
3. the on-line determination method of zinc ion concentration in electroplate liquid according to claim 2, it is characterized in that: the Pressure Drop of sample stream is low to moderate 1Bar by dividing potential drop by described on-line sample, the temperature of sample stream is made to be reduced to less than 30 DEG C by cooling, the granularity of sample stream is made to be reduced to below 20um by cascade filtration, then enter on-line determination instrument to sample, filter effect is guaranteed by hot water back flush after sample pretreatment terminates, reducing filter service amount, carrying out pretreatment system from safeguarding.
4. the on-line determination method of zinc ion concentration in electroplate liquid according to claim 2, it is characterized in that: described on-line sample is included in the on-line sample processing time of sample pretreatment sample time, on-line sample constantly flows into and flows out in sampling line, sampler, guarantees the real-time that on-line determination instrument samples.
5. the on-line determination method of zinc ion concentration in electroplate liquid according to claim 1, it is characterized in that: in described titrant, EDTA content is 0.15mol/L, described sample volume is 1.00ml.
6. the on-line determination method of zinc ion concentration in electroplate liquid according to claim 1, is characterized in that: within the sample determination time, added ammonia buffer solution, EDTA titration zinc ion calculate measurement result.
7. the on-line determination method of zinc ion concentration in electroplate liquid according to claim 1, it is characterized in that: in maintenance time, the titration cup of analyzer being cleaned of described on-line determination instrument, terminate rear first by discharging of waste liquid by clear water flushing titration cup 1 time, mensuration before measuring, pickle is adopted to rinse titration cup 1 time to remove precipitation by metallic ion thing in titration process, then clear water is adopted to rinse titration cup 2 times, each flushing process flushing waste automatic-discharging, being included in an on-line sample determination period from maintenance time of described on-line determination instrument.
8. the on-line determination method of zinc ion concentration in electroplate liquid according to claim 1, it is characterized in that: described on-line determination instrument carries out emptying to the titration unit of on-line determination instrument in reset time, to get rid of bubble in titration unit quantity tube, described on-line determination instrument reset time is 3 minutes, described on-line determination instrument reseting procedure automatically performs after often carrying out 9*n on-line sample determination period, and is included in an on-line sample determination period.
9. the on-line determination method of zinc ion concentration in electroplate liquid according to claim 1, it is characterized in that: switched by stream in described on-line determination instrument estimating precision acknowledging time, concentration known mark liquid is added online analyzer and carries out estimating precision confirmation, described on-line determination instrument estimating precision acknowledging time is 15 minutes, described on-line determination instrument estimating precision confirms that process automatically performs after often carrying out 10*n on-line sample determination period, and takies an on-line sample determination period.
10. the on-line determination method of zinc ion concentration in electroplate liquid according to claim 1, it is characterized in that: sample message is automatically transferred to host computer by described on-line determination instrument after each on-line sample determination period terminates, sample message comprises sample determination time, on-line sample, precision confirmation sample and measured value.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410264901.1A CN105223257B (en) | 2014-06-16 | 2014-06-16 | The on-line determination method of zinc ion concentration in electroplate liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410264901.1A CN105223257B (en) | 2014-06-16 | 2014-06-16 | The on-line determination method of zinc ion concentration in electroplate liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105223257A true CN105223257A (en) | 2016-01-06 |
| CN105223257B CN105223257B (en) | 2019-04-23 |
Family
ID=54992329
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410264901.1A Active CN105223257B (en) | 2014-06-16 | 2014-06-16 | The on-line determination method of zinc ion concentration in electroplate liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105223257B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021147814A1 (en) * | 2020-01-20 | 2021-07-29 | 昆明瀚创科技有限公司 | Method for measuring hydroxide concentration in zinc sulfate solution |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61147151A (en) * | 1984-12-20 | 1986-07-04 | Fuji Electric Co Ltd | Analysis of zinc in zinc naphthenate |
| CN1104334A (en) * | 1994-04-29 | 1995-06-28 | 清华大学 | Automatic potentiometric titrimeter |
| CN101738427A (en) * | 2008-11-25 | 2010-06-16 | 上海精密科学仪器有限公司 | On-line automatic potentiometric titration |
| CN103063801A (en) * | 2011-10-19 | 2013-04-24 | 沈阳理工大学 | Rapid online analysis method for main component in alkaline galvanization electroplate liquid |
| CN203069564U (en) * | 2013-01-16 | 2013-07-17 | 许清传 | Full-automatic titrator |
-
2014
- 2014-06-16 CN CN201410264901.1A patent/CN105223257B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61147151A (en) * | 1984-12-20 | 1986-07-04 | Fuji Electric Co Ltd | Analysis of zinc in zinc naphthenate |
| CN1104334A (en) * | 1994-04-29 | 1995-06-28 | 清华大学 | Automatic potentiometric titrimeter |
| CN101738427A (en) * | 2008-11-25 | 2010-06-16 | 上海精密科学仪器有限公司 | On-line automatic potentiometric titration |
| CN103063801A (en) * | 2011-10-19 | 2013-04-24 | 沈阳理工大学 | Rapid online analysis method for main component in alkaline galvanization electroplate liquid |
| CN203069564U (en) * | 2013-01-16 | 2013-07-17 | 许清传 | Full-automatic titrator |
Non-Patent Citations (2)
| Title |
|---|
| 郝晓玉 等: "电位滴定法测定电镀液中硫酸镍、硫酸镁含量", 《第七届全国仪器分析及样品预处理学术研讨会论文集》 * |
| 郭志刚 等: "锌酸盐镀锌液中锌测定的改进", 《电镀与精饰》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021147814A1 (en) * | 2020-01-20 | 2021-07-29 | 昆明瀚创科技有限公司 | Method for measuring hydroxide concentration in zinc sulfate solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105223257B (en) | 2019-04-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN201514406U (en) | Water quality on-line monitoring system | |
| CN203405441U (en) | Instrument for detecting COD (chemical oxygen demand) of high-chlorine wastewater on line by basic potassium permanganate method | |
| CN104677969A (en) | Online electroplate liquid detecting system and online electroplate liquid detecting method | |
| CN102445488A (en) | Multiparameter water quality heavy metal automatic online monitor based on anodic stripping voltammetry | |
| CN212228867U (en) | Online analysis intelligent management and control system for aluminum oxidation tank liquid | |
| Kokkinos et al. | Determination of Pb (II) by sequential injection/stripping analysis at all-plastic electrochemical fluidic cells with integrated composite electrodes | |
| CN103278424A (en) | Quantitative evaluation method for continuous casting billet center porosity or center shrinkage cavity | |
| CN102513278B (en) | System and method for carrying out coating pretreatment of metallic workpiece | |
| CN202710508U (en) | Full-automatic test device for determining lead in plating of tinned plate | |
| CN101308115B (en) | Continuous annealing oven ammonia on-line testing device and method of use | |
| CN210647485U (en) | Automatic cleaning device for online detection pH meter | |
| CN105223257A (en) | The on-line determination method of zinc ion concentration in electroplate liquid | |
| CN112485315A (en) | High-hardness wastewater scaling ion online monitoring system and method | |
| CN203798801U (en) | Mobile rapid analysis experimental car for monitoring water vapor of power plant | |
| CN209387605U (en) | A kind of alkali electroless nickel in-line analyzer | |
| CN204737771U (en) | Adjust water quality analysis front processor of pH valve on line | |
| CN209798104U (en) | Alkaline chemical nickel automatic analysis adding system | |
| CN210894114U (en) | Automatic calibrating installation of circulating water concentration multiplying power | |
| CN102590320A (en) | Electrochemical method for detecting trace trivalent inorganic arsenic by using mercaptoethylamine modified electrode | |
| WO2023010806A1 (en) | Method for measuring alkalinity of water sample | |
| CN108152462A (en) | Power plant boiler water vapor surveillance device | |
| CN112326873A (en) | Online monitoring system for chloride ion content in industrial circulating cooling water | |
| CN111855754B (en) | Water hardness detection probe, sensor, detection method and water softener | |
| CN209878693U (en) | Zinc-zinc ratio analysis device | |
| CN218727001U (en) | Chemical plating detection system |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | 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 | ||
| CP03 | Change of name, title or address |
Address after: No. 3520 Tongji Road, Baoshan District, Shanghai, 201900 Patentee after: Baowu equipment Intelligent Technology Co., Ltd Address before: 201900, 335, Pu Pu Road, Shanghai, Baoshan District Patentee before: SHANGHAI BAOSTEEL INDUSTRY TECHNOLOGICAL SERVICE Co.,Ltd. |
|
| CP03 | Change of name, title or address |