CN106336024A - Isophorone diamine tetramethylene phosphonic acid or sodium salt thereof, preparation method and application - Google Patents
Isophorone diamine tetramethylene phosphonic acid or sodium salt thereof, preparation method and application Download PDFInfo
- Publication number
- CN106336024A CN106336024A CN201610908960.7A CN201610908960A CN106336024A CN 106336024 A CN106336024 A CN 106336024A CN 201610908960 A CN201610908960 A CN 201610908960A CN 106336024 A CN106336024 A CN 106336024A
- Authority
- CN
- China
- Prior art keywords
- isophorone diamine
- formaldehyde
- preparation
- acid
- methylenephosphonic acid
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention belongs to the field of water treatment and particularly relates to isophorone diamine tetramethylene phosphonic acid or a sodium salt thereof, a preparation method of both and application to oilfield water injection or boiler water utilization. The isophorone diamine tetramethylene phosphonic acid or the sodium salt thereof is very excellent in chemical stability, can adapt to long-term high-hardness, high-alkalinity, high-temperature, high-H2S, high-sulfate bacterium, high-iron bacterium and high-oxidizing environments, and is wide in water quality adapting range. The preparation method is simple to operate, the prepared isophorone diamine tetramethylene phosphonic acid or the sodium salt thereof is excellent in scale inhabitation and corrosion inhibition effect when applied to oilfield water injection or boiler water utilization, and the scale inhibition rate reaches 85% or above.
Description
Technical field
The invention belongs to water treatment field, more particularly, to isophorone diamine four methylenephosphonic acid or its sodium salt and preparation method
And application.
Background technology
Organic phospho acid (salt) antisludging agent is the class phosphorus system water treatment agent starting the sixties in 20th century to apply, because it is only
Special scale-inhibiting properties make the development of water treatment agent make a breakthrough.Experienced the development of decades, organic phosphine is as scale inhibition
Inhibition still occupies leading position in water treatment field.Organic phosphine anti-incrustation corrosion inhibitor mainly has methylenephosphonic acid class and carboxyl phosphonic acid
(acyl) two big class, the former has very strong scale prevention ability to Calcium Carbonate, calcium sulfate and calcium silicates, and can stablize ferrum, zinc, manganese well
Oxide, dispersibility is strong, is particularly well-suited to high concentration multiple and runs, the primary raw material of its synthesis is fat polyamine and phosphorous
Sour (Phosphorous chloride .), and the latter has good Calcium Carbonate and calcium phosphate scale prevention ability in cooling water system, had again
Grain dispersibility and certain corrosion inhibition, almost inoperative with chlorine, be a kind of multi-functional medicament, its molecular weight 2000 with
On, the primary raw material of synthesis is the polymer containing carboxyl, therefore thinks that it is organic phospho acid with the coalition of polymer it is clear that front
The synthesis material of the latter two is sufficiently expensive, and synthesis technique is complicated.
The Chinese invention patent of Application No. 97108420.3 discloses the system of a kind of urea groups four methylenephosphonic acid and its sodium salt
Preparation Method and purposes, the method is with carbamide, phosphorous acid (Phosphorous chloride .), formaldehyde for Material synthesis urea groups four methylenephosphonic acid, by
Amine in carbamide is amide, rather than real amino, because the sucting electronic effect of carbonyl is so that the electron cloud on amino is close
Degree reduces the nucleophilic displacement of fluorine of the carbonyl being unfavorable on amino and formaldehyde.Therefore this reaction is not easy to carry out.
The Chinese invention patent of Application No. 201510255372.3 discloses 1,3- hexamethylene dimethylamine four methylenephosphonic acid
Synthesis technique, 1,3- hexamethylene dimethylamine four methylenephosphonic acid has scale inhibition, inhibition and bactericidal property concurrently, is resistant to certain high temperature ring
Border, but there is sulfate antibacterial, easily lost effect by these bacterial decomposition in the environment of high iron bacteria, additionally, due to
Hexamethylene dimethylamine has 3 kinds of isomerss, and also difference is larger for the methylenephosphonic acid anti-incrustation corrosion inhibitor effect of 3 kinds of structure synthesis, impact
Its whole structure.
Although existing organic phospho acid and phosphonic acid polymers have excellent scale inhibitor and dispersive property, can adapt in
Certain hardness and hot environment, but be applied to the acidity such as oil recovery, boiler higher, rich in oxidisability antibacterial, anaerobe, continue
During the harsh conditions such as high temperature, it is easily decomposed to the low-molecular-weight inorganic matters such as positive phosphorus, thus losing the water treatmenting performances such as scale inhibitor.
Therefore develop a kind of chemical stability superior, high rigidity, high alkalinity, hot environment can be adapted to for a long time, and high
h2S, the environment of high-sulfate antibacterial, high iron bacteria and strong oxidizing property, and scale inhibition performance high organic phospho acid (salt) antisludging agent tool
There is significant realistic meaning.
Content of the invention
For overcoming the shortcoming of above-mentioned prior art presence, the invention provides a kind of new fatty Cycloamine derivative, that is, different
Isophoronediamine four methylenephosphonic acid or its sodium salt, this compound chemical stability is very superior, and scale inhibition effect is excellent, to water quality
Subject range width.
The present invention also provides the preparation method of above-mentioned isophorone diamine four methylenephosphonic acid or its sodium salt, this preparation method letter
Single easy to operate；
Present invention also offers the application of above-mentioned isophorone diamine four methylenephosphonic acid or its sodium salt.
A kind of fat Cycloamine derivative, molecular structural formula is:
When in formula, r is h, referred to as isophorone diamine four methylenephosphonic acid, molecular formula is: c9h16n2(ch2po3h2)4, molecular weight is:
532, it is light yellow transparent solution；When in formula, r is na, referred to as isophorone diamine four methene Alendronate salt, molecular formula is:
c9h16n2(ch2po3na2)4, molecular weight is 708, is light yellow transparent solution.
A kind of preparation method of above-mentioned isophorone diamine four methylenephosphonic acid, with isophorone diamine, phosphorous acid and formaldehyde
For raw material, isophorone diamine and phosphorous acid are added in reactor, salt adding acid adjusts ph value to 2 ~ 5, is warming up to 80 ~ 100
DEG C Deca formaldehyde, completion of dropping improves temperature and continues reaction to terminal, and evaporation and concentration removes hcl and formaldehyde obtains isophorone two
Amine four methylenephosphonic acid solution；
Preferably, the mol ratio of described isophorone diamine, phosphorous acid and formaldehyde is 1:4 ~ 5:5 ~ 8；Described Deca formaldehyde
Time is 0.5 ~ 3 hour；Described formaldehyde completion of dropping improves temperature to 105 ~ 120 DEG C, continues reaction 1 ~ 5 hour.
A kind of preferred preparation method of above-mentioned isophorone diamine four methylenephosphonic acid is, with isophorone diamine, Asia
Phosphoric acid and formaldehyde are raw material, and the mol ratio of three kinds of raw materials is 1:4 ~ 5:5 ~ 6, and isophorone diamine and phosphorous acid are added to reaction
In kettle, add hydrochloric acid to adjust ph value to 3 ~ 4, be warming up to 90 ~ 95 DEG C of Deca formaldehyde, time for adding is 1 ~ 2h, completion of dropping heats up
Continue reaction 2 ~ 3 hours to 110 ~ 115 DEG C, vacuum distillation remove hcl and formaldehyde to obtain isophorone diamine four methylenephosphonic acid molten
Liquid.
A kind of preparation method of above-mentioned isophorone diamine four methene Alendronate salt, with isophorone diamine four methylenephosphonic acid
Solution and sodium hydroxide are raw material, add sodium hydroxide in isophorone diamine four methylenephosphonic acid solution, adjust solution ph
To 6.0-8.0, filter, collect precipitation and be isophorone diamine four methene Alendronate salt.
The application in oil-field flooding or boiler feed water of a kind of above-mentioned isophorone diamine four methylenephosphonic acid or its sodium salt；Its
Described in isophorone diamine four methylenephosphonic acid or its sodium salt can be used alone or with other water treatment agents compound make
With its amount ranges is 5-80ppm.
Beneficial effect
Isophorone diamine four methylenephosphonic acid provided by the present invention or its sodium salt, chemical stability is very superior, can adapt to
In long-term high rigidity, high alkalinity, high temperature, high h2S, the environment of high-sulfate antibacterial, high iron bacteria and strong oxidizing property, to water quality
Subject range width；The present invention provide preparation method simple to operation, isophorone diamine four methylenephosphonic acid of preparation and its
Sodium salt applies scale inhibitor excellent effect in oil-field flooding or boiler feed water, and scale inhibition performance reaches more than 85%.
Specific embodiment
The present invention is further illustrated in conjunction with the embodiments it should explanation, and the description below is merely to explain this
Invention, is not defined to its content.
Embodiment 1
With isophorone diamine, phosphorous acid and formaldehyde as raw material, according to the ratio for 1:4:5 for the mol ratio by isophorone diamine and
Phosphorous acid is added in reactor；Heat and be stirred continuously, control temperature≤50 DEG C, with hydrochloric acid regulating system ph value to 3, heat up
To 95 DEG C, Deca formaldehyde, 1 hour completion of dropping；Improve temperature to 110 DEG C, continue reaction 3 hours；Vacuum distillation remove hcl and
Formaldehyde, obtains isophorone diamine four methylenephosphonic acid pale yellow transparent aqueous solution.
Isophorone diamine four methylenephosphonic acid of method described above preparation and sodium hydroxide are raw material, are adjusted with sodium hydroxide
Isophorone diamine four methylenephosphonic acid ph value, to 7.0, filters, and collects precipitation, obtains isophorone diamine four methene Alendronate salt.
Embodiment 2
With isophorone diamine, phosphorous acid and formaldehyde as raw material, according to the ratio for 1:5:8 for the mol ratio by isophorone diamine and
Phosphorous acid is added in reactor；Heat and be stirred continuously, control temperature≤50 DEG C, with hydrochloric acid regulating system ph value to 5；Heat up
To 100 DEG C, Deca formaldehyde, 3 hours completion of dropping；Improve temperature to 105 DEG C, continue reaction 5 hours；Vacuum distillation removes hcl
And formaldehyde, obtain isophorone diamine four methylenephosphonic acid pale yellow transparent aqueous solution.
Isophorone diamine four methylenephosphonic acid of method described above preparation and sodium hydroxide are raw material, are adjusted with sodium hydroxide
Isophorone diamine four methylenephosphonic acid ph value, to 8.0, filters, obtains isophorone diamine four methene Alendronate salt.
Embodiment 3
With isophorone diamine, phosphorous acid and formaldehyde as raw material, according to the ratio for 1:4:7 for the mol ratio by isophorone diamine and
Phosphorous acid is added in reactor；Heat and be stirred continuously, control temperature≤50 DEG C, with hydrochloric acid regulating system ph value to 2；Heat up
To 80 DEG C, Deca formaldehyde, 0.5 hour completion of dropping；Improve temperature to 115 DEG C, continue reaction 5 hours；Vacuum distillation removes hcl
And formaldehyde, obtain isophorone diamine four methylenephosphonic acid pale yellow transparent aqueous solution.
Isophorone diamine four methylenephosphonic acid of method described above preparation and sodium hydroxide are raw material, are adjusted with sodium hydroxide
Isophorone diamine four methylenephosphonic acid ph value, to 6.0, filters, obtains final product isophorone diamine four methene Alendronate salt.
Embodiment 4
With isophorone diamine, phosphorous acid and formaldehyde as raw material, according to the ratio for 1:4.5:8 for the mol ratio by isophorone diamine
It is added in reactor with phosphorous acid；Heat and be stirred continuously, control temperature≤50 DEG C, with hydrochloric acid regulating system ph value to 2.0；
It is warming up to 80 DEG C, Deca formaldehyde, 3 hours completion of dropping；Improve temperature to 120 DEG C, continue reaction 1 hour；Vacuum distillation removes
Hcl and formaldehyde, obtain isophorone diamine four methylenephosphonic acid pale yellow transparent aqueous solution.
Isophorone diamine four methylenephosphonic acid of method described above preparation and sodium hydroxide are raw material, are adjusted with sodium hydroxide
Isophorone diamine four methylenephosphonic acid ph value, to 7.0, filters, obtains final product isophorone diamine four methene Alendronate salt.
Applicating example
Isophorone diamine four methylenephosphonic acid prepared by above-described embodiment is taken to add in boiler water-filling, chemical feeding quantity is
30ppm, tests scale inhibition performance (%) by gb/t 16632-2008 (mensure tosca methods of water treatment agent scale-inhibiting properties), its
Result is shown in as table 1 below:
Table 1
Isophorone diamine four methylenephosphonic acid prepared by above-described embodiment is taken to add in simulation oil field water filling, addition is
50ppm, in wherein said simulation oil field water filling, each group is divided into: iron content is 0.5mg/l, solid suspension (suspended particle
A diameter of 3 m) concentration be 5mg/l, oil content be 10mg/l, total salinity be 5000mg/l, dissolved oxygen concentration be 0.5mg, two
Sulfur oxide content is 10mg/l, saprophytic bacteria 104Individual/l, sulfate reducting bacteria 102Individual/l, by gb/t 16632-2008 (at water
The mensure tosca method of reason agent scale-inhibiting properties) test scale inhibition performance (%), its result is shown in as table 2 below:
Table 2
Claims (9)
1. a kind of fat Cycloamine derivative is it is characterised in that molecular structural formula is:
When in formula, r is h, referred to as isophorone diamine four methylenephosphonic acid, molecular formula is c9h16n2(ch2po3h2)4, molecular weight is:
532, it is light yellow transparent solution；When in formula, r is na, referred to as isophorone diamine four methene Alendronate salt, molecular formula is:
c9h16n2(ch2po3na2)4, molecular weight is 708, is light yellow transparent solution.
2. a kind of preparation method of isophorone diamine four methylenephosphonic acid described in claim 1 is it is characterised in that with different Fo Er
Ketone diamidogen, phosphorous acid and formaldehyde are raw material, and isophorone diamine and phosphorous acid are added in reactor, add hydrochloric acid to adjust ph
It is worth to 2 ~ 5, is warming up to 80 ~ 100 DEG C of Deca formaldehyde, completion of dropping improves temperature and continues reaction to terminal, evaporation and concentration removes hcl
Obtain isophorone diamine four methylenephosphonic acid solution with formaldehyde.
3. preparation method according to claim 2 is it is characterised in that described isophorone diamine, phosphorous acid and formaldehyde
Mol ratio be 1:4 ~ 5:5 ~ 8.
4. preparation method according to claim 2 is it is characterised in that the time of described Deca formaldehyde is 0.5 ~ 3 hour.
5. preparation method according to claim 2 it is characterised in that described formaldehyde completion of dropping improve temperature to 105 ~
120 DEG C, continue reaction 1 ~ 5 hour.
6. the isophorone diamine four methylenephosphonic acid preparation method described in a kind of claim 1 is it is characterised in that with isophorone
Diamidogen, phosphorous acid and formaldehyde are raw material, and the mol ratio of three kinds of raw materials is 1:4 ~ 5:5 ~ 6, and isophorone diamine and phosphorous acid are added
Enter in reactor, add hydrochloric acid to adjust ph value to 3 ~ 4, be warming up to 90 ~ 95 DEG C of Deca formaldehyde, time for adding is 1 ~ 2h, Deca
Finish, be warming up to 110 ~ 115 DEG C and continue reaction 2 ~ 3 hours, vacuum distillation removes hcl and formaldehyde obtains isophorone diamine tetramethyl
Fork phosphonic acids solution.
7. a kind of preparation method of the isophorone diamine four methene Alendronate salt described in claim 1 is it is characterised in that with different
Isophoronediamine four methylenephosphonic acid solution and sodium hydroxide are raw material, add hydrogen in isophorone diamine four methylenephosphonic acid solution
Sodium oxide, adjusts solution ph to 6.0-8.0, filters, and collects precipitation and is isophorone diamine four methene Alendronate salt.
8. isophorone diamine four methylenephosphonic acid described in a kind of any one of claim 1-7 or its sodium salt are in oil-field flooding or pot
Application in stove water.
9. application according to claim 8 is it is characterised in that described isophorone diamine four methylenephosphonic acid or its sodium salt
Can be used alone or with other water treatment agent compounding uses, its amount ranges be 5-80ppm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610908960.7A CN106336024B (en) | 2016-10-17 | 2016-10-17 | Four methylenephosphonic acid of isophorone diamine or its sodium salt and preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610908960.7A CN106336024B (en) | 2016-10-17 | 2016-10-17 | Four methylenephosphonic acid of isophorone diamine or its sodium salt and preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106336024A true CN106336024A (en) | 2017-01-18 |
| CN106336024B CN106336024B (en) | 2019-10-25 |
Family
ID=57840079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610908960.7A Active CN106336024B (en) | 2016-10-17 | 2016-10-17 | Four methylenephosphonic acid of isophorone diamine or its sodium salt and preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106336024B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834010A (en) * | 2014-03-21 | 2014-06-04 | 山东省泰和水处理有限公司 | Rosin-based grafted polyaspartic acid and preparation method thereof |
| CN104891685A (en) * | 2015-05-19 | 2015-09-09 | 山东省泰和水处理有限公司 | A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) |
-
2016
- 2016-10-17 CN CN201610908960.7A patent/CN106336024B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834010A (en) * | 2014-03-21 | 2014-06-04 | 山东省泰和水处理有限公司 | Rosin-based grafted polyaspartic acid and preparation method thereof |
| CN104891685A (en) * | 2015-05-19 | 2015-09-09 | 山东省泰和水处理有限公司 | A synthesis process of 1,3-cyclohexanebis(methylamine) tetra(methylenephosphonic acid) |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106336024B (en) | 2019-10-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103265696B (en) | Dendrimer with pentaerythritol core terminal and phosphonic acid terminal group, preparation method and uses thereof | |
| CN103254228A (en) | Preparation method and application of dendritic polymer ethanediamine nuclear polyamide octo-methanephosphonic acid | |
| CN101519244B (en) | Compound scale inhibitor for treating recirculated cooling water and preparation method thereof | |
| CN103242365B (en) | A kind of preparation of branch-shape polymer polyamide-amide eight methylene phosphonic acid and application thereof | |
| CN102167451B (en) | Composite multiple dirt dispersion agent for oilfield flooding treatment and preparation method thereof | |
| CN106396141A (en) | Scale inhibitor for oilfield water injection | |
| CN109566643A (en) | Oil field Compositional type fungicide and preparation method | |
| CN104310600A (en) | Environment-friendly composite water treatment agent and application thereof | |
| CN102583785B (en) | Circulating cooling water corrosion inhibitor, and preparation and application thereof | |
| CN103991974A (en) | Oilfield reinjection water scale inhibitor and preparation method thereof | |
| CN103254428B (en) | Trimethylolpropane dendritic polymer with nuclear-end phosphonic acid end group as well as preparation method and application for same | |
| CN103819011B (en) | Corrosion and scale inhibitor for oil and gas fields and petrochemical industry | |
| CN107021564A (en) | A kind of Multifunctional water stabilizer | |
| CN105152370B (en) | A kind of preparation method of bi-imidazoline phosphonate corrosion inhibiting and descaling agent | |
| CN104925966B (en) | A kind of oil field system anti-incrustation corrosion inhibitor | |
| CN105254821B (en) | Terpolymer and multifunctional water treating agent and preparation method containing the copolymer | |
| CN104341602B (en) | A kind of method for improving sulfonated polyacrylamide solution viscosity | |
| CN101186396A (en) | Environment-friendly type composite corrosion-inhibiting anti-sludging agent for softening water quality and circulating chilled water | |
| CN106336024A (en) | Isophorone diamine tetramethylene phosphonic acid or sodium salt thereof, preparation method and application | |
| CN102229619A (en) | Tetraethylenepentamine heptamethylene phosphonic acid and preparation technology thereof | |
| CN102229618A (en) | Hexamethylenediamine tetramethylene phosphonic acid disodium salt and its production process | |
| CN103739094A (en) | Scale inhibition and dispersion agent | |
| CN103190439A (en) | Compound biocide for circulating cooling water and preparation method thereof | |
| CN102578088A (en) | Compound agent with effects of sterilization, corrosion inhibition and scale inhibition | |
| CN102887592A (en) | Scale inhibitor composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Address after: 277 100 No. 1 Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province Applicant after: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. Address before: 277100 Zhongtai Fine Chemical Industrial Park, Zaozhuang Town, Shandong Economic Development Zone, Wang Zhen Village, middle Town, Zaozhuang City Applicant before: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province 277100 Patentee after: Shandong Taihe Technology Co.,Ltd. Address before: No.1, Shiliquan East Road, Shizhong District, Zaozhuang City, Shandong Province 277100 Patentee before: SHANDONG TAIHE WATER TREATMENT TECHNOLOGIES Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |