CN108002555A - A kind of phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water - Google Patents
A kind of phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water Download PDFInfo
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- CN108002555A CN108002555A CN201711306035.8A CN201711306035A CN108002555A CN 108002555 A CN108002555 A CN 108002555A CN 201711306035 A CN201711306035 A CN 201711306035A CN 108002555 A CN108002555 A CN 108002555A
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- parts
- phosphate
- cooling water
- circulating cooling
- antisludging agent
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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
- C02F5/12—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 nitrogen
- C02F5/125—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 nitrogen combined with inorganic substances
-
- 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
- C02F2103/023—Water in cooling circuits
-
- 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
-
- 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
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Abstract
The invention discloses a kind of phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water, the component of following parts by weight is included：25~50 parts of 20~40 parts of poly-epoxy succinic acid, 10~30 parts of multiple copolymer, 1~5 part of azole compounds, 5~10 parts of soluble zinc salt, 5~10 parts of organic acid and deionized water.Compared with phosphorus system now, zinc system formula, when antisludging agent of the present invention is used for industrial circulating cooling water, there is without phosphorus, nontoxic, biodegradable environmental-friendly characteristic, there is no emission pollution problem, can substantially reduce sewage disposal expense.
Description
Technical field
The present invention relates to a kind of industrial circulating cooling water inorganic agent, and in particular to one kind is suitable for industrial circulating cooling water and uses
Phosphate-free corrosion inhibition antisludging agent.
Background technology
At present, domestic cooling water treatment agent largely belongs to organic phosphine formula, and Some Enterprises also use Phos formula.To the greatest extent
Pipe phosphorus is nontoxic, but is used as nutrient source, it makes body eutrophication, promotes microorganism particularly algae excessive propagation, causes lake water
Wawter bloom, red tide of sea etc. endanger, and destroy the ecological balance.European and American developed countries have started to prohibit phosphorus limit phosphorus, some cities of China and ground
Area limits the discharge of phosphorus.In terms of long term growth trend, the production and application of phosphorus system water treatment agent will be limited
System, and substituted by phosphate-free water treatment agent.The 1990s, poly-epoxy succinic acid was developed by the Betz Success in Experiment in the U.S.
Come, poly-epoxy succinic acid is without phosphorus, non-nitrogen, biodegradable, has scale inhibition and inhibition double effects concurrently, while can be with other antisludging agents
Cooperative effect is produced, improves the scale inhibition efficiency of formula, the basis of phosphate-free water treatment agent formula has been established in its exploitation.Polycyclic oxygen amber
Amber acid is a kind of real Green Water Treatment Reagents, there is the incomparable environmental advantages of other antisludging agents, and application prospect is non-
It is often wide.
The content of the invention
There is provided a kind of cold suitable for industrial cycle it is an object of the invention to overcome the shortcomings of the prior art part
But the phosphate-free corrosion inhibition antisludging agent of water.
To achieve the above object, the technical solution taken of the present invention is：A kind of nothing suitable for industrial circulating cooling water
Phosphorus corrosion inhibiting and descaling agent, includes the component of following parts by weight：20~40 parts of poly-epoxy succinic acid, 10~30 parts of multiple copolymer, azoles
25~50 parts of 1~5 part of class compound, 5~10 parts of soluble zinc salt, 5~10 parts of organic acid and deionized water.
It is major pharmaceutical agent that the present invention, which selects poly-epoxy succinic acid, utilizes the association between poly-epoxy succinic acid and multiple copolymer
Same effect, improves the scale inhibition efficiency of no-phosphate corrosion scale inhibition formula, improves the scope of application of the water treatment agent, while reduce polycyclic
Oxydisuccinic acid dosage, beneficial to cost-effective.Present invention addition organic acid, improves upper content limit of the zinc salt in alkaline solution,
Lift the corrosion inhibition of formula.Each component in the formula of antisludging agent of the present invention cooperates, and has without phosphorus, non-nitrogen, delays
Erosion scale-inhibiting properties are prominent and fungicide compatibility is good, are suitable for the advantages that high rigidity high alkalinity high concentration multiple operation.
As the preferred embodiment of the phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, institute
State the component for including following parts by weight suitable for the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water：Include following parts by weight
Component：25~35 parts of poly-epoxy succinic acid, 15~25 parts of multiple copolymer, 2~5 parts of azole compounds, soluble zinc salt 5~8
30~40 parts of part, 5~8 parts of organic acid and deionized water.
Corrosion and scale inhibition performance using the antisludging agent of above-mentioned formula is more excellent.
As the preferred embodiment of the phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, institute
State the component for including following parts by weight suitable for the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water：Poly-epoxy succinic acid 30
Part, 20 parts of multiple copolymer, 2 parts of azole compounds, 8 parts of soluble zinc salt, 5 parts of organic acid and 35 parts of deionized water.
Corrosion and scale inhibition performance using the antisludging agent of above-mentioned formula is the most excellent, and rate of corrosion is lower, resistance calcium and resistance zinc effect
Most preferably.
As the preferred embodiment of the phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, institute
State in multiple copolymer containing at least one of carboxyl, hydroxyl, amide groups and sulfonic group.
Carboxylic acid functional in multiple copolymer, it is to Ca2+、Mg2+、Fe3+Plasma has stronger sequestering power, no
Only scattered and cohesion, moreover it is possible to disturb lattice normally to arrange in inorganic scale crystallization process, so as to reach scale inhibition, antiscale
Effect；And hydroxyl, amide groups are to hindering Ca3(PO4)2Dirt is beneficial；Particularly sulfonic group is to Ca3(PO4)2Dirt has good suppression energy
Power, can effectively dispersing metal oxides, stablize zinc salt.
As the preferred embodiment of the phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, institute
Multiple copolymer is stated as at least one of a~c：A. the bipolymer of acrylic acid and hydroxypropyl acrylate；B. acrylic acid with
The bipolymer of 2- acrylamides-methyl propane sulfonic acid；C. acrylic acid, hydroxypropyl acrylate and 2- acrylamides-methyl-prop sulphur
The terpolymer of acid.
Preferable scale inhibition antiscaling effect can be reached using above-mentioned copolymer, and can effectively dispersing metal oxides, stabilization
Zinc salt, resistance calcium, resistance zinc significant effect.
As the preferred embodiment of the phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, institute
State the terpolymer that multiple copolymer is acrylic acid, hydroxypropyl acrylate and 2- acrylamides-methyl propane sulfonic acid.
Using the scale inhibition effect of the terpolymer of acrylic acid, hydroxypropyl acrylate and 2- acrylamides-methyl propane sulfonic acid
Most preferably.
As the preferred embodiment of the phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, institute
Azole compounds are stated as at least one of benzotriazole, methylbenzotriazole and mercapto benzothiazole sodium salt.
As the preferred embodiment of the phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, institute
It is zinc chloride and/or zinc sulfate to state soluble zinc salt.
As the more preferably embodiment of the phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water,
The organic acid is citric acid and/or itaconic acid.
Citric acid and itaconic acid can preferably improve upper content limit of the zinc salt in alkaline solution, lift the inhibition of formula
Performance.
The beneficial effects of the present invention are：The present invention provides a kind of no-phosphate corrosion suitable for industrial circulating cooling water
Antisludging agent, compared with phosphorus system now, zinc system formula, when antisludging agent of the present invention is used for industrial circulating cooling water, has without phosphorus, nothing
Malicious, biodegradable environmental-friendly characteristic, there is no emission pollution problem, can substantially reduce sewage disposal expense.
Embodiment
Embodiment 1
A kind of embodiment of phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, the present embodiment
The phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water includes the component of following parts by weight：Poly-epoxy succinic acid 30
Part, 20 parts of multiple copolymer, 2 parts of azole compounds, 8 parts of soluble zinc salt, 5 parts of organic acid and 35 parts of deionized water；
Wherein, the multiple copolymer is acrylic acid and the bipolymer of hydroxypropyl acrylate；The azole compounds
For benzotriazole；The soluble zinc salt is zinc chloride；The organic acid is citric acid.
The preparation method of phosphate-free corrosion inhibition antisludging agent described in the present embodiment suitable for industrial circulating cooling water is：To go from
Sub- water, poly-epoxy succinic acid, multiple copolymer, azole compounds, soluble zinc salt and organic acid sequentially add container in proportion
In, be stirred at room temperature 3 it is small when up to the phosphate-free corrosion inhibition antisludging agent.
Embodiment 2
A kind of embodiment of phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, the present embodiment
The phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water includes the component of following parts by weight：Poly-epoxy succinic acid 30
Part, 20 parts of multiple copolymer, 2 parts of azole compounds, 8 parts of soluble zinc salt, 5 parts of organic acid and 35 parts of deionized water；
Wherein, the multiple copolymer is acrylic acid and the bipolymer of 2- acrylamides-methyl propane sulfonic acid；The azoles
Class compound is benzotriazole；The soluble zinc salt is zinc chloride；The organic acid is citric acid.
It is suitable for the same embodiment of preparation method of the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water described in the present embodiment
1。
Embodiment 3
A kind of embodiment of phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, the present embodiment
The phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water includes the component of following parts by weight：Poly-epoxy succinic acid 30
Part, 20 parts of multiple copolymer, 2 parts of azole compounds, 8 parts of soluble zinc salt, 5 parts of organic acid and 35 parts of deionized water；
Wherein, the multiple copolymer is acrylic acid, hydroxypropyl acrylate, the ternary of 2- acrylamides-methyl propane sulfonic acid
Copolymer；The azole compounds are benzotriazole；The soluble zinc salt is zinc chloride；The organic acid is citric acid.
It is suitable for the same embodiment of preparation method of the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water described in the present embodiment
1。
Embodiment 4
A kind of embodiment of phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, the present embodiment
The phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water includes the component of following parts by weight：Poly-epoxy succinic acid 20
Part, 10 parts of multiple copolymer, 5 parts of azole compounds, 5 parts of soluble zinc salt, 10 parts of organic acid and 50 parts of deionized water；
Wherein, the multiple copolymer is acrylic acid, hydroxypropyl acrylate, the ternary of 2- acrylamides-methyl propane sulfonic acid
Copolymer；The azole compounds are benzotriazole；The soluble zinc salt is zinc chloride；The organic acid is citric acid.
It is suitable for the same embodiment of preparation method of the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water described in the present embodiment
1。
Embodiment 5
A kind of embodiment of phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, the present embodiment
The phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water includes the component of following parts by weight：Poly-epoxy succinic acid 40
Part, 30 parts of multiple copolymer, 1 part of azole compounds, 10 parts of soluble zinc salt, 10 parts of organic acid and 25 parts of deionized water；
Wherein, the multiple copolymer is acrylic acid, hydroxypropyl acrylate, the ternary of 2- acrylamides-methyl propane sulfonic acid
Copolymer；The azole compounds are mercapto benzothiazole sodium salt；The soluble zinc salt is zinc chloride；The organic acid is lemon
Lemon acid.
Embodiment 6
A kind of embodiment of phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, the present embodiment
The phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water includes the component of following parts by weight：Poly-epoxy succinic acid 25
Part, 25 parts of multiple copolymer, 5 parts of azole compounds, 5 parts of soluble zinc salt, 5 parts of organic acid and 30 parts of deionized water；
Wherein, the multiple copolymer is acrylic acid, hydroxypropyl acrylate, the ternary of 2- acrylamides-methyl propane sulfonic acid
Copolymer；The azole compounds are methylbenzotriazole；The soluble zinc salt is zinc chloride；The organic acid is clothing health
Acid.
It is suitable for the same embodiment of preparation method of the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water described in the present embodiment
1。
Embodiment 7
A kind of embodiment of phosphate-free corrosion inhibition antisludging agent of the present invention suitable for industrial circulating cooling water, the present embodiment
The phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water includes the component of following parts by weight：Poly-epoxy succinic acid 35
Part, 15 parts of multiple copolymer, 2 parts of azole compounds, 8 parts of soluble zinc salt, 8 parts of organic acid and 40 parts of deionized water；
Wherein, the multiple copolymer is acrylic acid, hydroxypropyl acrylate, the ternary of 2- acrylamides-methyl propane sulfonic acid
Copolymer；The azole compounds are benzotriazole；The soluble zinc salt is zinc sulfate；The organic acid is itaconic acid.
It is suitable for the same embodiment of preparation method of the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water described in the present embodiment
1。
Embodiment 8
The phosphate-free corrosion inhibition antisludging agent that embodiment 1~7 is suitable for industrial circulating cooling water carries out inhibition experiment, static resistance
Dirt experiment and static resistance zinc dirt experiment, the specific method of experiment are as follows：
Inhibition is tested：Inhibition assessment method is with reference to GB/T18175-2000《Water treatment agent corrosion inhibition measures rotary hanging plate
Method》.Experiment condition：It is 30mg/L to add dose, and temperature control (50 ± 1) DEG C, rotating speed 75r/min, experiment water is prepares water, in fact
It is carbon steel A to test lacing film3Standard lacing film.
Static-state scale inhibition is tested：The test of calcium carbonate scale inhibition performance is with reference to GB/T16632-2008《Water treatment agent scale-inhibiting properties are evaluated
Method tosca method》.Experiment condition：It is 30mg/L to add dose, and temperature control (80 ± 1) DEG C, experiment water quality is artificial
Prepare water (Ca2+And HCO3 -Concentration is 250mg/L), experimental period 10h.
Static state resistance zinc dirt experiment：Stablize the evaluation method reference of zinc salt《China PetroChemical Corporation cools down water analysis
And test method》(static-state scale inhibition assessment method 403).Dose 30mg/L is added, experiment water quality manually prepares water (Ca2+And HCO3 -
Concentration is 250mg/L), zinc ion 5mg/L (1.5 times of concentration, containing zinc ion in formula), temperature control (80 ± 1) DEG C, experiment
Time 10h.
Experimental result is shown in Table 1.
1 analysis of experimental results of table
| Group | Add dose (mg/L) | Rate of corrosion (mm/a) | Hinder calcium scale rate, % | Hinder zinc dirt rate, % |
| Embodiment 1 | 30 | 0.0328 | 95.8 | 82.4 |
| Embodiment 2 | 30 | 0.0321 | 96.4 | 82.0 |
| Embodiment 3 | 30 | 0.0312 | 97.2 | 83.7 |
| Embodiment 4 | 30 | 0.0312 | 96.1 | 82.5 |
| Embodiment 5 | 30 | 0.0321 | 95.4 | 82.7 |
| Embodiment 6 | 30 | 0.0320 | 95.7 | 83.1 |
| Embodiment 7 | 30 | 0.0318 | 96.1 | 82.7 |
It can be seen that the excellent performance of phosphate-free corrosion inhibition antisludging agent of the present invention, corrosion rate ＜ from the experimental result of table 1
0.004mm/a (better than Sinopec Group to the regulatory requirements of recirculated water operational effect, corrosion rate≤0.075mm/a), resistance
Calcium carbonate scale rate ＞ 95%, resistance zinc dirt rate ＞ 80%.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than the present invention is protected
The limitation of scope is protected, although being explained in detail with reference to preferred embodiment to the present invention, those of ordinary skill in the art should
Understand, can be to technical scheme technical scheme is modified or replaced equivalently, without departing from the essence of technical solution of the present invention
And scope.
Claims (9)
1. a kind of phosphate-free corrosion inhibition antisludging agent suitable for industrial circulating cooling water, it is characterised in that include following parts by weight
Component：20~40 parts of poly-epoxy succinic acid, 10~30 parts of multiple copolymer, 1~5 part of azole compounds, soluble zinc salt 5~10
25~50 parts of part, 5~10 parts of organic acid and deionized water.
2. as claimed in claim 1 be suitable for industrial circulating cooling water phosphate-free corrosion inhibition antisludging agent, it is characterised in that comprising with
The component of lower parts by weight：It is 25~35 parts of poly-epoxy succinic acid, 15~25 parts of multiple copolymer, 2~5 parts of azole compounds, solvable
Property 30~40 parts of 5~8 parts of zinc salt, 5~8 parts of organic acid and deionized water.
3. as claimed in claim 1 be suitable for industrial circulating cooling water phosphate-free corrosion inhibition antisludging agent, it is characterised in that comprising with
The component of lower parts by weight：30 parts of poly-epoxy succinic acid, 20 parts of multiple copolymer, 2 parts of azole compounds, 8 parts of soluble zinc salt, have
35 parts of 5 parts of machine acid and deionized water.
4. it is suitable for the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water as claimed in claim 1, it is characterised in that described more
Contain at least one of carboxyl, hydroxyl, amide groups and sulfonic group in membered copolymer.
5. it is suitable for the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water as claimed in claim 1, it is characterised in that described more
Membered copolymer is at least one of a~c：A. the bipolymer of acrylic acid and hydroxypropyl acrylate；B. acrylic acid and 2- third
The bipolymer of acrylamide-methyl propane sulfonic acid；C. acrylic acid, hydroxypropyl acrylate and 2- acrylamides-methyl propane sulfonic acid
Terpolymer.
6. it is suitable for the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water as claimed in claim 1, it is characterised in that described more
Membered copolymer is the terpolymer of acrylic acid, hydroxypropyl acrylate and 2- acrylamides-methyl propane sulfonic acid.
7. it is suitable for the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water as claimed in claim 1, it is characterised in that the azoles
Class compound is at least one of benzotriazole, methylbenzotriazole and mercapto benzothiazole sodium salt.
8. as claimed in claim 1 be suitable for industrial circulating cooling water phosphate-free corrosion inhibition antisludging agent, it is characterised in that it is described can
Soluble zinc salt is zinc chloride and/or zinc sulfate.
9. it is suitable for the phosphate-free corrosion inhibition antisludging agent of industrial circulating cooling water as claimed in claim 1, it is characterised in that described to have
Machine acid is citric acid and/or itaconic acid.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181668A (en) * | 2018-09-17 | 2019-01-11 | 天津大港油田滨港集团博弘石油化工有限公司 | A kind of sewage matches application of the calcium and magnesium antisludging agent in tertiary oil recovery |
| CN109835989A (en) * | 2019-04-02 | 2019-06-04 | 常州工程职业技术学院 | A kind of recirculated cooling water composite scale inhibitor and preparation method thereof |
| CN110028169A (en) * | 2019-04-22 | 2019-07-19 | 苏州安峰环保技术有限公司 | A kind of no-phosphate corrosion scale inhibition one agent and preparation method for processing cycle cooling water |
| CN110835174A (en) * | 2019-11-27 | 2020-02-25 | 江苏琪朗生物科技有限公司 | Phosphorus-free industrial circulating water composite corrosion and scale inhibitor |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109181668A (en) * | 2018-09-17 | 2019-01-11 | 天津大港油田滨港集团博弘石油化工有限公司 | A kind of sewage matches application of the calcium and magnesium antisludging agent in tertiary oil recovery |
| CN109835989A (en) * | 2019-04-02 | 2019-06-04 | 常州工程职业技术学院 | A kind of recirculated cooling water composite scale inhibitor and preparation method thereof |
| CN110028169A (en) * | 2019-04-22 | 2019-07-19 | 苏州安峰环保技术有限公司 | A kind of no-phosphate corrosion scale inhibition one agent and preparation method for processing cycle cooling water |
| CN110835174A (en) * | 2019-11-27 | 2020-02-25 | 江苏琪朗生物科技有限公司 | Phosphorus-free industrial circulating water composite corrosion and scale inhibitor |
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