CN105884049B - Recirculated cooling water initial stage inorganic agent and recirculating cooling water system initial stage processing method - Google Patents
Recirculated cooling water initial stage inorganic agent and recirculating cooling water system initial stage processing method Download PDFInfo
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- CN105884049B CN105884049B CN201610037031.3A CN201610037031A CN105884049B CN 105884049 B CN105884049 B CN 105884049B CN 201610037031 A CN201610037031 A CN 201610037031A CN 105884049 B CN105884049 B CN 105884049B
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- 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
- C02F5/105—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 combined with inorganic substances
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- 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
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- 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
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- 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
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Abstract
The subject to be solved by the invention is to provide a kind of recirculated cooling water initial stage inorganic agent, can reduce be used to form initial stage anticorrosion epithelium needed for phosphorus concentration and while zinc concentration, anticorrosion ability and antiscaling effect are obtained in the form of a kind of medicament.Solution of the invention is to provide a kind of recirculated cooling water initial stage inorganic agent, it is used to be added in the starting of recirculating cooling water system in the water system and forms initial stage anticorrosion epithelium in the metal part surface of the water system, it wherein, is that a medicament is made by the copolymer (AA/HAPS based polymer) of phosphorus compound and zinc compound and acrylic acid and hydroxyl allyloxy propane sulfonic acid and/or its salt to form.So as to be converted into PO in water system4Total phosphorus concentration become 15~30mgPO4/ L, zinc concentration become 5~20mgZn/L, the concentration of AA/HAPS based polymer becomes 20~60mg solid/L mode and adds the initial stage inorganic agent.
Description
Technical field
The present invention relates to a kind of when newly installing standby starting, equipment when operating again for being added in recirculated cooling water
To form the initial stage inorganic agent and recirculating cooling water system of initial stage anticorrosion epithelium in the metal part surface of the water system
Initial stage processing method.
Background technique
All the time, after during operation stopping when being operated as the new equipment of factory, due to progress time-based maintenance again
The method for treating water of recirculating cooling water system when running proposes a kind of method in patent document 1, so that total phosphorus concentration
As 70~120mgPO4/ L, phosphate is added in water system as the mode of 10~30mgZn/L for zinc concentration and zinc impregnation is closed
Object, so that the metal part surface in heat exchanger etc. forms initial stage anticorrosion epithelium.
It is described in the patent document 1, the case where the situation due to process object generates high-temperature portion (for example,
While operating heat exchanger, implement initial stage anticorrosion epithelium formed processing the case where etc.) etc. whens, in order to prevent by anticorrosion
Calcium in ingredient and water system is formed by caused by series of calcium phosphate scale is excessively precipitated, adheres in metal part surface not
Good influence as the polyelectrolyte for having the effect of that series of calcium phosphate scale is prevented to be precipitated and/or adhere to, adds as needed
Add be as solid component acrylic acid series polymeric compounds of 50~300mg/L or so etc. low-molecular weight polymer.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2011-202243 bulletin.
Summary of the invention
In recent years, due to the raising of the reinforcing to draining control, people expect to reduce the phosphorus and zinc concentration in draining, because
This, people expect to reduce the phosphorus and zinc concentration for being used to form initial stage anticorrosion epithelium in recirculating cooling water system.
In addition, needing at least 3 to carry out the processing and scale counter-measure that are used to form initial stage anticorrosion epithelium simultaneously
Kind treating chemicals, that is, phosphate, zinc compound and low-molecular weight polymer, moreover, in medicament addition, Adding medicine control, drug
Management etc. needs cumbersome labour, and therefore, people, which are also contemplated that, improves it.
The subject of the invention is to provide a kind of recirculated cooling waters with the initial stage of initial stage inorganic agent and recirculating cooling water system
Processing method, in the same of the phosphorus concentration and zinc concentration for reducing the initial stage anticorrosion epithelium being used to form in recirculating cooling water system
When, additionally it is possible to obtain antiscaling effect.
The inventors of the present invention be solve the above subject and discussion has been repeated, as a result, it has been found that, by with phosphorus compound and
Zinc compound combines the specific low-molecular weight polymer of addition together, can reduce and is used to form needed for initial stage anticorrosion epithelium
Phosphorus concentration and zinc concentration, in addition it is possible to obtain antiscaling effect.
The present invention is based on the discovery that complete, and main idea is as follows.
[1] a kind of recirculated cooling water initial stage inorganic agent is for being added in the starting of recirculating cooling water system
The initial stage inorganic agent of initial stage anticorrosion epithelium is formed in the water system in the metal part surface of the water system, which is characterized in that
It is by the copolymer of phosphorus compound and zinc compound and acrylic acid and hydroxyl allyloxy propane sulfonic acid and/or its salt (under
Face, referred to as " AA/HAPS based polymer ") it a medicament is made forms.
[2] such as the recirculated cooling water initial stage inorganic agent in [1], which is characterized in that the AA/HAPS based polymer be with
The ratio of molar ratio 70~90:10~30 contains the Component units from acrylic acid and comes from hydroxyl allyloxy propane sulfonic acid
And/or the copolymer that the Component units and weight average molecular weight of its salt are 1000~400000.
[3] such as the recirculated cooling water initial stage inorganic agent in [1] or [2], which is characterized in that the phosphorus compound is to be selected from
One or more of group as composed by the salt of orthophosphoric acid, hexa metaphosphoric acid, phosphonic acids and these acid, also, the zinc
Compound is zinc chloride and/or zinc sulfate.
[4] the recirculated cooling water initial stage inorganic agent such as in any one of [1] to [3], which is characterized in that it is containing 5
The AA/HAPS system of the phosphorus compound of~20 weight %, the zinc compound of 2~10 weight %, 5~30 weight %
The aqueous solution of polymer.
[5] the initial stage processing method of a kind of recirculating cooling water system is in the starting of recirculating cooling water system at this
The metal part surface of water system forms the initial stage processing method of initial stage anticorrosion epithelium, which is characterized in that so that the water system
Interior is converted into PO4Total phosphorus concentration become 15~30mgPO4/ L, zinc concentration become 5~20mgZn/L, AA/HAPS based polymer
Concentration become 20~60mg solid/L mode and add phosphorus compound and zinc compound and acrylic acid and hydroxyl allyloxy
The copolymer of propane sulfonic acid and/or its salt (hereinafter, referred to as " AA/HAPS based polymer ").
[6] such as the initial stage processing method of the recirculating cooling water system in [5], which is characterized in that the AA/HAPS system polymerization
Object is to contain Component units from acrylic acid with the ratio of molar ratio 70~90:10~30 and from hydroxyl allyloxy propane
The copolymer that the Component units of sulfonic acid and/or its salt and weight average molecular weight are 1000~400000.
[7] such as [5] or the initial stage processing method of the recirculating cooling water system in [6], which is characterized in that the phosphorus compound
It is selected from one or more of group as composed by orthophosphoric acid, hexa metaphosphoric acid, phosphonic acids and these sour salt, and institute
Stating zinc compound is zinc chloride and/or zinc sulfate.
[8] such as the initial stage processing method of the recirculating cooling water system in any one of [5] to [7], which is characterized in that will be described
Calcium hardness in water system is adjusted to 50~150mgCaCO3/L。
[9] such as the initial stage processing method of the recirculating cooling water system in any one of [5] to [8], which is characterized in that described
Recirculated cooling water initial stage inorganic agent described in any one of [1] to [4] of 150~300mg/L is added in water system.
By means of the invention it is possible to reduce the initial stage anticorrosion epithelium being used to form in recirculating cooling water system phosphorus concentration and
Zinc concentration, in addition it is possible to obtain antiscale effect while obtaining the anticorrosion ability generated by the formation of anticorrosion epithelium
Fruit.
The initial stage inorganic agent of recirculated cooling water through the invention can obtain above-mentioned work in the form of a medicament
With effect, and the burden that related medicament addition, Adding medicine control, drug control can be substantially reduced etc..
Detailed description of the invention
Fig. 1 is the schematic diagram for indicating the structure of heat-transfer area evaluation experimental device used in embodiment.
Fig. 2 is the schematic diagram for indicating the structure of determination of corrosion rate device used in embodiment.
Also, it is as follows to the description of symbols in attached drawing:
1 test water tank；
2 evaluation pipes；
3 developmental tubes；
4 heaters；
5 extra feed tanks；
10 beakers；
11 SS sensors；
12 SUS sensors；
13 SUS sensors；
14 blenders；
15 corrosion instrument.
Specific embodiment
In the following, the embodiment that the present invention will be described in detail.
[the initial stage processing method of recirculating cooling water system]
The initial stage processing method of recirculating cooling water system of the invention is in the starting of recirculating cooling water system in the water
The metal part surface of system forms the initial stage processing method of initial stage anticorrosion epithelium, which is characterized in that so that in the water system
Be converted into PO4Total phosphorus concentration become 15~30mgPO4/ L, zinc concentration become 5~20mgZn/L, AA/HAPS based polymer
Concentration becomes 20~60mg solid/L, and (" mg solid/L " indicates that the mg/L of the net portion (pure point) of AA/HAPS based polymer is dense
Degree) mode add being total to for phosphorus compound and zinc compound and acrylic acid and hydroxyl allyloxy propane sulfonic acid and/or its salt
Polymers (hereinafter, referred to as " AA/HAPS based polymer ").
In addition, as the metal parts in the present invention as object, preferably Ferrious material component, especially carbon steel portion
Part.As recirculating cooling water system, preferably open loop formula cooling water system.
In above patent document 1, although the addition for acrylic acid series polymeric compounds is recorded, in patent
In document 1, and the details of used acrylic acid series polymeric compounds is not known, in addition, also not closing phosphorus compound, zinc impregnation
The record that a medicament is added is made in object and AA/HAPS based polymer, moreover, being also not given to the note of following enlightenments
It carries: if adding AA/HAPS based polymer together with phosphorus compound and zinc compound, can reduce and be used to form initial stage anticorrosion
The amount of phosphorus compound needed for film and zinc compound.
Compared with the case where being not added with AA/HAPS based polymer, if added together with phosphorus compound and zinc compound low
AA/HAPS based polymer in polydispersity polymer, then can significantly reduce the total phosphorus concentration for being used to form initial stage anti-corrosion film
And zinc concentration, the present invention are completed based on the new discovery.
In the present invention, by being used together AA/HAPS based polymer with zinc compound with phosphorus compound, even if water system
Interior total phosphorus concentration and zinc concentration is that low concentration can also obtain sufficient anticorrosion ability, therefore, and is not combined AA/HAPS system
The case where polymer, is compared, and can significantly reduce the usage amount of phosphorus compound and zinc compound, and can reduce these at
Sufficient anticorrosion ability is obtained on the basis of dividing the concentration in water system, therefore, with following advantage.
(1) it is able to suppress the usage amount of the Related Component of the carrying capacities of environment such as phosphorus compound, zinc compound.
(2) in the past, when applying thermic load, in order to inhibit the scale of calcium phosphate, it is poly- to need to add superfluous low molecular weight
The new of low-molecular weight polymer gelation can be generated if improving the polymer concentration in water system for antiscale by closing object
Problem still in the present invention, by using AA/HAPS based polymer, is able to suppress the usage amount of phosphorus compound, as a result,
The amount of low-molecular weight polymer can be reduced, as a result, the gelation of low-molecular weight polymer can be prevented.
(3) in the previous method, it needs to add total phosphorus concentration 100mgPO4/ L, zinc concentration 20mgZn/L, low molecular weight
Polymer concentration 60mg solid/L or so, therefore, if a medicament is made in they, additive amount will will become thousands of mg/
L, this is simultaneously unrealistic.Therefore, according to previous method, a medicament is not made but adds three medicaments respectively and still passes through
Since the use concentration of each ingredient is reduced, therefore a medicament can be made, moreover, place when medicine management, dosing in the present invention
Reason also becomes easy.
< AA/HAPS based polymer >
AA/HAPS based polymer is compared with other low-molecular weight polymers, for example, with acrylic acid (AA) and 2- acryloyl
Amine-2- methyl-1-propane sulfonic acid (AMPS) copolymer (hereinafter, referred to " AA/AMPS based polymer ") is compared, corruption with higher
Lose inhibitory effect the Forming ability of epithelium (initial stage processing), at this point, as with phosphorus compound and zinc compound associated with
Low-molecular weight polymer is very effective.
As AA/HAPS based polymer, preferably with the ratio of molar ratio (AA:HAPS molar ratio) 70~90:10~30
Containing the Component units from acrylic acid (AA) and from alkali such as hydroxyl allyloxy propane sulfonic acid (HAPS) and/or its sodium salts
The copolymer that the Component units and weight average molecular weight of the HAPS salt of metal salt etc. are 1000~400000.
If AA:HAPS molar ratio and molecular weight can not obtain good antiscaling effect, separately other than the range
Outside, can not be reduced by the combination with phosphorus compound and zinc compound for total phosphorus concentration needed for obtaining anticorrosion ability and
Zinc concentration.
The AA/HAPS molar ratio of AA/HAPS based polymer, more preferably 70~90:10~30.In addition, AA/HAPS system is poly-
The weight average molecular weight for closing object is more preferably 5000~50000.In addition, above-mentioned weight average molecular weight is based on gel permeation chromatography
The value for being converted into standard polypropylene acid of (GPC method).
For AA/HAPS based polymer, can be used AA/HAPS molar ratio, weight average molecular weight different two kinds with
On.
< phosphorus compound >
As phosphorus compound, it is able to use orthophosphoric acid and/or its salt, such as sodium phosphate, potassium phosphate, disodium hydrogen phosphate, phosphorus
Sour hydrogen dipotassium, sodium dihydrogen phosphate, potassium dihydrogen phosphate, in addition to this, additionally it is possible to use 1-Hydroxy ethylene-1,1-diphosphonic acid
(HEDP), 2- phosphonobutane -1,2, the phosphonic acids such as 3- tricarboxylic acids (PBTC), amino trimethyl phosphonic acids and/or its salt, pyrophosphoric acid and/
Or the polymer phosphates, such as potassium pyrophosphate, sodium pyrophosphate such as its salt, tripolyphosphate and/or its salt, hexa metaphosphoric acid and/or its salt etc.
The pyrophosphoric acids such as hexa metaphosphoric acids alkali metal salt, the Sodium Acid Pyrophosphates such as alkali metal pyrophosphate salts, calgon, hexa metaphosphoric acid potassium
Dihydric salt etc..It can be used alone, can also be used in combination of two or more.
Wherein, the material of anticorrosion epithelium, preferably orthophosphoric acid and/or its alkali metal salt, six to be formed partially as that can promote
Phosphoric acid and/or its alkali metal salt, phosphonic acids and/or its alkali metal salt.
< zinc compound >
As zinc compound, the preferably zinc salts such as zinc chloride, zinc sulfate can be used alone zinc compound,
It can be used in combination of two or more.
< initial stage handles >
In the present invention, in the starting of recirculating cooling water system, addition phosphorus compound, zinc compound and AA/HAPS system
Polymer is so as to be converted into PO in recirculating cooling water system4Total phosphorus concentration become 15~30mgPO4/ L, zinc concentration become 5~
The concentration of 20mgZn/L, AA/HAPS based polymer becomes 20~60mg solid/L.
If total phosphorus concentration and zinc concentration are lower than the lower limit of the range, sufficient anticorrosion ability can not be obtained.Such as
Fruit is higher than the upper limit of the range, then can not achieve the purpose of the present invention, i.e., cannot reduce total phosphorus concentration and zinc concentration.
That is, in the patent document 1, so that total phosphorus concentration becomes 70~120mgPO4/ L, zinc concentration become 10~
The mode of 30mgZn/L is added, and still, compared with this existing method, in the present invention, passes through AA/HAPS based polymer
Combination, can make total phosphorus concentration become 15~30mgPO4/ L, zinc concentration become 5~20mgZn/L, anti-so as to make to be formed initial stage
Total phosphorus concentration needed for corroding epithelium reduces about 70%, and zinc concentration can also be made to reduce about 50% or so.
In addition, if the addition concentration of AA/HAPS based polymer be lower than above range lower limit, be unable to fully obtain by
The reducing effect of antiscaling effect caused by AA/HAPS based polymer and total phosphorus concentration and zinc concentration.If AA/HAPS system
The addition concentration of polymer is higher than the above-mentioned upper limit, then the phosphorus as anti-corrosive ingredi, zinc can be made excessively to disperse in water, therefore,
It becomes difficult to be used as anticorrosion epithelium.
In the present invention, from the aspect of antiscaling effect, addition phosphorus compound, zinc compound and the polymerization of AA/HAPS system
The calcium hardness of the recirculating cooling water system of object is preferably 50~150mgCaCO3/ L, particularly preferably 50~100mg CaCO3/L。
If the calcium hardness of water system is excessively high, sufficient antiscaling effect can not be obtained sometimes.When water system calcium hardness compared with
When low, the problem of precipitation almost without scale, but on the other hand, the phosphorus compound and calcium by addition cannot be fully formed
Effect and generate anticorrosion epithelium is formed by by phosphorus and calcium, so as to make anticorrosion ability be deteriorated.Therefore, in this hair
In bright, concentration management preferably is carried out by modes such as discharges, to become the calcium hardness.Even if in addition, carrying out discharge water
It, can be by adding or removing calcium nitrate, calcium chloride etc. when adjusting and dealing with objects the water quality of water system and also offset from the range
Calcium hardness ingredient carry out water quality adjustment.
In addition, the pH for carrying out water system when initial stage processing according to the present invention is preferably 6.0~7.0.If pH is higher than upper
The upper limit is stated, then the iron dissolved out from Ferrious material component is less, therefore, cannot be fully formed on Ferrious material parts surface
As the ferric phosphate of anticorrosion epithelium ingredient, and if being lower than above-mentioned lower limit, corrosivity becomes strong, and object metal processed is
Other existing metal materials are likely to occur the enhancement of temporary corrosion in system.For the adjusting method of pH, without special
Restriction, however, it is preferred to pass through method of the acid to be adjusted of addition hydrochloric acid, sulfuric acid etc..
In addition, in the present invention, it is preferred to adding phosphorus compound, zinc compound and AA/HAPS based polymer and making initial stage pH
Adjusting is 10~40mgCaCO in the M basicity of the water system of above range3/L。
Above-mentioned initial stage processing is generally implemented under conditions of room temperature.
In the present invention, in the starting of recirculating cooling water system, as described above, being added phosphorus compound, zinc impregnation is closed
Object and AA/HAPS based polymer will carry out the initial stage treatment process to become the initial stage treatment process of above-mentioned concentration range
During be set as 24~96 hours, be particularly preferably set as 24~48 hours.If the processing time at initial stage is too short, it is unable to shape
At the superior anticorrosion epithelium of anticorrosion ability, and too long, the effect that the time matches can not be obtained and handled.
[recirculated cooling water initial stage inorganic agent]
Recirculated cooling water of the invention is suitable for the initial stage of the recirculating cooling water system of aforementioned present invention with initial stage inorganic agent
In the implementation of processing method, be a medicament is made of the phosphorus compound, zinc compound and AA/HAPS based polymer and
At.
Initial stage inorganic agent of the invention is preferably the institute of the phosphorus compound containing 5~20 weight %, 2~10 weight %
State zinc compound, 5~30 weight % the AA/HAPS based polymer aqueous solution, preferably: by the conduct of 150~300mg/L
The initial stage inorganic agent of the invention of the preparation of the form of a this liquid is added in recirculating cooling water system, and will be recycled cold
But the total phosphorus concentration in water system, zinc concentration and AA/HAPS based polymer concentration are set in afore mentioned concentration limits, implement as a result,
Initial stage processing method of the invention.
In addition, dephosphorization chemical combination can be contained in initial stage inorganic agent of the invention not damaging within the scope of the purpose of the present invention
Medicament other than object, zinc compound and AA/HAPS based polymer, for example, can containing for adjust calcium hardness calcium compound,
For adjusting the acid etc. of pH.
Embodiment
In the following, being further elaborated with the present invention by enumerating embodiment.
[addition medicament]
In following embodiments and comparative example, the details of polymer used in the preparation of inorganic agent is such as in the early stage
Under.
AA/HAPS polymer I:AA:HAPS molar ratio is 80:20, the polymer that weight average molecular weight is 10000；
AA/HAPS polymer II:AA:HAPS molar ratio is 90:10, the polymer that weight average molecular weight is 10000；
AA/HAPS polymer III:AA:HAPS molar ratio is 65:35, the polymer that weight average molecular weight is 10000；
AA/AMPS polymer I:AA:AMPS molar ratio is 80:20, the polymer that weight average molecular weight is 10000；
MA polymer I: the homopolymer for the maleic acid that weight average molecular weight is 1000.
[evaluation of anticorrosion ability]
[embodiment 1]
The preparation > of < initial stage inorganic agent
Initial stage inorganic agent 1 of the invention is prepared, is the phosphonic acids by containing 20 weight % (total phosphoric acid concentration): orthophosphoric acid=
Zinc chloride, 35 weights of the mixture (hereinafter, referred to as " mixing phosphorus compound ") of 1:1 (weight ratio), 10 weight % (total zinc concentration)
The aqueous solution for measuring the AA/HAPS polymer I of % (total solid content concentration) is formed.
< tests water >
Wood raised path between farm fields water (calcium hardness 40mgCaCO out of office3/ L, M basicity is 40mgCaCO3/ L) in, so that calcium hardness becomes
60mgCaCO3The mode of/L adds the aqueous solution (calcium chloride water) of 10% calcium hardness, and as test water.The test
The pH of water is that 6.0, M basicity is 30mgCaCO3/L。
< experimental rig >
Use heat-transfer area evaluation experimental device shown in FIG. 1.
The experimental rig is that the test water in test water tank (100L capacity) 1 is made to pass through water circulating pump P1With circular route L1、
L2It is recycled in developmental tube 3, evaluation pipe 2 made of iron is inserted into the developmental tube 3 and makes its dipping.It is being recycled back to streamline
L2Middle setting flow control valve V.In addition, being heated by heater (thermocouple) 4 pairs of evaluation pipes 2.
5 be extra feed tank (300L capacity), as needed, the water in extra feed tank 5 can be passed through test water replenishment pump P2、
And through feeding waterline L3It is supplied to test water tank 1.L4It is overflow line.
< experimental condition >
It is heated using heater 4, and is adjusted in a manner of making the internal temperature for evaluating pipe 2 become 90 DEG C.
It is set as 2 days during the flow velocity for testing water is set as 0.5m/s, initial stage processing.
The initial stage inorganic agent 1 of 200mg/L is added in test water in test water tank 1 to be tested, after measurement test
Evaluate the corrosion loss amount of pipe 2.
In addition, adding the initial stage inorganic agent 1 of 200mg/L in test water, it is converted into PO4Total phosphorus concentration become
20mgPO4/ L, zinc oxide concentration become 10mgZn/L, AA/HAPS polymer I concentration as 35mg solid/L.
It shows the result in table 1.
[embodiment 2]
Test water in add 300mg/L initial stage inorganic agent 1, will test water in mixing phosphorus compound, zinc chloride and
The concentration of AA/HAPS polymer I is adjusted as shown in table 1, in addition to this, is tested similarly to Example 1, by result
It is shown in Table 1.
[comparative example 1]
Initial stage inorganic agent 1 is not added in test water and is tested similarly to Example 1, is shown the result in table 1.
[comparative example 2]
The initial stage inorganic agent 1 of 100mg/L is added in test water, and the mixing phosphatization in test water is closed as shown in table 1
The concentration of object, zinc chloride and AA/HAPS polymer I is adjusted, and in addition to this, is tested similarly to Example 1, will tie
Fruit is shown in Table 1.
[comparative example 3]
100mgPO is added in test water4The hexa metaphosphoric acid of/L, the zinc chloride of 20mgZn/L, 60mg solid/L AA/
AMPS polymer is to substitute initial stage inorganic agent 1, in addition to this, is tested similarly to Example 1, shows the result in table 1.
Table 1
As shown in Table 1, by adding initial stage inorganic agent of the invention to become defined concentration, in the phosphorus for reducing water system
On the basis of concentration and zinc concentration, higher anticorrosion ability can be obtained.
[evaluation of scale inhibitory effect]
[embodiment 3]
The preparation > of < initial stage inorganic agent
Mixing phosphorus compound, the 10 weight % by containing 20 weight % (total phosphoric acid concentration) are prepared similarly to Example 1
The zinc chloride of (total zinc concentration), 35 weight % (total solid content concentration) AA/HAPS polymer I aqueous solution formed this hair
Bright initial stage inorganic agent 1.
< tests water >
Wood raised path between farm fields water (calcium hardness 40mgCaCO out of office3/ L, M basicity is 40mgCaCO3/ L) in, so that calcium hardness becomes
50mgCaCO3The mode of/L adds 10% calcium hardness solution (calcium chloride solution), as test water.The pH of the test water is
6.2, M basicity are 30mgCaCO3/L。
< experimental rig >
Heat-transfer area evaluation experimental device shown in FIG. 1 is used similarly to Example 1.
< experimental condition >
It is heated using heater 4, and is adjusted such that the internal temperature of evaluation pipe 2 becomes 90 DEG C.Water will be tested
Flow velocity be set as 0.5m/s, initial stage processing during be set as 2 days.
The initial stage inorganic agent of 200mg/L is added in test water in test water tank 1 to be tested, measurement is attached after testing
Evaluation pipe 2 on scale amount, to calculate attachment speed.
It shows the result in table 2.
In addition, the target value of the attachment speed of scale is 20mg/cm2Below/the moon.
[embodiment 4~6, reference example 1,2]
It in test preparation water, is adjusted by the addition to 10% calcium hardness solution, using being set as calcium shown in table 2
The test water of hardness is tested similarly to Example 3 in addition to this, is shown the result in table 2.
Table 2
It as shown in Table 2, is 50~150mgCaCO in calcium hardness3When/L, it can be obtained using initial stage inorganic agent of the invention
Good scale inhibitory effect.
[evaluation of anticorrosion ability and scale inhibitory effect]
[embodiment 7~11, reference example 3, comparative example 4~6]
The preparation > of < initial stage inorganic agent
It prepares as being contained shown in mixing phosphorus compound, phosphonic acids or orthophosphoric acid, zinc chloride and table 3 with concentration shown in table 3
The initial stage inorganic agent 2~8 that the aqueous solution of polymer is formed.In addition, mixing phosphorus compound, phosphonic acids and orthophosphoric acid concentration are total phosphoric acid
Concentration, zinc oxide concentration are total zinc concentrations, and polymer concentration is total solid content concentration.
Table 3
In addition, being converted into PO when adding the initial stage inorganic agent 2~8 of 200mg/L in testing water4Total phosphorus concentration become
20mgPO4/ L, zinc oxide concentration become 10mgZn/L, polymer concentration becomes 35mg solid/L, and when adding 100mg/L, it changes
It is counted as PO4Total phosphorus concentration become 10mgPO4/ L, zinc oxide concentration become 5mgZn/L, polymer concentration become 17.5mg solid/
L is converted into PO when adding 80mg/L4Total phosphorus concentration become 8mgPO4/ L, zinc oxide concentration are dense as 4mgZn/L, polymer
Degree becomes 14mg solid/L,
{ evaluation of anticorrosion ability }
< tests water >
1) during initial stage processing
Add that 10% calcium hardness aqueous solution (calcium chloride water), (magnesium sulfate is water-soluble for 10% magnesium aqueous solution in pure water
Liquid), 5%M basicity aqueous solution (sodium bicarbonate aqueous solution) is so that they respectively become 60mgCaCO3/L、30mgCaCO3/L、
60mgCaCO3/L.The pH of the test water is 8.0.
With initial stage inorganic agent shown in the addition table 4 of defined concentration shown in table 4 in the test water.
Using the test water as initial stage treatment fluid.
2) corrode acceleration period
Wood raised path between farm fields water (calcium hardness 40mgCaCO out of office3/ L, M basicity is 40mgCaCO3/ L, chloride, sulfate ion difference
For in 20mg/L), 10% chloride ion solution (sodium chloride solution) of addition, 10% sulfate ion solution (metabisulfite solution) with
Chloride ion concentration, sulfate ion concentration is set to respectively become 100mg/L.
Accelerate liquid for the test water as corrosion.
< test method >
Use determination of corrosion rate device shown in Fig. 2.
As shown in Fig. 2, each initial stage treatment fluid is added in 1L beaker 10, setting SS sensor 11 (SS400 (10 φ ×
30mm)), SUS sensor 12 (SUS (10 φ × 30mm)) and SUS sensor 13 (SUS (10 φ × 30mm)), then in room
Temperature starts to stir using blender 14.
After 2 days, test water is switched to corrosion and accelerates liquid, carries out stirring in one day again using blender.
Then, corrosion rate (mdd) is measured using corrosion instrument (manufacture of east Ji Yan company) 15.
{ evaluation of scale inhibitory effect }
< tests water >
In wood raised path between farm fields water out of office, 10% calcium hardness aqueous solution (calcium chloride water), 10% magnesium aqueous solution (magnesium sulfate water are added
Solution), 5%M basicity aqueous solution (sodium bicarbonate aqueous solution) is so that they respectively become 60mgCaCO3/L、30mgCaCO3/L、
60mgCaCO3/L。
In the test water, initial stage inorganic agent shown in table 4 is added to add concentration shown in table 4.
< test method >
Using heat-transfer area experimental rig shown in FIG. 1, by testing water replenishment pump P2And through feeding waterline L3To test water
It is fed, so that the residence time of test water tank 1 becomes 24 hours.
It is heated using 4 pairs of evaluation pipes 2 of heater so that its internal temperature becomes 90 DEG C.Water is tested with the speed of 0.5m/s
Degree carries out water flowing in 48 hours.
After the test, evaluation pipe 2 is removed, the attachment being attached on heat-transfer area is dried, weight is then measured.
According to attachment object amount as a result, calculating scale adheres to speed (mg/cm2/ the moon=mcm)
{ test result }
Test result is shown in Table 4.
Table 4
Following content as shown in Table 4.
About embodiment 7~11 it is found that corrosion rate, scale attachment speed are held at lower level, by using
AA/HAPS based polymer can form good anticorrosion epithelium.The AA/HAPS of AA/HAPS based polymer used in reference example 3
Molar ratio deviates from preferred scope of the invention, although scale inhibitory effect is good, corrosion rate is high.Comparative example 4 uses AA/
AMPS based polymer substitutes AA/HAPS based polymer, although scale inhibitory effect is good, corrosion rate is high.For making
For the comparative example 5 of MA homopolymer, corrosion rate is maintained at lower level, still, inhibits effect in the scale of heat-transfer area
Fruit is insufficient, is unpractical.
Comparative example 6 is the situation for indicating that the additive amount of initial stage inorganic agent of the invention is less, in order to obtain anticorrosion ability
With scale inhibitory effect, it is known that need to add the initial stage inorganic agent of normal concentration or more.
According to the above results it is found that using AA/HAPS based polymer, it is preferable to use the AA/ of defined AA/HAPS molar ratio
The initial stage treatment effect of the initial stage inorganic agent of the invention of HAPS based polymer is superior.
Claims (7)
1. a kind of recirculated cooling water initial stage inorganic agent is for being added to the water system in the starting of recirculating cooling water system
The initial stage inorganic agent of initial stage anticorrosion epithelium is formed in system and in the metal part surface of the water system, which is characterized in that
The recirculated cooling water is that phosphorus compound and zinc compound and copolymer are made to a medicament to form with initial stage inorganic agent,
Also, the copolymer is acrylic acid and hydroxyl allyloxy propane sulfonic acid and/or hydroxyl allyloxy propane sulfonate
Copolymer,
Also, the copolymer of the acrylic acid and hydroxyl allyloxy propane sulfonic acid and/or hydroxyl allyloxy propane sulfonate
It is to be contained with the ratio of molar ratio 70~90:10~30 from the Component units of acrylic acid and from hydroxyl allyloxy third
The copolymerization that the Component units of alkyl sulfonic acid and/or hydroxyl allyloxy propane sulfonate and weight average molecular weight are 1000~400000
Object,
Also, the recirculated cooling water is the phosphorus compound containing 5~20 weight %, 2~10 weight % with initial stage inorganic agent
The zinc compound, 5~30 weight % the acrylic acid and hydroxyl allyloxy propane sulfonic acid and/or hydroxyl allyloxy
The aqueous solution of the copolymer of propane sulfonate.
2. recirculated cooling water as described in claim 1 initial stage inorganic agent, wherein the phosphorus compound is selected from by positive phosphorus
One or more of acid, hexa metaphosphoric acid, composed group of salt of phosphonic acids and these acid, also, the zinc compound
It is zinc chloride and/or zinc sulfate.
3. a kind of initial stage processing method of recirculating cooling water system, wherein it is in the starting of recirculating cooling water system at this
The metal part surface of water system forms the initial stage processing method of initial stage anticorrosion epithelium, which is characterized in that
Phosphorus compound and zinc compound and copolymer are added, so as to be converted into PO in the water system4Total phosphorus concentration become 15
~30mgPO4/ L, zinc concentration become 5~20mgZn/L, the concentration of copolymer becomes 20~60mg solid/L,
Also, the copolymer is acrylic acid and hydroxyl allyloxy propane sulfonic acid and/or hydroxyl allyloxy propane sulfonate
Copolymer,
Also, the copolymer of the acrylic acid and hydroxyl allyloxy propane sulfonic acid and/or hydroxyl allyloxy propane sulfonate
It is to be contained with the ratio of molar ratio 70~90:10~30 from the Component units of acrylic acid and from hydroxyl allyloxy third
The Component units of alkyl sulfonic acid and/or hydroxyl allyloxy propane sulfonate and weight average molecular weight are 1000~400000 copolymerization
Object.
4. the initial stage processing method of recirculating cooling water system as claimed in claim 3, wherein the phosphorus compound be selected from by
One or more of orthophosphoric acid, hexa metaphosphoric acid, composed group of salt of phosphonic acids and these acid, also, the zinc impregnation
Closing object is zinc chloride and/or zinc sulfate.
5. the initial stage processing method of recirculating cooling water system as described in claim 3 or 4, wherein by the calcium of the water system
Hardness is adjusted to 50~150mgCaCO3/L。
6. the initial stage processing method of recirculating cooling water system as described in claim 3 or 4, wherein add in the water system
Add the recirculated cooling water of any of claims 1 or 2 initial stage inorganic agent of 150~300mg/L.
7. the initial stage processing method of recirculating cooling water system as claimed in claim 5, wherein added in the water system
The recirculated cooling water of any of claims 1 or 2 initial stage inorganic agent of 150~300mg/L.
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| CN107228575B (en) * | 2017-06-28 | 2019-02-19 | 内蒙古京宁热电有限责任公司 | A kind of indirect air cooling unit circulation process for corrosion control |
| CN114853240B (en) * | 2022-04-21 | 2023-08-01 | 天津正达科技有限责任公司 | Natural balance ultra-high concentration multiple and zero emission control method for circulating cooling water system |
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| CN102730849A (en) * | 2011-03-30 | 2012-10-17 | 栗田工业株式会社 | Method for preventing scale from forming in cooling water system |
| CN102782190A (en) * | 2010-03-26 | 2012-11-14 | 栗田工业株式会社 | Treatment method of cooling water system |
| CN104099614A (en) * | 2014-07-31 | 2014-10-15 | 威海翔宇环保科技有限公司 | Pre-filming technique for industrial recycling cooling water |
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| JP4598330B2 (en) * | 2001-09-13 | 2010-12-15 | オルガノ株式会社 | Anticorrosion method |
| JP3945202B2 (en) * | 2001-09-28 | 2007-07-18 | 伯東株式会社 | Corrosion prevention method |
| JP4089648B2 (en) * | 2004-03-31 | 2008-05-28 | 栗田工業株式会社 | Corrosion prevention method |
| JP5720369B2 (en) * | 2011-03-30 | 2015-05-20 | 栗田工業株式会社 | Basic treatment method for cooling water system |
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| CN102782190A (en) * | 2010-03-26 | 2012-11-14 | 栗田工业株式会社 | Treatment method of cooling water system |
| CN102730849A (en) * | 2011-03-30 | 2012-10-17 | 栗田工业株式会社 | Method for preventing scale from forming in cooling water system |
| CN104099614A (en) * | 2014-07-31 | 2014-10-15 | 威海翔宇环保科技有限公司 | Pre-filming technique for industrial recycling cooling water |
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