CN108017165A - Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water - Google Patents
Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water Download PDFInfo
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- CN108017165A CN108017165A CN201610938850.5A CN201610938850A CN108017165A CN 108017165 A CN108017165 A CN 108017165A CN 201610938850 A CN201610938850 A CN 201610938850A CN 108017165 A CN108017165 A CN 108017165A
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- phosphorus composite
- eorrosion snhibiter
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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
- C02F5/12—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
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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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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The present invention relates to circulating water cooling treatment field, the processing method of a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and recirculated cooling water is disclosed.The non-Phosphorus composite anti incrustation eorrosion snhibiter contains Carboxymethylinulin sodium, cyclodextrine derivatives and copolymer, and the copolymer contains the construction unit provided as the thiourea derivative shown in formula (I) and the construction unit provided by the unsaturated carboxylic acid of C3 C10；And application of the above-mentioned non-Phosphorus composite anti incrustation eorrosion snhibiter in circulating water cooling treatment；The processing method of recirculated cooling water includes adding above-mentioned non-Phosphorus composite anti incrustation eorrosion snhibiter into recirculated cooling water.Non-Phosphorus composite anti incrustation eorrosion snhibiter provided by the invention shows good scale inhibitor comprehensive performance, during applied to recirculated cooling water, can not only meet requirement of the recirculated cooling water to scale inhibition and inhibition, can also avoid environmental problem caused by existing phosphorous medicament.
Description
Technical field
The present invention relates to circulating water cooling treatment field, and in particular, to a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter and its should
With and recirculated cooling water processing method.
Background technology
In recirculating cooling water system, fouling and etching problem are primarily present.Scaling and corrosion in order to prevent, at present
Most convenient and effective method is that corrosion inhibiting and descaling agent is added in recirculated cooling water.But during cooling water use, with not
Disconnected circulation and concentration, water mineral content can be also continuously increased, and pipeline and equipment corrosion is aggravated with fouling, it is therefore desirable to
Corrosion inhibiting and descaling agent is added to improve cooling water quality, ensures equipment safety operation.And these chemical agents are most used as waste at last
It is discharged into environment.However, as increasingly improving for people's environmental consciousness is increasingly stringenter with environmental regulation, there is an urgent need to one
The environment amenable novel non-phosphate water treatment agent of kind.
Corrosion-mitigation scale-inhibition agent prescription is made of inhibition component and antiscaling dispersion component two parts.Excellent without phosphorus common of scale-inhibiting properties
Polymers class dirt dispersion agent kind is more, wherein being much applied successfully in actual production.And function admirable is without phosphorus
It is smaller that leeway may be selected in Polymer corrosion inhibitor.
Carboxymethylinulin（CMI）It is that carboxylic group is contained by the primary alconol on inulin molecules or secondary alcohol groups and monoxone etc.（-
COOH）Compound substitution reaction occurs in alkaline conditions and is formed.The research of Carboxymethylinulin start from the 1990s,
In terms of concentrating on the synthesis of Carboxymethylinulin and its research of scale-inhibiting properties.Data shows that CMI can be dropped in the biology of holding inulin
New function is added on the basis of solution, renewable and nontoxic etc. characteristic, may be used as antisludging agent or heavy metal ion chelating agent.
It can inhibit CaCO in sugar industry3Crystallization, is used as removing additive of pollutant etc. in dyeing process.
Liu Ke face《The research of Carboxymethylinulin》Using inulin as raw material, pass through the list of the preparation process to Carboxymethylinulin
Factor Experiment and orthogonal experiment research, analyze influence of each single factor test to synthetic product Carboxymethylinulin substitution value, have found
Prepare the optimum process condition of Carboxymethylinulin.
However, Carboxymethylinulin is not readily dissolved in water, existing literature also not on Carboxymethylinulin corrosion inhibition and with
Other without phosphorus polymer water inorganic agents compound to form the report that composite slow-corrosion scale resistor is applied to circulating water cooling treatment.
The content of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter and its application with
And the processing method of recirculated cooling water.
To achieve these goals, on the one hand, the present invention provides a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter, this is without phosphorus compound
Anti-incrustation corrosion inhibitor contains Carboxymethylinulin sodium, cyclodextrine derivatives and copolymer；The copolymer contains by formula（I）Shown sulphur
The construction unit that urea derivative provides and the construction unit provided by the unsaturated carboxylic acid of C3-C10,
Wherein, R1、R2、R3And R4It is each independently H, the aliphatic chain of substituted or unsubstituted C2-C10, the aliphatic chain
For saturation or undersaturated, and R1、R2、R3And R4In it is at least one be undersaturated aliphatic chain.
On the other hand, the application the present invention provides above-mentioned non-Phosphorus composite anti incrustation eorrosion snhibiter in circulating water cooling treatment.
Another further aspect, the present invention provides a kind of processing method of recirculated cooling water, this method is included toward recirculated cooling water
It is middle to add above-mentioned non-Phosphorus composite anti incrustation eorrosion snhibiter.
The present inventor has found that Carboxymethylinulin sodium has certain corrosion inhibition, the copolymer after research
The solubility property of Carboxymethylinulin sodium can be increased, Carboxymethylinulin sodium, cyclodextrine derivatives and copolymer are used cooperatively can
To obtain more preferable anticorrosion-antiscaling effect, so as to more fully play the scale inhibition and corrosion inhibition of Carboxymethylinulin sodium, improve multiple
The anticorrosion-antiscaling effect of medicament is closed, reduces the usage amount of single medicament, while is had to the suspended matter in recirculated cooling water preferable
Flocculating effect.
Non-Phosphorus composite anti incrustation eorrosion snhibiter provided by the invention has good scale inhibition and corrosion inhibition, applied to circulating cooling
Water, can not only meet requirement of the recirculated cooling water to scale inhibition and inhibition, can also avoid ring caused by existing phosphorous medicament
Border problem.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Embodiment
The embodiment of the present invention is described in detail below.It is it should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The endpoint of disclosed scope and any value are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of a scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
In the present invention, in the case where not making conversely explanation, the term " limiting viscosity " used refers to individual molecule pair
The contribution of solution viscosity, is the viscosity for reflecting polymer characteristics, its value does not become with concentration, and unit is deciliter/gram（dL/g）, pole
Limit viscosity is often used as measuring for molecular weight, usually uses capillary viscometer（Such as Ubbelohde viscometer）Measure；Unless stated otherwise
（Such as embodiment and comparative example）, the content or weight involved in the present invention are with solid content（The content or weight of solute）Meter.
The present invention provides a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter, which contains Carboxymethylinulin
Sodium, cyclodextrine derivatives and copolymer；The copolymer contains by formula（I）Construction unit that shown thiourea derivative provides and
The construction unit provided by the unsaturated carboxylic acid of C3-C10,
Wherein, R1、R2、R3And R4It is each independently H, the aliphatic chain of substituted or unsubstituted C2-C10, the aliphatic chain
For saturation or undersaturated, and R1、R2、R3And R4In it is at least one be undersaturated aliphatic chain.C3-C10 refers to carbon atoms
Number is 3-10（Such as 3,4,5,6,7,8,9 or 10）, C2-C10 refers to that carbon atom quantity is 2-10（Such as 2,3,4,5,6,7,8,9 or
10）.
Wherein, the unsaturated carboxylic acid can be double bond containing carboxylic acid.Preferably, the unsaturated carboxylic acid for acrylic acid,
At least one of maleic acid, methacrylic acid and methylene-succinic acid.
Preferably, the unsaturated fatty chain is alkenyl or alkenylalkyl, and the aliphatic chain of the saturation is alkyl or hydroxyl alkane
Base.It is highly preferred that the thiourea derivative is allylthiourea, Allyl thiourea, N, N'- diallyl -2- thiocarbamides, N, N'-
In diallyl -2- thiocarbamides, N- (2- ethoxys)-N'-2- Allyl thioureas and N- (2- ethoxys)-N'-2- allylthioureas
At least one.
According to the present invention, the content ratio of thiourea derivative in copolymer and unsaturated carboxylic acid is had no particular limits, only
Scale inhibition and corrosion inhibition can be played.The weight ratio of the thiourea derivative and unsaturated carboxylic acid is preferably 1-5：1（Should
Weight ratio is characterized with the weight ratio prepared between each monomer used in copolymer）.The limiting viscosity of the copolymer is
0.05-0.16dL/g, is preferably 0.08-0.12dL/g.
The preparation method for the copolymer that the present invention uses can include：At 50-95 DEG C, by monomer, initiator and molecule
Amount conditioning agent is mixed, then the reaction was continued the 1-4h at 75-95 DEG C, wherein, the monomer includes thiourea derivative and insatiable hunger
And carboxylic acid.
Wherein, as the thiourea derivative of monomer and the dosage of unsaturated carboxylic acid and it is specifically chosen as it was previously stated, herein
Repeat no more.
According to preferred embodiment, the mode of the mixing is when preparing copolymer：
（a）The solution of the solution of monomer and initiator is added dropwise in the solution of molecular weight regulator respectively, or
（b）The solution of the solution of monomer and molecular weight regulator is added dropwise in the solution of initiator respectively, or
（c）The solution of initiator is added dropwise in the mixed solution of molecular weight regulator and monomer.
In the mode of mixing（a）、（b）Or（c）In, rate of addition is not required particularly.For example, mode（a）In, it is single
The rate of addition of the solution of body is 30-400mL/h, and the rate of addition of the solution of initiator is 5-120mL/h.Mode（b）In, it is single
The rate of addition of the solution of body is 30-400mL/h, and the rate of addition of the solution of molecular weight regulator is 5-120mL/h.Mode
（c）In, the rate of addition of the solution of initiator is 5-120mL/h.
It should be strongly noted that mode（c）The mixed solution middle-molecular-weihydroxyethyl conditioning agent of middle-molecular-weihydroxyethyl conditioning agent and monomer
Concentration can be 5-100g/L.Mode（c）The concentration of monomer can be in the mixed solution of middle-molecular-weihydroxyethyl conditioning agent and monomer
80-250g/L。
In a preferred embodiment, the mode of the mixing is：The solution of the solution of monomer and initiator is dripped respectively
Add in the solution of molecular weight regulator.In the preferred embodiment, the dropwise addition of the solution of solution and initiator to monomer
Speed does not require particularly, it is contemplated that anticorrosion-antiscaling property more preferably copolymer is obtained, it is highly preferred that the drop of the solution of monomer
Acceleration is 30-400mL/h, more preferably 60-200mL/h.It is highly preferred that the rate of addition of the solution of initiator is 5-
120mL/h, more preferably 15-100mL/h.
In a preferred embodiment, at 50-95 DEG C, monomer, initiator and molecular weight regulator are mixed
Mode is preferably the mode being added dropwise.Can with while be added dropwise while be warming up to 75-95 DEG C（Preferably 80-90 DEG C）, can also be directly in 75-
95℃（Preferably 80-90 DEG C）At a temperature of be added dropwise.Below in a manner of（a）Exemplified by be specifically described：By the molten of monomer
The mode that the solution of liquid and initiator is added dropwise in the solution of molecular weight regulator respectively can be to heat up when being added dropwise（Specifically
Ground, can start to be added dropwise at 50-70 DEG C, then heat up when being added dropwise, cause the temperature of reaction system after completion of dropwise addition to reach 75-
95℃（Preferably 80-90 DEG C））, or directly at 75-95 DEG C（Preferably 80-90 DEG C）At a temperature of be added dropwise.More
In the case of preferable, by the way of being heated up while being added dropwise.
In a preferred embodiment, the monomer includes thiourea derivative and unsaturated carboxylic acid, the solution of the monomer
Can be the solution of thiourea derivative and the solution of unsaturated carboxylic acid（Individually it is added dropwise during use）, or thiourea derivative and
The mixed solution of unsaturated carboxylic acid（The two is configured to be added dropwise together after mixed solution during use）.Under preferable case, list is used
Body（Thiourea derivative and unsaturated carboxylic acid）Mixed solution, it is highly preferred that the concentration of the mixed solution of the monomer is 0.3-
1kg/L.It is well known by those skilled in the art that the solution of unsaturated carboxylic acid can be by by the acid anhydrides and solvent of unsaturated carboxylic acid
Obtained after mixing, it is clear that the use of acid anhydrides is also within the scope of the invention, and this will not be detailed here.
In the preparation method of copolymer, the initiator can be used with conventional dosage, it is preferable that the initiator
Dosage be the total dosage of monomer 2-12%.The concentration of the solution of the initiator can be 20-720g/L.
In the preparation method of copolymer, the species of the initiator is not required particularly, can be that this area is normal
Advise the various radical initiators that use, it is preferable that the initiator is（It is water-soluble）Persulfate, more preferably persulfuric acid
At least one of ammonium, potassium peroxydisulfate and sodium peroxydisulfate, more preferably ammonium persulfate.
In the preparation method of copolymer, the molecular weight regulator can be used according to conventional dosage, it is preferable that institute
The dosage for stating molecular weight regulator is the 2-12% of the total dosage of monomer.The concentration of the solution of the molecular weight regulator can be 20-
720g/L。
In the preparation method of copolymer, to the species of the molecular weight regulator, there is no particular limitation, can be this
The common various materials with reproducibility in field（Reducing agent）, it is preferable that the molecular weight regulator is（It is water-soluble）Sulfurous
Hydrochlorate,（It is water-soluble）Pyrosulfite and（It is water-soluble）At least one of alkanol of C3-C6, more preferably sodium hydrogensulfite,
At least one of potassium bisulfite, sodium pyrosulfite, potassium metabisulfite and isopropanol（It is most preferably a kind of）, more preferably
Sodium hydrogensulfite.Wherein,（It is water-soluble）The alkanol of C3-C6 is preferably saturated alkoxides, such as the saturated alkoxides of C3, C4, C5 or C6.
According to the present invention, Carboxymethylinulin sodium can be by inulin in alkalescence（If pH is 10-13）Under the conditions of with a chloroethene
Acid carries out etherification reaction and obtains.The size of the substitution value of Carboxymethylinulin sodium is had no particular limits, can be that this area is normal
The substitution value of rule.The substitution value refers to the substituted number of hydroxyl in average each fructofuranose unit in Carboxymethylinulin sodium
Amount, that is, reflect the degree of inulin carboxymethylation reaction, each fructofuranose unit has 3 hydroxyls, therefore substitution value is up to
3.Preferably, the substitution value of the Carboxymethylinulin sodium is 0.3-2, more preferably 0.6-1.2.
According to the present invention, the species of cyclodextrine derivatives is had no particular limits, can is commonly used in the art
The substituted compound with cyclodextrin precursor structure of water soluble cyclodextrin derivant, i.e. hydroxyl.Preferably, the cyclodextrin
Derivative is selected from carboxymethyl-alpha-cyclodextrin, methyl-B-cyclodextrin, hydroxypropyl-β-cyclodextrin, Sulfobutyl ether β _ cyclodextrin, carboxylic first
At least one of group-beta-cyclodextrin and carboxymethyl-gamma-cyclodextrin.
According to the present invention, the amount ratio of Carboxymethylinulin sodium, cyclodextrine derivatives and copolymer is had no particular limits,
As long as scale inhibition and corrosion inhibition can be played.In the non-Phosphorus composite anti incrustation eorrosion snhibiter of the present invention, Carboxymethylinulin sodium, ring
The amount ratio of dextrin derivative and copolymer can be in interior variation in a big way.Preferably, Carboxymethylinulin sodium, cyclodextrin spread out
The weight ratio of biology and copolymer is 1：0.1-10：0.1-5, more preferably 1：0.2-5：0.2-3.
According to the present invention, the non-Phosphorus composite anti incrustation eorrosion snhibiter also contains heterocyclic compound, to further enhance the present invention
Non-Phosphorus composite anti incrustation eorrosion snhibiter suppresses the function of copper corrosion.Heterocyclic compound refers to the organic compound containing heterocycle structure in molecule
Thing, i.e., outside the atom carbon atom of composition ring, also containing at least one hetero atom, most common hetero atom is nitrogen-atoms, sulphur is former
Son or oxygen atom.
Wherein, the species and dosage of heterocyclic compound are had no particular limits, can is commonly used in the art miscellaneous
Cycle compound, is preferably five yuan and hexa-member heterocycle and fused ring compound.Five member ring heterocyclic compound includes furans, thiophene, pyrroles, thiophene
Azoles and imidazoles；6-membered heterocyclic compound includes pyridine, pyrazine, pyrimidine and pyridazine；Fused ring compound is two or more
The polycyclic organic compound that phenyl ring or heterocycle are formed with shared ring side, such as naphthalene, indoles and purine.Preferably, the heterocycle
Compound is 2-mercaptobenzothiazole and/or benzotriazole.Preferably, the weight of the heterocyclic compound and Carboxymethylinulin sodium
It is 0.02-0.2 to measure ratio：1, more preferably 0.05-0.1：1.
According to the present invention, the non-Phosphorus composite anti incrustation eorrosion snhibiter also contains zinc salt.Do not have to the species and dosage of ring zinc salt
Special limitation, can be water-soluble zinc salt commonly used in the art.Preferably, the zinc salt is zinc sulfate and/or chlorination
Zinc.Preferably, with Zn2+Weight meter, the zinc salt and Carboxymethylinulin sodium weight ratio are 0.05-0.5：1, more preferably 0.1-
0.2：1.
According to the present invention, to the preparation method of the non-Phosphorus composite anti incrustation eorrosion snhibiter, there is no particular limitation, can be this
The preparation method of field routine.It is also no special to the charging sequence of each component when preparing the non-Phosphorus composite anti incrustation eorrosion snhibiter
Other restriction.For example, the preparation method of the non-Phosphorus composite anti incrustation eorrosion snhibiter can be to derive Carboxymethylinulin sodium, cyclodextrin
Thing and copolymer are directly mixed together according to certain weight ratio.If the non-Phosphorus composite anti incrustation eorrosion snhibiter is female for concentration
Liquid, the preparation method of the non-Phosphorus composite anti incrustation eorrosion snhibiter can be：By Carboxymethylinulin sodium, cyclodextrine derivatives, copolymer,
Zinc salt（It is selectable）And heterocyclic compound（It is selectable）And suitable quantity of water is uniformly mixed, you can is made required without phosphorus compound
Anti-incrustation corrosion inhibitor.
In the present invention, the non-Phosphorus composite anti incrustation eorrosion snhibiter can also contain solvent, such as water.With without phosphorus composite scale inhibition
On the basis of the gross weight of agent, the sum of content of component in addition to solvent is can be with 25-100 weight %.According to the present invention preferably
Embodiment, the non-Phosphorus composite anti incrustation eorrosion snhibiter are made of mentioned component.
Present invention also offers application of the above-mentioned non-Phosphorus composite anti incrustation eorrosion snhibiter in circulating water cooling treatment.
Wherein, the dosage of the non-Phosphorus composite anti incrustation eorrosion snhibiter（The sum of valid density of i.e. each component）Preferably 10-
50mg/L recirculated cooling waters, more preferably 20-40mg/L recirculated cooling waters.
Present invention also offers a kind of processing method of recirculated cooling water, this method is included before being added in toward recirculated cooling water
The non-Phosphorus composite anti incrustation eorrosion snhibiter stated.
Wherein, the dosage of the non-Phosphorus composite anti incrustation eorrosion snhibiter（The sum of valid density of i.e. each component）Preferably 10-
50mg/L recirculated cooling waters, more preferably 20-40mg/L recirculated cooling waters.
According to the present invention, each component in the non-Phosphorus composite anti incrustation eorrosion snhibiter can individually add according to said ratio
Enter in recirculated cooling water to the content needed, each component first can also be configured to composite scale-inhibiting corrosion inhibitor and then addition circulation is cold
But the content needed in water to each component.
According to the present invention, the composite scale-inhibiting corrosion inhibitor is 100- particularly suitable for processing the sum of calcium hardness and total alkalinity
300mg/L（Moisturizing, namely raw water）Medium hardness, moderate alkalinity water quality be not required to adjust pH value recirculated cooling water.
Composite scale-inhibiting corrosion inhibitor provided by the invention shows good scale inhibitor comprehensive performance, applied to circulating cooling
During water, requirement of the recirculated cooling water to scale inhibition and inhibition is not only met, it is thus also avoided that because using ring caused by phosphorous medicament
Border problem.
The present invention will be described in detail by way of examples below.In following embodiments and comparative example：
Carboxymethylinulin sodium is purchased from Carbomer companies of the U.S.（Solid content is 20 weight %）.
Copolymer is self-control medicament, and preparing the method for copolymer includes：At 80 DEG C, by monomer solution and initiator mistake
Ammonium sulfate solution is added dropwise in molecular weight regulator metabisulfite solution respectively, is added dropwise in heating, during completion of dropwise addition
Temperature is 90 DEG C, then the reaction was continued the 2h at 90 DEG C, and the monomer is thiourea derivative, unsaturated carboxylic acid and unsaturated sulfonic acid.
Wherein, allylthiourea, Allyl thiourea, N, N'- diallyl -2- thiocarbamides and N- (2- ethoxys)-N'-2- third
Alkenyl thiocarbamide is purchased from lark prestige Science and Technology Ltd., and solid content is 98 weight %；Ammonium persulfate, potassium peroxydisulfate, persulfuric acid
Sodium, sodium pyrosulfite, sodium hydrogensulfite, isopropanol are purchased from Beijing chemical reagents corporation, and analysis is pure；Acrylic acid is purchased from Tianjin light
Multiple fine chemistry industry research institute, analysis are pure；Maleic anhydride is purchased from Beijing Yili Fine Chemicals Co., Ltd., and analysis is pure；Methyl-prop
Olefin(e) acid and methylene-succinic acid are purchased from Shanghai Yi Kang chemical materials Co., Ltd, and solid content is not less than 99 weight %.
The assay method of the solid content of copolymer is as follows：
About 1.0g or so samples are weighed, 0.0002g is accurate to, is placed in the flat weighing disk weighed, careful shake makes medicine
Agent is flowed naturally, is formed one layer of uniform film in ware bottom, is then placed in electrically heated drying cabinet, is begun to warm up from room temperature, in 120
At DEG C after dry 4h, weighed once until constant weight every half an hour.Taken out after constant weight, be put into drier and be cooled to room temperature,
Weigh.
Solid content calculation formula is：Solid content=[(m2-m1)/m]×100%
m2：Dried medicament and weighing disk weight, g
m1：Weighing disk net weight, g
m：Weigh the quality of medicament, g
Carboxymethyl-alpha-cyclodextrin, methyl-B-cyclodextrin, carboxymethyl-gamma-cyclodextrin, hydroxypropyl-β-cyclodextrin, sulphur fourth
Group-beta-cyclodextrin and alpha-cyclodextrin are purchased from Shandong Binzhou Zhi Yuan bio tech ltd, and solid content is not less than 98 weights
Measure %.
Benzotriazole is not less than 99 weight % purchased from Tianjin recovery fine chemistry industry research institute, solid content.
In following embodiments and comparative example, the water quality of experiment raw water 1 and 2 is as shown in table 1, takes experiment raw water 1 and 2 to mend respectively
Add calcium ion, the calcium hardness of experiment raw water and total alkalinity is concentrated 5 times and is used as test water 1 and 2.
In table 1, calcium hardness, total alkalinity, total hardness are with CaCO3Meter.Calcium hardness is according to standard GB/T/T 6910-
2006《Boiler feed water and cooling water analysis method, calcium catalyst, compleximetry》Measure；Total alkalinity is according to standard GB/T/T
15451-2006《The measure of industrial circulating cooling water, total alkali and phenolphthalein alkalinity》Measure；Total hardness refers to Ca in water2+And Mg2+It is total
Amount, according to GB/T 15452-2006《The measure of total hardness in industrial circulating cooling water, EDTA titrations》Measure；Cl-According to mark
Quasi- GB/T15453-2008 measure；SO4 2-Measured according to standard GB/T 14642-2009；PH value is according to standard GB/T6920-
1986 measure；Electrical conductivity is measured according to standard GB/T 6908-2008；It is total molten solid according to standard GB/T 14415-2007 measure.
In table 1, pH is without unit；The unit of electrical conductivity is μ s/cm；Its counit is mg/L.
Table 1
| Test raw water | Calcium hardness | Total alkalinity | Total hardness | Cl- | SO4 2- | pH | Electrical conductivity | It is total molten solid |
| Test raw water 1 | 102 | 135 | 136 | 14 | 35 | 7.8 | 190 | 290 |
| Test water 1 | 510 | 675 | 680 | 70 | 175 | 7.9 | 900 | 1450 |
| Test raw water 2 | 53 | 54 | 69 | 20 | 13 | 7.4 | 102 | 112 |
| Test water 2 | 318 | 324 | 414 | 120 | 78 | 7.5 | 612 | 672 |
Embodiment 1
30g Carboxymethylinulin sodium is weighed respectively（Substitution value is 1）, 10g carboxymethyls-alpha-cyclodextrin and 30g copolymer 1s（30
DEG C when Limiting Viscosity be 0.098dl/g, be dissolved in 20ml water for sodium pyrosulfite 6g, ammonium persulfate 1.2g is dissolved in 65ml water, monomer
Allylthiourea 30.7g, acrylic acid 30g and 70ml water polymerize to obtain, and solid content is 29.7 weight %）, add in 30g water, shake
It is even, obtain composite scale-inhibiting corrosion inhibitor medicament stoste S1.
The prepared composite scale-inhibiting corrosion inhibitor medicament stoste S1 of 1g are taken to be separately added into 10L test waters 1 and 2 so that water
The content of middle Carboxymethylinulin sodium, carboxymethyl-alpha-cyclodextrin and copolymer is respectively 6mg/L, 10mg/L and 9mg/L, is then pressed
Resistance calcium carbonate scale performance measurement and corrosion inhibition measure are carried out according to the method in test case 1.
Embodiment 2
3.14g zinc chloride are weighed, are dissolved in 15g copolymers 2（Limiting Viscosity is 0.088dl/g at 30 DEG C, is sodium pyrosulfite
3.6g is dissolved in 20ml water, and ammonium persulfate 2.4g is dissolved in 65ml water, monomer allylthiourea 33.7g, maleic anhydride 27g and 70ml water
Polymerization obtains, and solid content is 30.3 weight %）In, then add 45g Carboxymethylinulin sodium（Substitution value is 0.6）With 18g methyl-
Beta-cyclodextrin, adds 8.86g water, shakes up, and obtains composite scale-inhibiting corrosion inhibitor medicament stoste S2.
The prepared composite scale-inhibiting corrosion inhibitor medicament stoste S2 of 0.9g are taken to be separately added into 10L test waters 1 and 2 so that
Carboxymethylinulin sodium in water, methyl-B-cyclodextrin, the content of copolymer and zinc ion are respectively 9mg/L, 18mg/L, 4.5mg/L
And 1.5mg/L, then resistance calcium carbonate scale performance measurement is carried out according to the method in test case 1 and corrosion inhibition measures.
Embodiment 3
1g benzotriazole is weighed, is dissolved in 20g copolymers 3（Limiting Viscosity is 0.109dl/g at 30 DEG C, is over cure
Sour ammonium 3g is dissolved in 20ml water, and ammonium persulfate 3.6g is dissolved in 65ml water, monomer allylthiourea 36.7g, methacrylic acid 24g and
70ml water polymerize to obtain, and solid content is 31 weight %）In, then add 80g Carboxymethylinulin sodium（Substitution value is 0.8）With 6g carboxylics
Methyl-y-cyclodextrin, adds 13g water, shakes up, and obtains composite scale-inhibiting corrosion inhibitor medicament stoste S3.
The prepared composite scale-inhibiting corrosion inhibitor medicament stoste S3 of 1.2g are taken to be separately added into 10L test waters 1 and 2 so that
Carboxymethylinulin sodium in water, carboxymethyl-gamma-cyclodextrin, the content of copolymer and benzotriazole be respectively 16mg/L, 6mg/L,
6mg/L and 1mg/L, then carries out resistance calcium carbonate scale performance measurement according to the method in test case 1 and corrosion inhibition measures.
Embodiment 4
40g Carboxymethylinulin sodium is weighed respectively（Substitution value is 1.2）, 10g hydroxypropyl-β-cyclodextrins and 30g copolymers 4
（Limiting Viscosity is 0.082dl/g at 30 DEG C, is dissolved in 25ml water for sodium pyrosulfite 5.4g, and ammonium persulfate 3.6g is dissolved in 50ml water,
Monomer allylthiourea 39.8g, methylene-succinic acid 21g and 75ml water polymerize to obtain, and solid content is 30.8 weight %）, add
In 20g water, shake up, obtain composite scale-inhibiting corrosion inhibitor medicament stoste S4.
The prepared composite scale-inhibiting corrosion inhibitor medicament stoste S4 of 1g are taken to be separately added into 10L test waters 1 and 2 so that water
The content of middle Carboxymethylinulin sodium, hydroxypropyl-β-cyclodextrin and copolymer is respectively 8mg/L, 10mg/L and 9mg/L, is then pressed
Resistance calcium carbonate scale performance measurement and corrosion inhibition measure are carried out according to the method in test case 1.
Embodiment 5
20g Carboxymethylinulin sodium is weighed respectively（Substitution value is 1.5）, 20g Sulfobutyl ether β _ cyclodextrins and 30g copolymers 5
（Limiting Viscosity is 0.085dl/g at 30 DEG C, for sodium pyrosulfite 4.2g is dissolved in 30ml water, ammonium persulfate 4.8g is dissolved in 65ml water,
Monomer allylthiourea 42.9g, acrylic acid 18g and 65ml water polymerize to obtain, and solid content is 29.3 weight %）, add in 30g water,
Shake up, obtain composite scale-inhibiting corrosion inhibitor medicament stoste S5.
The prepared composite scale-inhibiting corrosion inhibitor medicament stoste S5 of 1g are taken to be separately added into 10L test waters 1 and 2 so that water
The content of middle Carboxymethylinulin sodium, Sulfobutyl ether β _ cyclodextrin and copolymer is respectively 4mg/L, 20mg/L and 9mg/L, is then pressed
Resistance calcium carbonate scale performance measurement and corrosion inhibition measure are carried out according to the method in test case 1.
Embodiment 6
20g Carboxymethylinulin sodium is weighed respectively（Substitution value is 1）, 4g methyl-B-cyclodextrins and 40g copolymers 6（At 30 DEG C
Limiting Viscosity is 0.099dl/g, is sodium pyrosulfite 4.8g and 20ml water, and sodium peroxydisulfate 4.2g is dissolved in 65ml water, monomer propylene
Base thiocarbamide 45.9g, methacrylic acid 15g and 75ml water polymerize to obtain, and solid content is 30.1 weight %）, add in 36g water, shake
It is even, obtain composite scale-inhibiting corrosion inhibitor medicament stoste S6.
The prepared composite scale-inhibiting corrosion inhibitor medicament stoste S6 of 1g are taken to be separately added into 10L test waters 1 and 2 so that water
Middle Carboxymethylinulin sodium, methyl-B-cyclodextrin, the content of copolymer are respectively 4mg/L, 4mg/L, 12mg/L, then according to survey
Method in examination example 1 carries out resistance calcium carbonate scale performance measurement and corrosion inhibition measure.
Comparative example 1
40g Carboxymethylinulin sodium is weighed respectively（Substitution value is 1）, 10g alpha-cyclodextrins and 6g poly-aspartates（Pole at 30 DEG C
Limit viscosity is 0.069dl/g, and solid content is 50 weight %）, add in 44g water, shake up, obtain medicament stoste D1.
Prepared 1g medicaments stoste D1 is taken to be separately added into 10L test waters 1 and 2 so that Carboxymethylinulin sodium in water,
The content of alpha-cyclodextrin and poly-aspartate is respectively 8mg/L, 10mg/L and 3mg/L, then according to the method in test case 1 into
Row resistance calcium carbonate scale performance measurement and corrosion inhibition measure.
Comparative example 2
20g Carboxymethylinulin sodium is weighed respectively（Substitution value is 0.6）With 10g alpha-cyclodextrins, add in 70g water, shake up, obtain
To medicament stoste D2.
Prepared 1g medicaments stoste D2 is taken to be separately added into 10L test waters 1 and 2 so that Carboxymethylinulin sodium in water
Content with alpha-cyclodextrin is respectively 4mg/L and 10mg/L, then carries out resistance calcium carbonate scale performance according to the method in test case 1
Measure and corrosion inhibition measure.
Comparative example 3
40g copolymers 6 are weighed, is added in 60g water, is shaken up, obtain medicament stoste D3.
Prepared 1g medicaments stoste D3 is taken to be separately added into 10L test waters 1 and 2 so that the content of copolymer in water
For 12mg/L, then resistance calcium carbonate scale performance measurement is carried out according to the method in test case 1 and corrosion inhibition measures.
Comparative example 4
47g Carboxymethylinulins sodium and 15.6g carboxymethyls-alpha-cyclodextrin are weighed respectively, are added in 37.4g water, are shaken up, obtain
Composite scale-inhibiting corrosion inhibitor medicament stoste D4.
Prepared 1g medicaments stoste D4 is taken to be separately added into 10L test waters 1 and 2 so that Carboxymethylinulin sodium in water
It is respectively 9.4mg/L and 15.6mg/L with carboxymethyl-alpha-cyclodextrin content, then carries out resistance carbon according to the method in test case 1
Sour calcium scale performance measurement and corrosion inhibition measure.
Comparative example 5
50g Carboxymethylinulins sodium and 45g copolymer 1s are weighed respectively, are added in 5g water, are shaken up, obtain composite scale inhibition
Agent medicament stoste D5.
Prepared 1g medicaments stoste D5 is taken to be separately added into 10L test waters 1 and 2 so that Carboxymethylinulin sodium in water
It is respectively 10mg/L and 15mg/L with copolymer level, then carries out resistance calcium carbonate scale performance according to the method in test case 1 and survey
Fixed and corrosion inhibition measure.
Comparative example 6
13.2g carboxymethyls-alpha-cyclodextrin and 35.4g copolymer 1s are weighed respectively, are added in 51.4g water, are shaken up, answered
Close anti-incrustation corrosion inhibitor medicament stoste D6.
Prepared 1g medicaments stoste D6 is taken to be separately added into 10L test waters 1 and 2 so that carboxymethyl-α-ring paste in water
Essence and copolymer level are respectively 13.2mg/L and 11.8mg/L, then carry out resistance calcium carbonate scale according to the method in test case 1
Performance measurement and corrosion inhibition measure.
Comparative example 7
Medicament is prepared according to the method for embodiment 1, unlike, carboxymethyl-alpha-cyclodextrin replaces with alpha-cyclodextrin, shakes
It is even, obtain composite scale-inhibiting corrosion inhibitor medicament stoste D7.
Prepared 1g medicaments stoste D7 is taken to be separately added into 10L test waters 1 and 2, then according to the side in test case 1
Method carries out resistance calcium carbonate scale performance measurement and corrosion inhibition measure.
Comparative example 8
Medicament is prepared according to the method for embodiment 1, unlike, 30g copolymers replace with 18g poly-aspartates（30℃
When limiting viscosity be 0.069dl/g, solid content is 50 weight %）, add in 42g water, shake up, obtain composite scale-inhibiting corrosion inhibitor medicine
Agent stoste D8.
Prepared 1g medicaments stoste D8 is taken to be separately added into 10L test waters 1 and 2, then according to the side in test case 1
Method carries out resistance calcium carbonate scale performance measurement and corrosion inhibition measure.
Comparative example 9
Weigh 83.3g copolymer 1s to add in 16.7g water, obtain composite scale-inhibiting corrosion inhibitor medicament stoste D9, shake up so that
Copolymer level is 25mg/L in water.
Prepared 1g medicaments stoste D9 is taken to be separately added into 10L test waters 1 and 2, then according to the side in test case 1
Method carries out resistance calcium carbonate scale performance measurement and corrosion inhibition measure.
Test case 1
This test case is evaluating the anticorrosion-antiscaling property of the composite scale-inhibiting corrosion inhibitor of embodiment 1-6 and comparative example 1-9.
" blank sample " represents to be not added with non-Phosphorus composite anti incrustation eorrosion snhibiter, but other processing steps and experiment（Or test）Step
Identical test water sample.
（1）Hinder calcium carbonate scale performance measurement method：
The test water 1 and 2 that medicament has been added in each embodiment and comparative example is interior using appearance in 80 ± 1 DEG C of waters bath with thermostatic control
Measuring bottle method stands 10h, after cooling residue Ca in sampling analysis water2+Concentration, while do blank sample, and calculate scale inhibition performance.Knot
Fruit is shown in Table 2（Test water 1）With 3（Test water 2）.
The definition of scale inhibition performance is the scale inhibition efficiency of corrosion inhibiting and descaling agent, and the calculation formula of scale inhibition performance is：
Scale inhibition performance=（C-C0）/（nC1-C0）× 100%, wherein,
C：Residue Ca in water after cooling2+Concentration（mg/L）
C0：The Ca of blank sample2+Concentration（mg/L）
C1：Ca in raw water2+Concentration（mg/L）
n：Test the cycles of concentration of raw water calcium hardness and total alkalinity
（2）Corrosion inhibition assay method：
20# quality carbon steel test pieces are fixed on lacing film instrument, test piece then is completely immersed in each embodiment and comparative example throws
In the test water 1 and 2 for having added medicament, steady temperature is 40 ± 1 DEG C, keeps rotating speed to rotate 72h for 75rpm, before record experiment
The weight of test piece afterwards, calculates average corrosion rate.It the results are shown in Table 2（Test water 1）With 3（Test water 2）.
The inhibition efficiency defined as corrosion inhibiting and descaling agent of average corrosion rate, average corrosion rate（F）Calculation formula be：
F=（C×△W）/（A×T×ρ）, wherein,
C：Computational constant, with mm/a（Millimeter/year）For unit when, C=8.76 × 107mm/a
△W：The corrosion weight loss of test specimen（g）
A：The area of test specimen（cm2）
T：The corrosion test time（h）
ρ：The density of material for test（kg/m3）, ρ=7.85 × 103kg/m3
（3）Flocculating effect assay method：
Kaolin is added in the test water 1 and 2 of table 1（Purchased from Tianjin great Mao chemical reagent factories）, make its turbidity be
15mg/L, adds phosphate-free corrosion inhibition antisludging agent, after experiment according still further to the method shown in embodiment and comparative example（After 0.5h）Take
2 centimetres of underwater depth water sample analysis turbidity, the test method of turbidity is spectrophotometry（Surveyed according to standard GB/T 15893
It is fixed）.It the results are shown in Table 2（Test water 1）With 3（Test water 2）.
Table 2
Table 3
Can be seen that non-Phosphorus composite anti incrustation eorrosion snhibiter provided by the invention from the data in table 2 and 3 has good synthesis
Scale inhibition and corrosion inhibition.Specifically, it not only has excellent resistance CaCO3Dirty function, also has good corrosion inhibition, can
Meet requirement of the recirculated cooling water to scale inhibition and inhibition.In addition, non-Phosphorus composite anti incrustation eorrosion snhibiter provided by the invention is at the same time to following
Suspended matter in ring cooling water has preferable flocculating effect.
Especially, comparing embodiment 1 and comparative example 1-9 can be seen that in the case where reducing or replacing certain component,
It is unable to reach the technique effect of the good anticorrosion-antiscaling property of the present invention.
The preferred embodiment of the present invention described in detail above, still, during present invention is not limited to the embodiments described above
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (12)
- A kind of 1. non-Phosphorus composite anti incrustation eorrosion snhibiter, it is characterised in that the non-Phosphorus composite anti incrustation eorrosion snhibiter contain Carboxymethylinulin sodium, Cyclodextrine derivatives and copolymer；The copolymer contain as shown in formula (I) thiourea derivative provide construction unit and by The construction unit that the unsaturated carboxylic acid of C3-C10 provides,Wherein, R1、R2、R3And R4H, the aliphatic chain of substituted or unsubstituted C2-C10 are each independently, the aliphatic chain is full And/or it is undersaturated, and R1、R2、R3And R4In it is at least one be undersaturated aliphatic chain；The unsaturated carboxylic acid is preferably third At least one of olefin(e) acid, maleic acid, methacrylic acid and methylene-succinic acid.
- 2. non-Phosphorus composite anti incrustation eorrosion snhibiter according to claim 1, wherein, the unsaturated fatty chain is alkenyl or alkenyl Alkyl, the aliphatic chain of the saturation is alkyl or hydroxyalkyl；Preferably, the thiourea derivative is allylthiourea, acrylic Thiocarbamide, N, N'- diallyl -2- thiocarbamides, N, N'- diallyl -2- thiocarbamides, N- (2- ethoxys)-N'-2- Allyl thioureas and At least one of N- (2- ethoxys)-N'-2- allylthioureas.
- 3. non-Phosphorus composite anti incrustation eorrosion snhibiter according to claim 1 or 2, wherein, the thiourea derivative and unsaturated carboxylic The weight ratio of acid is 1-5：1；It is preferably 0.08-0.12dL/g and/or the limiting viscosity of the copolymer is 0.05-0.16dL/g.
- 4. non-Phosphorus composite anti incrustation eorrosion snhibiter according to claim 1 or 2, wherein, the substitution value of the Carboxymethylinulin sodium It is preferably 0.6-1.2 for 0.3-2.
- 5. non-Phosphorus composite anti incrustation eorrosion snhibiter according to claim 1 or 2, wherein, the cyclodextrine derivatives are selected from carboxylic first Base-alpha-cyclodextrin, methyl-B-cyclodextrin, hydroxypropyl-β-cyclodextrin, Sulfobutyl ether β _ cyclodextrin, carboxymethyl-beta-cyclodextrin and carboxylic At least one of methyl-y-cyclodextrin.
- 6. according to the non-Phosphorus composite anti incrustation eorrosion snhibiter described in any one in claim 1-5, wherein, Carboxymethylinulin sodium, ring The weight ratio of dextrin derivative and copolymer is 1：0.1-10：0.1-5, is preferably 1：0.2-5：0.2-3.
- 7. non-Phosphorus composite anti incrustation eorrosion snhibiter according to claim 1, wherein, the non-Phosphorus composite anti incrustation eorrosion snhibiter also contains Heterocyclic compound；Preferably, the heterocyclic compound is 2-mercaptobenzothiazole and/or benzotriazole；It is highly preferred that the weight ratio of the heterocyclic compound and Carboxymethylinulin sodium is 0.02-0.2：1, it is preferably 0.05-0.1： 1。
- 8. non-Phosphorus composite anti incrustation eorrosion snhibiter according to claim 1, wherein, the non-Phosphorus composite anti incrustation eorrosion snhibiter also contains Zinc salt；Preferably, the zinc salt is zinc sulfate and/or zinc chloride；It is highly preferred that with Zn2+Weight meter, the zinc salt and Carboxymethylinulin sodium weight ratio are 0.05-0.5：1, be preferably 0.1-0.2：1.
- 9. application of the non-Phosphorus composite anti incrustation eorrosion snhibiter in claim 1-8 described in any one in circulating water cooling treatment.
- 10. application according to claim 9, the dosage of the non-Phosphorus composite anti incrustation eorrosion snhibiter is cold for 10-50mg/L circulations But water, is preferably 20-40mg/L recirculated cooling waters.
- 11. a kind of processing method of recirculated cooling water, it is characterised in that addition right will during this method is included toward recirculated cooling water Seek the non-Phosphorus composite anti incrustation eorrosion snhibiter described in any one in 1-8.
- 12. processing method according to claim 11, the dosage of the non-Phosphorus composite anti incrustation eorrosion snhibiter is followed for 10-50mg/L Ring cooling water, is preferably 20-40mg/L recirculated cooling waters.
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