CN107522298A - 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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- CN107522298A CN107522298A CN201610445581.9A CN201610445581A CN107522298A CN 107522298 A CN107522298 A CN 107522298A CN 201610445581 A CN201610445581 A CN 201610445581A CN 107522298 A CN107522298 A CN 107522298A
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- composite anti
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- eorrosion snhibiter
- incrustation eorrosion
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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
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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 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 by dimethyl diallyl ammonium chloride, the construction unit provided by C3 C10 unsaturated carboxylic acid and the construction unit provided by C4 C10 acrylate；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 combination property, during applied to recirculated cooling water, can not only meet that recirculated cooling water to scale inhibition and the requirement of inhibition, can also avoid environmental problem caused by existing phosphorous medicament.
Description
Technical field
The present invention relates to circulating water cooling treatment field, in particular it relates 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.In order to prevent scaling and corrosion, 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 stricter 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 up 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) be by the primary alconol on inulin molecules or secondary alcohol groups and monoxone etc. containing carboxylic group (-
COOH compound) occurs substitution reaction in the basic conditions and 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 drop 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.
CaCO can be suppressed in sugar industry3Crystallization, it 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 technology 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 in the prior art, there is provided 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 invention provides a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter, and this is without phosphorus compound
Anti-incrustation corrosion inhibitor contains Carboxymethylinulin sodium, cyclodextrine derivatives and copolymer；The copolymer contains by the allyl of dimethyl two
Ammonium chloride provide construction unit and, by C3-C10 unsaturated carboxylic acid provide construction unit and the acrylic acid by C4-C10
The construction unit that ester provides.
On the other hand, the application the invention provides above-mentioned non-Phosphorus composite anti incrustation eorrosion snhibiter in circulating water cooling treatment.
Another further aspect, the present invention provide a kind of processing method of recirculated cooling water, and this method is included into recirculated cooling water
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 suspension 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, it can not only meet that recirculated cooling water to scale inhibition and the requirement of 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 end points 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 individual 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 opposite explanation, the term " limiting viscosity " used refers to individual molecule pair
The contribution of solution viscosity, it is the viscosity for reflecting polymer characteristicses, its value do not become with concentration, and unit is deciliter/gram (dL/g), pole
Limit viscosity is often used as measuring for molecular weight, is generally measured with capillary viscometer (such as Ubbelohde viscometer)；Unless stated otherwise
(such as embodiment and comparative example), the content or weight being related in of the invention are in terms of solid content (content or weight of solute).
The invention provides a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter, the non-Phosphorus composite anti incrustation eorrosion snhibiter contains Carboxymethylinulin
Sodium, cyclodextrine derivatives and copolymer；The copolymer contain by dimethyl diallyl ammonium chloride provide construction unit, by
The construction unit that C3-C10 unsaturated carboxylic acid provides and the construction unit of the acrylate offer by C4-C10.C3-C10 refers to
Carbon atom quantity be 3-10 (such as 3,4,5,6,7,8,9 or 10), C4-C10 refer to carbon atom quantity for 4-10 (such as 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 be acrylic acid,
At least one of maleic acid, methacrylic acid and methylene-succinic acid (itaconic acid).Preferably, the acrylate is propylene
Acid alkyl ester and/or acrylic acid hydroxy alkyl ester, more preferably methyl acrylate, ethyl acrylate, hydroxy-ethyl acrylate and propylene
At least one of sour hydroxypropyl acrylate.
According to the present invention, to the content of dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and acrylate in copolymer
Than having no particular limits, as long as scale inhibition and corrosion inhibition can be played.The dimethyl diallyl ammonium chloride, insatiable hunger
It is 1 with the weight of carboxylic acid and acrylate ratio：1.5-8：(the weight ratio is with preparing each monomer used in copolymer by 0.5-3
Between weight than characterize).The limiting viscosity of the copolymer is preferably 0.05-0.16dL/g, more preferably 0.065-
0.085dL/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 continues to react 1-4h under 75-95 DEG C (being preferably 85-95 DEG C), wherein, the monomer includes two
Methyl diallyl ammonium chloride, unsaturated carboxylic acid and acrylate.
Wherein, it is used as the dosage of the dimethyl diallyl ammonium chloride of monomer, unsaturated carboxylic acid and acrylate and specific
Selection is as it was previously stated, will not be repeated here.
According to preferred embodiment, the mode of the mixing is when preparing copolymer：
(a) solution of the solution of monomer and initiator is added dropwise in the solution of molecular weight regulator respectively, or
(b) solution of the solution of monomer and molecular weight regulator is added dropwise in the solution of initiator respectively, or
(c) solution of initiator is added dropwise in the mixed solution of molecular weight regulator and monomer.
In the mode (a), (b) or (c) of mixing, rate of addition is not required particularly.For example, in mode (a), it is single
The rate of addition of the solution of body is 25-200mL/h, and the rate of addition of the solution of initiator is 30-160mL/h.In mode (b),
The rate of addition of the solution of monomer is 25-200mL/h, and the rate of addition of the solution of molecular weight regulator is 20-120mL/h.Side
In formula (c), the rate of addition of the solution of initiator is 30-160mL/h.
It should be strongly noted that the mixed solution middle-molecular-weihydroxyethyl conditioning agent of mode (c) middle-molecular-weihydroxyethyl conditioning agent and monomer
Concentration can be 7.5-80g/L.The concentration of monomer can be in the mixed solution of mode (c) middle-molecular-weihydroxyethyl conditioning agent and monomer
0.37-0.67kg/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 25-200mL/h.It is highly preferred that the rate of addition of the solution of initiator is 30-160mL/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 be to be warming up to 75-95 DEG C (being preferably 85-95 DEG C) when being added dropwise, can also be directly in 75-
It is added dropwise at a temperature of 95 DEG C (being preferably 85-95 DEG C).It is specifically described below in a manner of exemplified by (a)：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 be heated up (specifically when being added dropwise
It ground, can start to be added dropwise at 50-70 DEG C, then be heated up when being added dropwise, cause the temperature of reaction system after completion of dropwise addition to reach 75-
95 DEG C (being preferably 85-95 DEG C)), or directly it is added dropwise at a temperature of 75-95 DEG C (being preferably 80-95 DEG C).More
In the case of preferable, by the way of being heated up while being added dropwise.
In a preferred embodiment, the monomer includes dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and propylene
Acid esters, the solution of the monomer can be solution, the solution and acrylic acid of unsaturated carboxylic acid of dimethyl diallyl ammonium chloride
The solution (being individually added dropwise during use) of ester, or dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and acrylate
Three (is configured to after mixed solution be added dropwise together) by mixed solution during use.Under preferable case, monomer (dimethyl diene is used
Propyl ammonium chloride, unsaturated carboxylic acid and acrylate) mixed solution, it is highly preferred that the concentration of the mixed solution of the monomer
For 0.6-1.2kg/L.It is well known by those skilled in the art that the solution of unsaturated carboxylic acid can be by by the acid of unsaturated carboxylic acid
Acid anhydride obtains after being mixed with solvent, it is clear that the use of acid anhydrides is also within the scope of the invention, will not be described in detail herein.
In the preparation method of copolymer, the initiator can be used with the dosage of routine, 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 15-120g/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 used, it is preferable that the initiator is (water solubility) 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 use according to the dosage of routine, 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
20-180g/L。
In the preparation method of copolymer, to the species of the molecular weight regulator, there is no particular limitation, can be this
The conventional various materials (reducing agent) with reproducibility in field, it is preferable that the molecular weight regulator is (water solubility) sulfurous
At least one of alkanol of hydrochlorate, (water solubility) pyrosulfite and (water solubility) C3-C6, more preferably sodium hydrogensulfite,
At least one of potassium bisulfite, sodium pyrosulfite, potassium metabisulfite and isopropanol (most preferably a kind of), more preferably
Sodium hydrogensulfite.Wherein, (water solubility) C3-C6 alkanol is preferably saturated alkoxides, such as C3, C4, C5 or C6 saturated alkoxides.
According to the present invention, Carboxymethylinulin sodium can by inulin under the conditions of alkaline (such as pH is 10-13) with a chloroethene
Acid carries out etherification reaction and obtained.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 the hydroxyl in Carboxymethylinulin sodium in average each fructofuranose unit
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 be 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 original
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, 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 BTA.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 conventional preparation method in field.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 (selectable) and heterocyclic compound (selectable) and suitable quantity of water are well mixed, you can are 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 content sum of the composition in addition to solvent is can be with 25-100 weight %.According to the excellent of the present invention
Embodiment is selected, the non-Phosphorus composite anti incrustation eorrosion snhibiter is made up 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 (the valid density sum of i.e. each composition) of the non-Phosphorus composite anti incrustation eorrosion snhibiter is 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 (the valid density sum of i.e. each composition) of the non-Phosphorus composite anti incrustation eorrosion snhibiter is preferably 10-
50mg/L recirculated cooling waters, more preferably 20-40mg/L recirculated cooling waters.
According to the present invention, each composition 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 composition 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 composition.
According to the present invention, the composite scale-inhibiting corrosion inhibitor is 100- particularly suitable for processing calcium hardness and total alkalinity sum
300mg/L (moisturizing, namely raw water) medium hardness, the recirculated cooling water for being not required to adjust pH value of moderate alkalinity water quality.
Composite scale-inhibiting corrosion inhibitor provided by the invention shows good scale inhibitor combination property, applied to circulating cooling
During water, recirculated cooling water is not only met to scale inhibition and the requirement of inhibition, 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 examples 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 continues reaction 2h at 90 DEG C, and the monomer is dimethyl diallyl ammonium chloride, unsaturated carboxylic acid and third
Olefin(e) acid ester.
Wherein, dimethyl diallyl ammonium chloride is purchased from Beijing Yi Nuokai Science and Technology Ltd.s, and solid content is 60 weight %；
Maleic anhydride, methacrylic acid and itaconic acid are purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and analysis is pure；Methyl acrylate,
Ethyl acrylate, hydroxy-ethyl acrylate and hydroxypropyl acrylate are purchased from Beijing Yili Fine Chemicals Co., Ltd., and analysis is pure；
Ammonium persulfate, potassium peroxydisulfate, sodium peroxydisulfate, sodium pyrosulfite, isopropanol are purchased from Beijing chemical reagents corporation, and analysis is pure.
The assay method of the solid content of copolymer is as follows：
About 1.0g or so water treatment agent product samples are weighed, 0.0002g is accurate to, is placed in the flat weighing disk weighed,
Careful shake makes medicament flow naturally, forms one layer of uniform film in ware bottom, is then placed in electrically heated drying cabinet, is opened from room temperature
Begin to heat, after drying 4h at 120 DEG C, weighed once until constant weight every half an hour.Take out, be put into drier after constant weight
Room temperature is cooled to, is weighed.
Solid content calculation formula is：Solid content=[(m2-m1)/m] × 100%, wherein,
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 %.
BTA is not less than 99 weight % purchased from Tianjin recovery fine chemistry industry research institute, solid content.
In following examples 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 alkali
Degree, total hardness are with CaCO3Meter.Calcium hardness is according to standard GB/T/T 6910-2006《Boiler feed water and cooling water analysis side
Method, calcium catalyst, compleximetry》Measure；Total alkalinity is according to standard GB/T/T 15451-2006《Industrial circulating cooling water,
The measure of total alkali and phenolphthalein alkalinity》Measure；Total hardness refers to Ca in water2+And Mg2+Total amount, according to GB/T 15452-2006《Work
The measure of total hardness in industry recirculated cooling water, EDTA titrations》Measure；Cl-Determined according to standard GB/T 15453-2008；
SO4 2-Determined according to standard GB/T 14642-2009；PH value determines according to standard GB/T 6920-1986；Electrical conductivity is according to standard
GB/T 6908-2008 are determined；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 Carboxymethylinulins sodium (substitution value 1), 10g carboxymethyls-alpha-cyclodextrin and 30g copolymer 1s (30 are weighed respectively
DEG C when limiting viscosity be 0.078dl/g, be dissolved in 80mL water, molecular weight regulator sodium pyrosulfite for initiator ammonium persulfate 4.8g
3.6g is dissolved in 50mL water, monomer diallyldimethylammonChloride Chloride 10g, methyl acrylate 6g, the polymerization of acrylic acid 48g and 25mL water
Obtain, solid content is 30.1 weight %), add in 30g water, shake up, obtain composite scale-inhibiting corrosion inhibitor medicament stoste S1.
The composite scale-inhibiting corrosion inhibitor medicament stoste S1 for taking 1g to prepare is 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
Carry out hindering calcium carbonate scale performance measurement and corrosion inhibition measure according to the method in test case 1.
Embodiment 2
3.14g zinc chloride are weighed, are dissolved in 15g copolymer 1s, then add 45g Carboxymethylinulins sodium (substitution value 0.6)
With 18g methyl-B-cyclodextrins, 8.86g water is added, is shaken up, obtain composite scale-inhibiting corrosion inhibitor medicament stoste S2.
The composite scale-inhibiting corrosion inhibitor medicament stoste S2 for taking 0.9g to prepare is 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 carry out hindering calcium carbonate scale performance measurement according to the method in test case 1 and corrosion inhibition determines.
Embodiment 3
1g BTAs are weighed, being dissolved in 20g copolymers 2, (limiting viscosity is 0.079dl/g at 30 DEG C, is over cure
Sour ammonium 2.4g is dissolved in 80mL water, and isopropanol 6g is dissolved in 50mL water, monomer diallyldimethylammonChloride Chloride 20g, acrylic acid hydroxypropyl
Ester 6g, maleic anhydride 42g and 25mL water polymerize to obtain, and solid content is 29.9 weight %) in, then add 80g Carboxymethylinulins
Sodium (substitution value 0.8) and 6g carboxymethyls-gamma-cyclodextrin, add 13g water, shake up, and obtain composite scale-inhibiting corrosion inhibitor medicament original
Liquid S3.
The composite scale-inhibiting corrosion inhibitor medicament stoste S3 for taking 1.2g to prepare is separately added into 10L test waters 1 and 2 so that
Carboxymethylinulin sodium in water, carboxymethyl-gamma-cyclodextrin, the content of copolymer and BTA be respectively 16mg/L, 6mg/L,
6mg/L and 1mg/L, then carry out hindering calcium carbonate scale performance measurement according to the method in test case 1 and corrosion inhibition determines.
Embodiment 4
40g Carboxymethylinulins sodium (substitution value 1.2), 10g hydroxypropyl-β-cyclodextrins and 30g copolymers 3 are weighed respectively
(limiting viscosity is 0.082dl/g at 30 DEG C, is dissolved in 70mL water for ammonium persulfate 7.2g, and sodium pyrosulfite 2.4g is dissolved in 50mL water,
Monomer diallyldimethylammonChloride Chloride 20g, methyl acrylate 9g, itaconic acid 39g and 30ml water polymerize to obtain, and solid content is
30.2 weight %), add in 20g water, shake up, obtain composite scale-inhibiting corrosion inhibitor medicament stoste S4.
The composite scale-inhibiting corrosion inhibitor medicament stoste S4 for taking 1g to prepare is 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
Carry out hindering calcium carbonate scale performance measurement and corrosion inhibition measure according to the method in test case 1.
Embodiment 5
20g Carboxymethylinulins sodium (substitution value 1.5), 20g Sulfobutyl ether β _ cyclodextrins and 30g copolymers 4 are weighed respectively
(limiting viscosity is 0.075dl/g at 30 DEG C, is dissolved in 70mL water for ammonium persulfate 1.2g, and sodium pyrosulfite 1.2g is dissolved in 40mL water,
Monomer diallyldimethylammonChloride Chloride 20g, hydroxy-ethyl acrylate 18g, methacrylic acid 30g and 30ml water polymerize to obtain, Gu
Content is 29.7 weight %), add in 30g water, shake up, obtain composite scale-inhibiting corrosion inhibitor medicament stoste S5.
The composite scale-inhibiting corrosion inhibitor medicament stoste S5 for taking 1g to prepare is 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
Carry out hindering calcium carbonate scale performance measurement and corrosion inhibition measure according to the method in test case 1.
Embodiment 6
20g Carboxymethylinulins sodium (substitution value 1), 4g methyl-B-cyclodextrins and 40g copolymers 5 are weighed respectively (at 30 DEG C
Limiting viscosity is 0.069dl/g, is dissolved in 70mL water for ammonium persulfate 6g, sodium pyrosulfite 1.2g is dissolved in 50mL water, monomer diformazan
Base diallyl ammonium chloride 30g, hydroxypropyl acrylate 18g, maleic anhydride 24g and 30ml water polymerize to obtain, solid content 30.1
Weight %), add in 36g water, shake up, obtain composite scale-inhibiting corrosion inhibitor medicament stoste S6.
The composite scale-inhibiting corrosion inhibitor medicament stoste S6 for taking 1g to prepare is 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 hindering calcium carbonate scale performance measurement and corrosion inhibition measure.
Comparative example 1
40g Carboxymethylinulins sodium (substitution value 1), 10g alpha-cyclodextrins and 6g poly-aspartates (pole at 30 DEG C are weighed respectively
Limit viscosity is 0.069dl/g, and solid content is 50 weight %), add in 44g water, shake up, obtain medicament stoste D1.
The 1g medicament stostes D1 prepared 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, is then entered according to the method in test case 1
Row resistance calcium carbonate scale performance measurement and corrosion inhibition measure.
Comparative example 2
20g Carboxymethylinulins sodium (substitution value 0.6) and 10g alpha-cyclodextrins are weighed respectively, are added in 70g water, are shaken up, obtain
To medicament stoste D2.
The 1g medicament stostes D2 prepared 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 hindering calcium carbonate scale performance according to the method in test case 1
Measure and corrosion inhibition measure.
Comparative example 3
Weighing 40g copolymers 6, (limiting viscosity is 0.072dl/g at 30 DEG C, is dissolved in 80mL for initiator ammonium persulfate 4.8g
Water, molecular weight regulator sodium pyrosulfite 3.6g are dissolved in 55mL water, monomer diallyldimethylammonChloride Chloride 10g, acrylic acid first
Ester 6g, acrylic acid 48g and 20mL water polymerize to obtain, and solid content is 30.2 weight %), add in 60g water, shake up, obtain medicament
Stoste D3.
The 1g medicament stostes D3 prepared 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 carry out hindering calcium carbonate scale performance measurement according to the method in test case 1 and corrosion inhibition determines.
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.
The 1g medicament stostes D4 prepared 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 dirt 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.
The 1g medicament stostes D5 prepared 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 hindering the survey of calcium carbonate scale performance according to the method in test case 1
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.
The 1g medicament stostes D6 prepared 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.
The 1g medicament stostes D7 prepared 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 hindering 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 (30 DEG C of 18g poly-aspartates
When limiting viscosity be 0.069dl/g, solid content is 50 weight %), add 42g water in, shake up, obtain composite scale-inhibiting corrosion inhibitor medicine
Agent stoste D8.
The 1g medicament stostes D8 prepared 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 hindering 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.
The 1g medicament stostes D9 prepared 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 hindering calcium carbonate scale performance measurement and corrosion inhibition measure.
Test case 1
This test case is evaluating the anticorrosion-antiscaling property of embodiment 1-6 and comparative example 1-9 composite scale-inhibiting corrosion inhibitor.
" 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) calcium carbonate scale performance measurement method is hindered：
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 remaining Ca in sampling analysis water2+Concentration, while do blank sample, and calculate scale inhibition performance.Knot
Fruit is shown in Table 2 (test waters 1) and 3 (test waters 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：Remaining 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 into each embodiment and comparative example throws
In the test water 1 and 2 for having added medicament, steady temperature is 40 ± 1 DEG C, and it is that 75rpm rotates 72h to keep rotating speed, before record experiment
The weight of test piece afterwards, calculate average corrosion rate.It the results are shown in Table 2 (test waters 1) and 3 (test waters 2).
The definition of average corrosion rate is the inhibition efficiency of corrosion inhibiting and descaling agent, and the calculation formula of average corrosion rate (F) is：
F=(C × Δ W)/(A × T × ρ), wherein,
C：When computational constant with mm/a (millimeter/year) is unit, C=8.76 × 107mm/a
ΔW：The corrosion weight loss (g) of test specimen
A：Area (the cm of test specimen2)
T：The corrosion test time (h)
ρ：Density (the kg/m of material for test3), ρ=7.85 × 103kg/m3
(3) flocculating effect assay method：
Kaolin (being purchased from Tianjin great Mao chemical reagent factories) is added in the test water 1 and 2 of table 1, makes its turbidity be
15mg/L, phosphate-free corrosion inhibition antisludging agent is added according still further to the method shown in embodiment and comparative example, experiment takes after terminating (after 0.5h)
2 centimetres of underwater depth water sample analysis turbidity, the method for testing of turbidity (are surveyed for AAS according to standard GB/T 15893
It is fixed).It the results are shown in Table 2 (test waters 1) and 3 (test waters 2).
Table 2
| Embodiment/comparative example | Scale inhibition performance (%) | Average corrosion rate (mm/a) | Turbidity (mg/L) |
| Embodiment 1 | 97.9 | 0.020 | 2.0 |
| Embodiment 2 | 98.5 | 0.019 | 1.9 |
| Embodiment 3 | 97.4 | 0.020 | 2.3 |
| Embodiment 4 | 98.8 | 0.018 | 2.0 |
| Embodiment 5 | 97.9 | 0.022 | 1.8 |
| Embodiment 6 | 98.1 | 0.024 | 1.6 |
| Comparative example 1 | 94.0 | 0.037 | 6.2 |
| Comparative example 2 | 65.6 | 0.088 | 6.9 |
| Comparative example 3 | 82.7 | 0.070 | 3.1 |
| Comparative example 4 | 63.7 | 0.085 | 7.0 |
| Comparative example 5 | 70.9 | 0.094 | 3.2 |
| Comparative example 6 | 61.9 | 0.081 | 3.0 |
| Comparative example 7 | 90.1 | 0.047 | 3.3 |
| Comparative example 8 | 93.0 | 0.040 | 6.9 |
| Comparative example 9 | 80.2 | 0.091 | 3.1 |
Table 3
| Embodiment/comparative example | Scale inhibition performance (%) | Average corrosion rate (mm/a) | Turbidity (mg/L) |
| Embodiment 1 | 97.8 | 0.022 | 2.1 |
| Embodiment 2 | 98.5 | 0.023 | 1.9 |
| Embodiment 3 | 98.3 | 0.025 | 2.0 |
| Embodiment 4 | 98.9 | 0.026 | 2.1 |
| Embodiment 5 | 98.3 | 0.028 | 2.2 |
| Embodiment 6 | 98.8 | 0.031 | 1.7 |
| Comparative example 1 | 94.1 | 0.046 | 6.0 |
| Comparative example 2 | 66.2 | 0.094 | 6.5 |
| Comparative example 3 | 84.3 | 0.078 | 3.2 |
| Comparative example 4 | 65.4 | 0.092 | 6.9 |
| Comparative example 5 | 72.8 | 0.098 | 3.2 |
| Comparative example 6 | 63.0 | 0.081 | 3.1 |
| Comparative example 7 | 91.2 | 0.047 | 3.3 |
| Comparative example 8 | 93.2 | 0.043 | 6.8 |
| Comparative example 9 | 82.3 | 0.099 | 3.5 |
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 good corrosion inhibition, can
Meet recirculated cooling water to scale inhibition and the requirement of inhibition.In addition, non-Phosphorus composite anti incrustation eorrosion snhibiter provided by the invention is simultaneously to following
Suspension 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 changing 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, the present invention are not limited in above-mentioned embodiment
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 contains by the construction unit of dimethyl diallyl ammonium chloride offer, by C3- The construction unit that C10 unsaturated carboxylic acid provides and the construction unit of the acrylate offer by C4-C10.
- 2. non-Phosphorus composite anti incrustation eorrosion snhibiter according to claim 1, wherein, the unsaturated carboxylic acid is acrylic acid, Malaysia At least one of acid, methacrylic acid and methylene-succinic acid, the acrylate is preferably methyl acrylate, acrylic acid second At least one of ester, hydroxy-ethyl acrylate and hydroxypropyl acrylate.
- 3. non-Phosphorus composite anti incrustation eorrosion snhibiter according to claim 1 or 2, wherein, the dimethyl diallyl ammonium chloride, The weight of unsaturated carboxylic acid and acrylate ratio is 1：1.5-8：0.5-3；And/or the limiting viscosity of the copolymer is 0.05-0.16dL/g, preferably 0.065-0.085dL/g.
- 4. non-Phosphorus composite anti incrustation eorrosion snhibiter according to claim 1 or 2, wherein, the substitution value of the Carboxymethylinulin sodium For 0.3-2, preferably 0.6-1.2.
- 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 of dextrin derivative and copolymer ratio is 1：0.1-10：0.1-5, 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 BTA；It is highly preferred that the weight ratio of the heterocyclic compound and Carboxymethylinulin sodium is 0.02-0.2：1, 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, 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, preferably 20-40mg/L recirculated cooling waters.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621362A (en) * | 2003-11-26 | 2005-06-01 | 北京燕化兴业技术开发公司 | Non-phosphorus compound scale and corrosion inhibitor for treatment of circulating cooling water |
| CN105621634A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor, and applications thereof in circulated cooling water treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1621362A (en) * | 2003-11-26 | 2005-06-01 | 北京燕化兴业技术开发公司 | Non-phosphorus compound scale and corrosion inhibitor for treatment of circulating cooling water |
| CN105621634A (en) * | 2014-11-03 | 2016-06-01 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor, and applications thereof in circulated cooling water treatment |
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