CN107522300A - The processing method of corrosion inhibiter and composite corrosion inhibitor and preparation method thereof and its application and recirculated water in aqueous corrosion is suppressed - Google Patents
The processing method of corrosion inhibiter and composite corrosion inhibitor and preparation method thereof and its application and recirculated water in aqueous corrosion is suppressed Download PDFInfo
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- CN107522300A CN107522300A CN201610445558.XA CN201610445558A CN107522300A CN 107522300 A CN107522300 A CN 107522300A CN 201610445558 A CN201610445558 A CN 201610445558A CN 107522300 A CN107522300 A CN 107522300A
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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
- 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
Abstract
The invention discloses a kind of corrosion inhibiter and composite corrosion inhibitor and preparation method thereof and the processing method of its application and recirculated water in aqueous corrosion is suppressed.The corrosion inhibiter contains compound and/or its salt and the condensation reaction products of the compound as shown in following formula II as shown in following formula I,In the Formulas I, R1For H or OH, R2For H or COOH, R3For COOH, CH2COOH orIn the formula II, R4For H, C1‑C4Alkyl, (CH2)n‑COOH、(CH2)4‑NH2、 Or CH2OH, wherein n and m are each independently selected from 1 and 2.The corrosion inhibiter has preferable slow release effect, and is not easy to be utilized by microorganism, content of microorganisms in water is influenceed in use smaller.
Description
Technical field
The present invention relates to water treatment field, in particular it relates to a kind of corrosion inhibiter and the corrosion inhibiter group containing the corrosion inhibiter
Compound；The invention further relates to a kind of preparation method of foregoing corrosion inhibiter；The present invention be further directed to a kind of foregoing corrosion inhibiter or
Application of the foregoing composite corrosion inhibitor of person in aqueous corrosion is suppressed；The present invention is further directed to a kind of processing side of recirculated water
Method.
Background technology
Cooling water is industry, the indispensable public work of enterprise, is to use water rich and influential family.Cold water process Posterior circle is made
With on the one hand can meeting requirement of the technical process to water treatment efficiency, ensure process units long period normal operation；The opposing party
Face can save industry water more than 98%, reduce greater amount of blowdown.In the course of industrial circulating cooling water technology development,
The metal erosion problem of water-filled pipe and heat exchanger is always the important research and development problem of research staff, water treating corrosion medicament
Research and development get most of the attention always.
In early days, phosphorus system water treating corrosion medicament can ensure industrial circulating water because of its high efficiency and the advantage of low cost operation
Cooling system and the safe longtime running of process units, and be widely applied in industrial circulating cooling water.However, in recent years
People gradually recognize pollution of the phosphorus-containing compound to water body, and the limitation for using and discharging to phosphorus-containing compound also gradually tends to
Strictly, thus researchers start exploitation other " green product " to substitute it.From the point of view of current scientific research progress, nothing
The organic compound and high molecular polymer of the poison labyrinth such as free of contamination, containing N, S, O are undoubtedly the preferred original of corrosion inhibiter
Material.
A kind of degradable without phosphorus composite slow-corrosion scale resistor is disclosed in Chinese patent application CN103332796A, and is had
Body discloses the without phosphorus composite slow-corrosion scale resistor by sodium sulphate, APG, poly-aspartate, carboxymethyl cellulose, polycyclic oxygen
Butanedioic acid, polymeric amino acid, sodium gluconate, lignin, methyl benzotriazole and deionized water composition.It is this by nontoxic no dirt
The organic compound of the labyrinth such as dye, containing N, S, O and the composite slow-corrosion scale resistor of high molecular polymer composition have really
There is corrosion and scale inhibition performance, and can effectively reduce chemical feeding quantity, and there is biodegradable, steady performance.It is however, this multiple
Close corrosion inhibiting and descaling agent to compound several materials together, its influence to microorganism is the superposition of many kinds of substance, in easy biology drop
Also easily utilized while solution by microorganism, cause the breeding of microorganism, be unfavorable for the recycling of cooling water.
The content of the invention
Present invention aims at provide a kind of corrosion inhibiter and composite corrosion inhibitor and preparation method thereof and it is suppressing water
The processing method of application and recirculated water in corrosion, so that while the corrosion mitigating effect of corrosion inhibiter is kept, friendly environment simultaneously to the greatest extent may be used
It is avoided that water treatment corrosion inhibitors is utilized by microorganism.
Therefore, according to the first aspect of the invention, there is provided a kind of corrosion inhibiter, the corrosion inhibiter contain as shown in following formula I
Compound and/or its salt and the condensation reaction products of the compound as shown in following formula II,
In the Formulas I, R1For H or OH, R2For H or COOH, R3For COOH, CH2- COOH or
In the formula II, R4For H, C1-C4Alkyl, (CH2)n-COOH、(CH2)4-NH2、 Or CH2- OH, wherein n and m are independently of one another
Selected from 1 and 2.
According to the second aspect of the invention, there is provided a kind of preparation method of corrosion inhibiter, the preparation method include：Contracting
Close under reaction condition, in the presence of a catalyst, aliphatic hydroxyl carboxylic acid and/or its salt are contacted in water with amino acid, formation
The corrosion inhibiter；Wherein, the aliphatic hydroxyl carboxylic acid has the structure as shown in following formula I；The amino acid has such as following formula II
Shown structure,
In the Formulas I, R1For H or OH, R2For H or COOH, R3For COOH, CH2- COOH or
In the formula II, R4For H, C1-C4Alkyl, (CH2)n-COOH、(CH2)4-NH2、 Or CH2- OH, wherein n and m are independently of one another
Selected from 1 and 2.
According to the third aspect of the present invention, there is provided a kind of corrosion inhibiter prepared by the method for the invention.
According to the fourth aspect of the present invention, there is provided a kind of composite corrosion inhibitor, the composite corrosion inhibitor contain inhibition
Agent and water-soluble inorganic zinc salt, the corrosion inhibiter are corrosion inhibiter of the present invention.
According to the fifth aspect of the present invention, there is provided a kind of corrosion inhibiter of the present invention, or it is of the present invention
Application of the composite corrosion inhibitor in aqueous corrosion is suppressed.
According to the sixth aspect of the invention, there is provided a kind of processing method of recirculated water, this method are included in water and added
Enter corrosion inhibiter of the present invention, or composite corrosion inhibitor of the present invention.
Compound shown in compound (and its salt) shown in Formulas I contained by corrosion inhibiter provided by the present invention and formula II
Condensation reaction products, which have, to be not easy to be utilized by microorganism, the more longlasting effect of drug effect, and in use to micro- life in water
Thing content influences less feature, it is can be widely applied in circulating water cooling treatment.It is moreover, provided by the present invention slow
Agent is lost when with water-soluble inorganic zinc salt compounding use, can embody preferable corrosion mitigating effect, the corrosion inhibition rate energy of carbon steel test piece
Enough reach more than 90.9%.Exploitation, the promotion and application of corrosion inhibiter provided by the present invention have larger economic benefit and society
Can benefit.
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 present inventor in order to research and develop it is a kind of can replace phosphorus-containing compound " green corrosion inhibitor " carry out largely
Experiment.Inventor is had found the addition of some aliphatic hydroxyl Barbiturates compounds in recirculated water, is had to Circulating Water Corrosion
Certain inhibitory action, more preferably, and this kind of compound is nontoxic for performance when particularly it is used cooperatively with bivalent metal ion, no
Environmental pollution can be caused.However, this kind of compound as corrosion inhibiter be added to recirculated water in use, but exist can be by micro- life
Thing is utilized, and nutrition is provided for microorganism, the shortcomings that promoting the growth and breeding of microorganism, and this shortcoming exactly constrain it is this kind of
The reason for development that the corrosion inhibiter that compound is used as uses.In once accidental chance, the inventors found that by fat
The product that race's hydroxycarboxylic acid and/or its salt are generated with amino acid progress condensation reaction, not only remains aliphatic hydroxyl carboxylic acid
Corrosion inhibition possessed by salt compounds, and this condensation product is also less prone to be utilized by microorganism, reduces microorganism
Growth and breeding.
Therefore, the present inventor provides a kind of corrosion inhibiter.The corrosion inhibiter contain as shown in following formula I compound and/
Or its salt and the condensation reaction products of the compound as shown in following formula II,
In the Formulas I, R1For H or OH, R2For H or COOH, R3For COOH, CH2- COOH or
In the formula II, R4For H, C1-C4Alkyl, (CH2)n-COOH、(CH2)4-NH2、 Or CH2- OH, wherein n and m are selected independently of one another
From 1 and 2.
In corrosion inhibiter provided by the present invention, compound shown in compound (and its salt) shown in contained Formulas I and formula II
Condensation reaction products have and be not easy to be utilized by microorganism, the more longlasting effect of drug effect, and in use to micro- in water
Biological content influences less feature, it is can be widely applied in circulating water cooling treatment.It is moreover, provided by the present invention slow
Agent is lost when with water-soluble inorganic zinc salt compounding use, can embody preferable corrosion mitigating effect, the corrosion inhibition rate energy of carbon steel test piece
Enough reach more than 90.9%.Exploitation, the promotion and application of corrosion inhibiter provided by the present invention have larger economic benefit and society
Can benefit.
In corrosion inhibiter provided by the present invention, compound (and its salt) and the compound as shown in following formula II according to Formulas I
The difference of rate of charge, the product of the condensation reaction can be the corresponding molecule of compound (and its salt) shown in the Formulas I of a molecule
Formula II shown in compound condensation reaction product, can also the corresponding polymolecular of compound (and its salt) shown in the Formulas I of a molecule
The product of the reaction of compound condensation shown in formula II；It can also be the corresponding molecular formula of compound (and its salt) shown in polymolecular Formulas I
The product of the reaction of compound condensation shown in II；It can also be the mixture of the product of aforementioned condensation reaction.
According to above-mentioned corrosion inhibiter provided by the present invention, for the ease of by its application in terms of aqueous corrosion is suppressed, generally
Need the molecular weight of control wherein condensation reaction products so that corresponding condensation reaction products can be dissolved in water, and then preferably real
Circulation in present water process.The preferably molecular weight distribution of the condensation reaction products is in 200-1000 scopes in the present invention
It is interior, it is preferably distributed in the range of 300-600.This corrosion inhibiter provided by the present invention can be by controlling compound shown in Formulas I
The inventory and reaction condition of compound shown in (and its salt) and formula II, point of the condensation reaction products to being obtained can be realized
The control of son amount.
" molecular weight " can be detected by mass spectrography and obtained in the present invention, and wherein mass spectrography scan mode is FTMS-p
ESI Full ms[100-1000]。
According to the present invention corrosion inhibiter, consider condensation reaction products water solubility and sustained release rate, preferably described formula
Compound shown in II is (0.5-8) with compound shown in the Formulas I and its mol ratio of salt：1, be preferably (1-4)：1.
According to the corrosion inhibiter of the present invention, compound shown in optional Formulas I includes but is not limited to gluconic acid, citric acid, wine
One or more in stone acid and malic acid, compound shown in preferably described Formulas I is gluconic acid.Chemical combination shown in optional Formulas I
The salt of thing is sodium salt and/or sylvite, and the salt of preferred aliphat hydroxycarboxylic acid is sodium gluconate and/or K-IAO.
According to the corrosion inhibiter of the present invention, compound shown in optional formula II includes but is not limited to glycine, valine, bright ammonia
In acid, isoleucine, serine, threonine, lysine, arginine, aspartic acid, glutamic acid, asparagine and paddy winter propylhomoserin
One or more.It is preferred that the amino acid is glycine, alanine, aspartic acid, serine, threonine, leucine, asparagus fern
One or more in acid amides, glutamic acid and lysine, more preferably described amino acid are aspartic acid.
According to the corrosion inhibiter of the present invention, wherein condensation reaction products be with compound shown in foregoing Formulas I and/or its salt with before
Compound shown in formula II is stated as raw material, when obtaining reaction product through condensation reaction, for the ease of the progress of reaction, and simplifies phase
The preparation method answered.This corrosion inhibiter provided by the present invention is directly applied without being purified to reaction product.
Preferably also contain water in the corrosion inhibiter in the present invention, and the solid content of the corrosion inhibiter is 25-55 weight %.
According to the corrosion inhibiter of the present invention, the assay method of wherein solid content includes：About 1.0g corrosion inhibiter samples are weighed, accurately
To 0.0002g, it is placed in the flat weighing disk weighed, careful shake makes corrosion inhibiter sample flow naturally, and one is formed in ware bottom
The uniform film of layer, is then placed in electrically heated drying cabinet, is begun to warm up from room temperature, small every half after drying 4h at 120 DEG C
When weigh once until constant weight.Taken out after constant weight, be put into drier and be cooled to room temperature, weighed.
Solid content calculation formula is：Solid content=[(m2-m1)/m] × 100%；
m2：Dried corrosion inhibiter sample and weighing disk weight, g；
m1：Weighing disk net weight, g；
m：Weigh the quality of corrosion inhibiter sample, g.
It is the non-phosphate inhibitor of a kind of " green " wherein not containing phosphorus-containing compound according to the corrosion inhibiter of the present invention.It is this
Corrosion inhibiter is green to application, can be long-term use of, without causing pollution of waterhead.
Meanwhile present invention also offers a kind of preparation method of corrosion inhibiter, the preparation method to include：In condensation reaction condition
Under, in the presence of a catalyst, aliphatic hydroxyl carboxylic acid and/or its salt and amino acid are contacted in water, form the corrosion inhibiter；
Wherein, the aliphatic hydroxyl carboxylic acid has the structure as shown in following formula I；The amino acid has the structure as shown in following formula II,
In the Formulas I, R1For H or OH, R2For H or COOH, R3For COOH, CH2- COOH orThe formula II
In, R4For H, C1-C4Alkyl, (CH2)n-COOH、CH2)4-NH2、 Or CH2- OH, wherein n and m are each independently selected from 1 and 2.
Corrosion inhibiter preparation method provided by the present invention, by promoting aliphatic hydroxyl carboxylic acid and/or its salt and amino acid
Generation condensation reaction, the condensation reaction products that can be dissolved in water being formed, this condensation reaction products, which have, to be not easy to be utilized by microorganism,
The more longlasting effect of drug effect, and then it is smaller it is influenceed in use on content of microorganisms in water, can be widely applied to follow
In ring cold water process.Moreover, corrosion inhibiter provided by the present invention can embody when with water-soluble inorganic zinc salt compounding use
Go out preferable corrosion mitigating effect, the corrosion inhibition rate of carbon steel test piece can reach more than 90.9%.Corrosion inhibiter provided by the present invention is opened
Hair, promotion and application have larger economic benefit and social benefit.
Preparation in accordance with the present invention, wherein for aliphatic hydroxyl carboxylic acid and/or the inventory of its salt and amino acid
Not particular/special requirement, can be real to a certain extent as long as containing above two raw material simultaneously and condensation reaction can occur
The existing purpose of the present invention.However, in order that reaction product (i.e. aforementioned condensation reaction product) is substantially all is dissolved in water, Yi Jiwei
The corrosion mitigating effect of the prepared corrosion inhibiter of optimization, the in the present invention preferably amino acid and aliphatic hydroxyl carboxylic acid and its salt
Mol ratio be (0.5-8)：1, more preferably (1-4)：1.
Preparation in accordance with the present invention, led wherein used aliphatic hydroxyl carboxylic acid and its salt can be water treatment agent
Domain conventional use of aliphatic hydroxyl carboxylic acid and its salt with corrosion inhibition, in the present invention preferred aliphat hydroxycarboxylic acid be
One or more in gluconic acid, citric acid, tartaric acid and malic acid.Meanwhile preferred aliphat hydroxyl carboxylic in the present invention
The salt of acid is sodium salt and/or sylvite, and more preferably described aliphatic hydroxyl carboxylate is sodium gluconate, K-IAO, lemon
One or more in sour trisodium, citric acid tri potassium, sodium tartrate and potassium tartrate.It is highly preferred that the aliphatic hydroxyl carboxylic
Hydrochlorate is sodium gluconate or K-IAO.
Preparation in accordance with the present invention, wherein used amino acid can be arbitrarily can be with foregoing aliphatic hydroxyl
Carboxylic acid occur condensation reaction amino acid, the amino acid that can be used in the present invention for example glycine, valine, leucine,
One in isoleucine, serine, threonine, lysine, arginine, aspartic acid, glutamic acid, asparagine and paddy winter propylhomoserin
Kind is a variety of.Preferably the amino acid is glycine, alanine, aspartic acid, serine, threonine, bright ammonia in the present invention
One or more in acid, asparagine, glutamic acid and lysine, more preferably aspartic acid.
Preparation in accordance with the present invention, the preferable corrosion inhibiter is with sodium gluconate or K-IAO and asparagus fern
Propylhomoserin is raw material, obtained prepared by condensation reaction.
Preparation in accordance with the present invention, wherein not special for the inventory of used catalyst and catalyst
Promoting aliphatic hydroxyl carboxylic acid and/or its salt and amino acid that condensation reaction occurs and is used it is required that it is referred to this area
Catalyst and catalyst conventional amount used.However, in order to promote reaction product (i.e. aforementioned condensation reaction product) substantially all molten
Yu Shui, and in order to optimize the corrosion inhibition of prepared corrosion inhibiter, in the present invention preferably the catalyst be sulfuric acid and/or
Nitric acid.More preferably described catalyst is using the mol ratio of pH meter and the aliphatic hydroxyl carboxylic acid and its salt as (0.4-6)：1,
Preferably (1.6-3)：1.
Do not have particular/special requirement to the concentration of sulfuric acid and nitric acid in the present invention, as long as the sulfuric acid and nitric acid that are added meet
Aforementioned molar ratio requirement.
Preparation in accordance with the present invention, wherein not having particular/special requirement for the condensation reaction condition, it can be
What this area routinely used can arbitrarily promote aliphatic hydroxyl carboxylic acid and/or its salt that condensation reaction occurs with amino acid
Condition.However, in order that reaction product (i.e. aforementioned condensation reaction product) is substantially all is dissolved in water, it is and made in order to optimize
The corrosion inhibition of standby corrosion inhibiter, in the present invention preferably the condensation reaction condition include：The contact is being enough to steam in water
Carried out at a temperature of going out, the container contacted preferably is placed in into temperature is in 100-180 DEG C of heating bath, the contact when
Between be 2-10 hours.
Preparation in accordance with the present invention, wherein the process in the condensation reaction is carried out under agitation, its
In do not have special requirement for the method for stirring, can carry out reasonable selection according to the model of reaction vessel, for example, including
But it is not limited to, magnetic rotor or stirring slurry stirring；Do not have particular/special requirement for mixing speed in the present invention, as long as promoting original
Material mixing is scattered relatively uniform, and will not splash.
Device of the present invention can be the reactor with condensate recycling device, during the course of the reaction, pass through oil
Bath heating causes temperature of reaction system to rise to reaction temperature and reacted, and with the progress of reaction, part is had in reaction system
Water vapour is volatized into condensate recycling device, and after the completion of reaction, the temperature of reaction system can raise, when detecting reaction system
Temperature start rise when, terminate reaction, to avoid the loss of active principle.Add in the heating bath that can be used in the present invention
Thermal medium includes but is not limited to dimethicone, methyl-silicone oil and other conduction oils.
Preparation in accordance with the present invention, wherein for being contacted instead with amino acid in aliphatic hydroxyl carboxylic acid and/or its salt
The addition of water does not have particular/special requirement during answering, as long as can be molten by aliphatic hydroxyl carboxylic acid or its salt and amino acid
Solution, and be advantageous to both and mix.In method provided by the present invention, for controlling reaction temperature, the water added is simultaneously
Will not all it discharge during the course of the reaction, it is understood some and remained in reaction product, preferably foregoing made in the present invention
The solid content of standby corrosion inhibiter is 25-55 weight %.The computational methods of solid content are already discussed above in the present invention,
This is repeated no more.
Meanwhile one kind is additionally provided in the present invention corrosion inhibiter is prepared by method provided by the present invention.By this hair
There are corrosion inhibiter prepared by bright described method the component essentially identical with the foregoing corrosion inhibiter of the present invention and effect, these contents to exist
It is foregoing to have been noted above, it will not be repeated here.
In addition, additionally providing a kind of composite corrosion inhibitor in the present invention, the composite corrosion inhibitor contains corrosion inhibiter and water
Insoluble inorganic zinc salt, the corrosion inhibiter are corrosion inhibiter of the present invention, or the corrosion inhibiter prepared by the method for the invention.
This composite corrosion inhibitor provided by the present invention, by by corrosion inhibiter of the present invention, or by the present invention
Corrosion inhibiter prepared by described method and water-soluble inorganic zinc salt compounding use, can embody preferable corrosion mitigating effect, carbon steel
The corrosion inhibition rate of test piece can reach more than 90.9%.The exploitation of composite corrosion inhibitor provided by the present invention, promotion and application tool
There are larger economic benefit and social benefit.
According to the composite corrosion inhibitor of the present invention, wherein not special for the dosage of corrosion inhibiter and water-soluble inorganic zinc
It is required that as long as the purpose of the present invention can be just realized to a certain extent containing both simultaneously.However, in order to further optimize this
The corrosion mitigating effect of invention composite corrosion inhibitor, the preferably corrosion inhibiter is with its total solids and the water-soluble nothing in the present invention
The weight ratio that machine zinc salt is counted using Zn-ef ficiency is 100：(5-25), preferably 100：(7.5-20).The survey of total solid in the present invention
Amount method may refer to preceding description.
According to the composite corrosion inhibitor of the present invention, wherein the water-soluble inorganic zinc salt can be normal in water treatment agent field
The various water-soluble inorganic zinc salts used are advised, as long as Zn can be produced after added in recirculated water2+, preferable case
Under, the water-soluble inorganic zinc salt is zinc sulfate and/or zinc nitrate.Particularly preferably zinc sulfate.In the present invention, the water solubility
Inorganic zinc salt generally refers in water solubility (20 DEG C, 1 atmospheric pressure under) as the inorganic zinc salt more than 1 weight %.
According to the composite corrosion inhibitor of the present invention, it can be obtained by existing various methods, such as can will be foregoing
The raw material of composite corrosion inhibitor mixes according to foregoing required ratio, the present invention to the condition of the mixing without particular/special requirement,
It will not be repeated here.
A kind of corrosion inhibiter of the present invention is additionally provided in the present invention, or prepared by method of the present invention
Corrosion inhibiter, or application of the composite corrosion inhibitor of the present invention in aqueous corrosion is suppressed.
In addition, additionally providing a kind of processing method of recirculated water in the present invention, this method, which is included in water, adds this hair
Bright described corrosion inhibiter, the corrosion inhibiter either prepared by method of the present invention or corrosion inhibiter of the present invention combine
Thing.
The processing method (application in aqueous corrosion is suppressed) of recirculated water according to the present invention, wherein by the present invention
Described corrosion inhibiter, or when the corrosion inhibiter prepared by method of the present invention is added in recirculated water, aliphatic hydroxyl carboxylic
Acid or the condensation reaction products of its salt and amino acid (corrosion inhibiter of the present invention), recirculated water can be added directly into without purification
In, preferably described corrosion inhibiter is using inventory of its total solids in recirculated water as 10-20mg/L.
The processing method (application in aqueous corrosion is suppressed) of recirculated water according to the present invention, wherein by the present invention
When described composite corrosion inhibitor is in recirculated water, can such as it be pressed using composite corrosion inhibitor of the present invention is preceding prepared
Added after according to aforementioned formula, each raw material is mixed in recirculated water, now the preferably composite corrosion inhibitor is with wherein corrosion inhibiter
Inventory of the total solids in recirculated water is 10-20mg/L；Can also be by each raw material according to composite corrosion inhibitor of the present invention
Aforementioned formula is directly added into without blend step in recirculated water, and now preferably corrosion inhibiter of the present invention is with its total solids
Inventory in recirculated water is 10-20mg/L, and inventory of the water-soluble inorganic zinc salt in recirculated water is 1.5-2.5mg/L.
Corrosion inhibiter and corrosion inhibiter of the present invention are further illustrated below with reference to specific preparation example 1 to 14 and embodiment 1 to 14
The beneficial effect of composition and preparation method thereof and the processing method of its application and recirculated water in aqueous corrosion is suppressed.
Each raw material employed in following examples and comparative is described as follows：
Sodium gluconate and K-IAO are purchased from lark prestige Science and Technology Ltd., and analysis is pure；
Citric acid and trisodium citrate are purchased from Chemical Reagent Co., Ltd., Sinopharm Group, and analysis is pure；
Sodium tartrate and sodium tartrate are purchased from Beijing chemical reagents corporation, and analysis is pure；
Glycine, alanine, L-Aspartic acid, glutamic acid and lysine are purchased from Aladdin reagent (Shanghai) limited public affairs
Department, analysis are pure；
The concentrated sulfuric acid is purchased from Tianjin recovery fine chemistry industry research institute, and analysis is pure, and concentration is 98 weight %；
Concentrated nitric acid is purchased from Beijing Yili Fine Chemicals Co., Ltd., and analysis is pure, and concentration is 68 weight %；
YSW-109 is purchased from the calm and peaceful Co., Ltd in Shandong, wherein containing polymeric scale inhibitor dispersant, non-phosphate inhibitor, zinc salt
Deng；
Hydroxy ethylene diphosphonic acid (HEDP) is purchased from the strong Yilong Industry Co., Ltd. in Luoyang, and effective content is 50 weight %.
In following examples, the total solid of reaction product and the measure of solid content
About 1.0g corrosion inhibiter samples are weighed, 0.0002g is accurate to, is placed in the flat weighing disk weighed, careful shake makes
Corrosion inhibiter sample flows naturally, forms one layer of uniform film in ware bottom, is then placed in electrically heated drying cabinet, adds since room temperature
Heat, after drying 4h at 120 DEG C, weighed once until constant weight every half an hour.Taken out after constant weight, be put into drier and cool down
To room temperature, weigh.
Total solid calculation formula is：Total solid=m2-m1；
Solid content calculation formula is：Solid content=[(m2-m1)/m] × 100%；
m2：Dried corrosion inhibiter sample and weighing disk weight, g；
m1：Weighing disk net weight, g；
m：Weigh the quality of corrosion inhibiter sample, g.
In following examples and comparative, the test side of the molecular weight of condensation reaction products in prepared reaction product
Method mass spectrography.Scan mode is FTMS-p ESI Full ms [100-1000].
Preparation example 1
In the four-hole boiling flask equipped with agitator, distilling apparatus and thermometer add sodium gluconate 21.8g (0.1mol),
Aspartic acid 26.6g (0.2mol) and 100ml water, start stirring, sodium gluconate and aspartic acid is fully dissolved mixing, so
Concentrated sulfuric acid 15.0g is added under room temperature (20 DEG C) afterwards and (contains H2SO40.15mol).Heating bath (the heating of foregoing flask will be built-in with
Medium is dimethicone) 100 DEG C are warming up to, react 10 hours, it is 30g that water is steamed in course of reaction, and remaining liq cools down
Corrosion inhibiter is produced, the product is designated as S1, and corrosion inhibiter S1 solid content is 29.5 weight % after measured, after measured corrosion inhibiter S1
The molecular weight distribution of middle condensation reaction products is in the range of 311-426.
Preparation example 2-5
The preparation method of corrosion inhibiter：With reference to the preparation method of corrosion inhibiter in preparation example 1, difference is that the dosage of each raw material has
Institute is different, and particular content is as shown in the table：
| Preparation example | 2 | 3 | 4 | 5 |
| Sodium gluconate (mol) | 0.1 | 0.1 | 0.1 | 0.1 |
| Aspartic acid (mol) | 0.1 | 0.4 | 0.05 | 0.8 |
| The concentrated sulfuric acid (contains H2SO4, mol) | 0.08 | 0.15 | 0.02 | 0.3 |
| Solid content (weight %) | 30.2 | 43.2 | 26.0 | 54.1 |
| Condensation reaction products range of molecular weight distributions | 311 | 311-541 | 311-489 | 311-656 |
Corrosion inhibiter prepared by preparation example 2-5 is designated as S2-S5.
Preparation example 6
Sodium gluconate 10.9g is added in the four-neck flask equipped with agitator, distilling apparatus and thermometer
(0.05mol), aspartic acid 16.6g (0.125mol) and 100ml water, start stirring, fill sodium gluconate and aspartic acid
Divide dissolving mixing, concentrated sulfuric acid 7.5g is then added under room temperature (20 DEG C) (contains H2SO4, 0.075mol).Foregoing flask will be built-in with
Heating bath (heating medium is dimethicone) be warming up to 140 DEG C, react 6 hours, it is 45g that water is steamed in course of reaction,
Remaining liq, which cools down, in flask produces water treatment corrosion inhibitors, and the product is designated as S6, and corrosion inhibiter S6 solid content is after measured
26.3 weight %, after measured in the corrosion inhibiter S6 molecular weight distribution of condensation reaction products in the range of 311-426.
Preparation example 7
Sodium gluconate 10.9g is added in the four-hole boiling flask equipped with agitator, distilling apparatus and thermometer
(0.05mol), aspartic acid 16.7g (0.125mol) and 100ml water, start stirring, fill sodium gluconate and aspartic acid
Divide dissolving mixing, concentrated sulfuric acid 10.0g is then added under room temperature (20 DEG C) (contains H2SO4, 0.1mol).Foregoing flask will be built-in with
Heating bath (heating medium is dimethicone) be warming up to 120 DEG C, react 3 hours, it is 35g that water is steamed in course of reaction,
Remaining liq, which cools down, in flask must produce water treatment corrosion inhibitors, and the product is designated as S7, and corrosion inhibiter S7 solid content is after measured
25.1 weight %, after measured in the corrosion inhibiter S7 molecular weight distribution of condensation reaction products in the range of 311-426.
Preparation example 8
Sodium gluconate 10.9g is added in the four-hole boiling flask equipped with agitator, distilling apparatus and thermometer
(0.05mol), aspartic acid 16.7g (0.125mol) and 80ml water, start stirring, make sodium gluconate and aspartic acid abundant
Dissolving mixing, concentrated nitric acid 13.9g is then added under room temperature (20 DEG C) and (contains HNO3, 0.15mol).Foregoing flask will be built-in with
Heating bath (heating medium is dimethicone) is warming up to 140 DEG C, reacts 6 hours, and it is 45g that water is steamed in course of reaction, burns
Remaining liq, which cools down, in bottle produces water treatment corrosion inhibitors, and the product is designated as S8, and corrosion inhibiter S8 solid content is 35.6 after measured
Weight %, after measured in the corrosion inhibiter S8 molecular weight distribution of condensation reaction products in the range of 311-426.
Preparation example 9
In the four-hole boiling flask equipped with agitator, distilling apparatus and thermometer add K-IAO 23.4g (0.1mol),
Aspartic acid 13.3g (0.1mol) and 100ml water, start stirring, K-IAO and aspartic acid is fully dissolved mixing, so
Concentrated nitric acid 3.7g is added under room temperature (20 DEG C) afterwards and (contains HNO3, 0.04mol).Heating bath (the heating of foregoing flask will be built-in with
Medium is dimethicone) it is warming up to 180 DEG C, react 6 hours, it is 55g that water is steamed in course of reaction, remaining liq in flask
Cool down and produce water treatment corrosion inhibitors, the product is designated as S9, and corrosion inhibiter S9 solid content is 41.7 weight % after measured, after measured
The molecular weight of condensation reaction products is 311 in corrosion inhibiter S9.
Preparation example 10
Sodium gluconate 10.9g is added in the four-hole boiling flask equipped with agitator, distilling apparatus and thermometer
(0.05mol), alanine 11.1g (0.125mol) and 100ml water, start stirring, make sodium gluconate and alanine fully molten
Solution mixing, concentrated nitric acid 13.7g is then added under room temperature (20 DEG C) and (contains HNO3, 0.15mol).Adding for foregoing flask will be built-in with
Heating bath (heating medium is dimethicone) is warming up to 130 DEG C, reacts 7 hours, and it is 50g that water is steamed in course of reaction, flask
Middle remaining liq, which cools down, produces water treatment corrosion inhibitors, and the product is designated as S10, and corrosion inhibiter S10 solid content is 36.4 after measured
Weight %, after measured in the corrosion inhibiter S10 molecular weight distribution of condensation reaction products in the range of 267-338.
Preparation example 11
In the four-hole boiling flask equipped with agitator, distilling apparatus and thermometer add trisodium citrate 29.4g (0.1mol),
Alanine 8.9g (0.1mol) and 100ml water, start stirring, trisodium citrate and alanine is fully dissolved mixing, Ran Hou
Concentrated sulfuric acid 8.0g is added under room temperature (20 DEG C) and (contains H2SO4, 0.08mol).Heating bath (the heating medium of foregoing flask will be built-in with
For dimethicone) it is warming up to 150 DEG C, react 4 hours, it be 50g that water is steamed in course of reaction, remaining liq cooling in flask
Water treatment corrosion inhibitors is produced, the product is designated as S11, and corrosion inhibiter S11 solid content is 31.8 weight % after measured, after measured should
The molecular weight of condensation reaction products is 263 in corrosion inhibiter S11.
Preparation example 12
Citric acid 19.2g (0.1mol) is added in the four-hole boiling flask equipped with agitator, distilling apparatus and thermometer, relies ammonia
Sour 21.9g (0.15mol) and 100ml water, start stirring, citric acid and lysine is fully dissolved mixing, then in room temperature (20
DEG C) under add concentrated sulfuric acid 10.0g (contain H2SO4, 0.1mol), by the heating bath for being built-in with foregoing flask, (heating medium is dimethyl
Silicone oil) it is warming up to 110 DEG C, react 8 hours, it is 30g that water is steamed in course of reaction, and remaining liq, which cools down, in flask must produce water
Corrosion inhibiter is handled, the product is designated as S12, and corrosion inhibiter S12 solid content is 45.9 weight % after measured, after measured the corrosion inhibiter
The molecular weight distribution of condensation reaction products is in the range of 320-448 in S12.
Preparation example 13
Sodium tartrate 19.8g (0.1mol), paddy are added in the four-hole boiling flask equipped with agitator, distilling apparatus and thermometer
Propylhomoserin 7.4g (0.05mol) and 100ml water, start stirring, sodium tartrate and glutamic acid is fully dissolved mixing, then in room temperature
Concentrated nitric acid 3.66g is added under (20 DEG C) and (contains HNO3, 0.04mol), by the heating bath for being built-in with foregoing flask, (heating medium is two
Methyl-silicone oil) it is warming up to 110 DEG C, react 2 hours, it is 25g that water is steamed in course of reaction, and remaining liq, which cools down, in flask produces
Water treatment corrosion inhibitors, the product are designated as S13, and corrosion inhibiter S13 solid content is 49.3 weight % after measured, the inhibition after measured
The molecular weight distribution of condensation reaction products is in the range of 279-411 in agent S13.
Preparation example 14
In the four-neck flask equipped with agitator, distilling apparatus and thermometer add potassium tartrate 11.7g (0.05mol),
Glycine 30.0g (0.4mol) and 100ml water, start stirring, potassium tartrate and glycine is fully dissolved mixing, then in room
Concentrated sulfuric acid 2.5g is added under warm (20 DEG C) and (contains H2SO4, 0.025mol).By the heating bath for being built-in with foregoing flask, (heating medium is
Dimethicone) it is warming up to 130 DEG C, react 6 hours, it is 40g that water is steamed in course of reaction, and remaining liq cools down in flask
Water treatment corrosion inhibitors is produced, the product is designated as S14, and corrosion inhibiter S14 solid content is 47.0 weight % after measured, after measured should
The molecular weight distribution of condensation reaction products is in the range of 207-264 in corrosion inhibiter S14.
Test one, microbiological effect experiment (the influence experiment of heterotroph in water sample)
Method of testing：After taking 200mL running water to stand half an hour, the heterotroph stoste 1-2mL of enrichment culture, stirring are added
Uniformly, with 15mgL-1Concentration (amount of total solid in corrosion inhibiter) corrosion inhibiter prepared by preparation example 1-14 is added into water
S1-S14, it is put into 29 ± 1 DEG C of incubator, the peculiar bacterium number amount in the separately sampled analysis water of 1h, 24h, 48h, 72h.Together
When be based on same test method, with blank sample, corrosion inhibiter DS1+ in corrosion inhibiter DS1-DS3, and comparative example 4 in comparative example 1 to 3
DS3 is as check experiment.Wherein：
" blank sample " is that the check experiment of any corrosion inhibiter is not added with the water of heterotroph stoste of enrichment culture is added；
" comparative example 1 " is that the production of lark prestige Science and Technology Ltd. is added in the water of heterotroph stoste of enrichment culture is added
Sodium gluconate (product is designated as DS1) check experiment；
" comparative example 2 " is that Tianjin five happinesses are added in the water of heterotroph stoste of enrichment culture is added with the limited public affairs of safe chemical industry
Take charge of the check experiment of the poly-aspartate (product is designated as DS2) of production；
" comparative example 3 " is to add Aladdin reagent (Shanghai) limited public affairs in the water of heterotroph stoste of enrichment culture is added
Take charge of the check experiment of the aspartic acid (product is designated as DS3) of production.
" comparative example 4 " is by weight 1 in the water of heterotroph stoste of enrichment culture is added：2 add lark prestige simultaneously
The sodium gluconate (product is designated as DS1) of Science and Technology Ltd.'s production and the day of Aladdin reagent (Shanghai) Co., Ltd. production
The check experiment of winter propylhomoserin (product is designated as DS3).
Test result：As shown in table 1.
Table 1.
It is can be seen that from the data in table 1 compared with blank sample, aliphatic hydroxyl carboxylate added in infected water sample
(DS1), poly-aspartate (DS2), aspartic acid (DS3) and aliphatic hydroxyl carboxylate (DS1) and aspartic acid (DS3)
Mixture when, heterotrophism bacterium number showed increased；And when adding according to corrosion inhibiter S1-S14 provided by the present invention, heterotrophism in water sample
Bacterium number amount and blank test are basically identical, it can thus be appreciated that the novel corrosion inhibitor will not promote in recirculated water the growth of microorganism and numerous
Grow.
Embodiment 1-14
Composite corrosion inhibitor：Corrosion inhibiter prepared by preparation example 1 to 14 and water-soluble inorganic zinc salt white vitriol are compounded
Formed, prepared composite corrosion inhibitor is designated as P1-P14, the composite corrosion inhibitor P1-P14 and the corrosion inhibiter S1-S14
Corresponding relation it is as shown in table 2 below：
Table 2
| Composite corrosion inhibitor | P1 | P2 | P3 | P4 | P5 | P6 | P7 |
| Corrosion inhibiter | S1 | S2 | S3 | S4 | S5 | S6 | S7 |
| Composite corrosion inhibitor | P8 | P9 | P10 | P11 | P12 | P13 | P14 |
| Corrosion inhibiter | S8 | S9 | S10 | S11 | S12 | S13 | S14 |
Test two：Corrosion inhibition is evaluated
In following corrosion inhibition evaluation, the water quality of test water is as shown in table 3, wherein Ca2+, total alkalinity and total hardness with
CaCO3Meter, Ca2+Calcium hardness is represented, the assay method of each parameter is as follows：
Ca2+：Reference standard GB/T 6910-2006；
Total alkalinity：Reference standard GB/T 15451-2006；
Total hardness：Reference standard GB/T 6909-2008；
Cl-：Reference standard GB/T 15453-2008；
SO4 2-：Reference standard GB/T 14642-2009；
PH value：Reference standard GB/T 6920-1986.
Table 3.
| Ca2+(mg/L) | Total alkalinity (mg/L) | Total hardness (mg/L) | Cl-(mg/L) | SO4 2-(mg/L) | pH |
| 500 | 100 | 700 | 700 | 200 | 8.0 |
The method of testing of corrosion inhibition is as follows：
The composite corrosion inhibitor that embodiments of the invention 1 to 14 are obtained carries out laboratory corrosion inhibition experiment.Specific side
Method includes：Composite corrosion inhibitor P1-P14 of the present invention is added separately in afore-mentioned test water, then tried 20# quality carbon steels
Piece is fixed on lacing film instrument (commercially available from Qin You instruments Chemical Co., Ltd.), is put into added with composite corrosion inhibitor P1- of the present invention
In P14 afore-mentioned test water, 45 ± 1 DEG C of steady temperature, rotating speed 75rpm is kept to rotate 72 hours, test piece before and after record experiment
Weight, calculate average corrosion rate and corrosion inhibition rate.Wherein, concentration of the composite corrosion inhibitor P1-P14 in afore-mentioned test water
As shown in (S+Zn) in table 4, the dosage of total solid in the corrosion inhibiter prepared by wherein S expressions according to embodiments of the present invention 1 to 14,
That Zn is represented is Zn2+Dosage.Meanwhile based on identical test condition, with blank sample, the water sulphur of single adding water soluble inorganic zinc salt seven
The Zn of sour zinc2+Corrosion inhibiter D5-D8 is as check experiment in sample and comparative example 5 to 8.Wherein：
" blank sample " is that the check experiment of any corrosion inhibiter is not added with test water；
" comparative example 5 " be in test water addition by lark prestige Science and Technology Ltd. production sodium gluconate with it is water-soluble
Property inorganic zinc salt white vitriol, which compounds, to be formed composite corrosion inhibitor (compound product is designated as D5, and it is in afore-mentioned test water
Concentration such as in table 4 shown in (S+Zn), wherein S represents the middle total solid dosage of sodium gluconate, and that Zn is represented is Zn2+Use
Amount) check experiment；
" comparative example 6 " be in test water addition by lark prestige Science and Technology Ltd. production sodium gluconate, I
The aspartic acid of fourth reagent (Shanghai) Co., Ltd. production compounds to form corrosion inhibiter group with water-soluble inorganic zinc salt white vitriol
(compound product is designated as D6 to compound, wherein each raw material is individually present, does not occur condensation reaction, and it is in afore-mentioned test water
Concentration such as in table 4 shown in (S+Zn), wherein S represents in sodium gluconate total solid in dosage/aspartic acid of total solid
Dosage, that Zn is represented is Zn2+Dosage) check experiment；
" comparative example 7 " is the calm and peaceful water treatment agent in Shandong that addition is produced by lark prestige Science and Technology Ltd. in test water
The YSW-109 of Co., Ltd's production (contains Zn2+) (product is designated as D7, (S+ in its concentration such as table 4 in afore-mentioned test water
Zn) shown in part) check experiment；
" comparative example 8 " is that by the Luoyang of lark prestige Science and Technology Ltd. production, imperial industry is limited by force for addition in test water
The hydroxy ethylene diphosphonic acid (HEDP) of company's production compounds to form corrosion inhibiter and combine with water-soluble inorganic zinc salt white vitriol
(compound product is designated as D8 to thing, and in its concentration such as table 4 in afore-mentioned test water shown in (S+Zn), wherein S is represented in HEDP
The dosage of total solid, that Zn is represented is Zn2+Dosage) check experiment.
Corrosion rate：The numerical value of test piece corrosion effect in unit interval.Such as metal erosion in unit area in the unit interval
Loss amount, unit are mm/a (millimeter/year).
Corrosion rate
In formula：
C：Computational constant, with mm/a (millimeter/year) for unit, C=8.76 × 107；
ΔW：The corrosion weight loss (g) of test specimen before and after experiment；
A：Corroded area (the cm of test specimen2)；
t：The time (h) of corrosion test；
ρ：Density (the kg/m of material for test3)。
Corrosion inhibition rate：The inhibition efficiency of corrosion inhibiter.
Corrosion inhibition rate calculation formula is：IE=100 × (W0-W1)/W0%
W0The corrosion weight loss (g) of test piece before and after being tested for blank solution；
W1To test front and rear test piece corrosion weight loss (g) added with corrosion inhibitor solution.
Test result：As shown in table 4.
Table 4.
| Composite corrosion inhibitor | (S+Zn) concentration (mgL-1) | Corrosion rate (mma-1) | Corrosion inhibition rate (%) |
| P1 | 17(15+2) | 0.025 | 96.2 |
| P2 | 17(15+2) | 0.027 | 95.9 |
| P3 | 17(15+2) | 0.028 | 95.7 |
| P4 | 17(15+2) | 0.060 | 90.9 |
| P5 | 17(15+2) | 0.039 | 94.0 |
| P6 | 17(15+2) | 0.033 | 95.0 |
| P7 | 17(15+2) | 0.034 | 94.8 |
| P8 | 17(15+2) | 0.037 | 94.4 |
| P9 | 17(15+2) | 0.040 | 93.9 |
| P10 | 17(15+2) | 0.041 | 93.8 |
| P11 | 17(15+2) | 0.045 | 93.2 |
| P12 | 17(15+2) | 0.042 | 93.6 |
| P13 | 17(15+2) | 0.050 | 92.4 |
| P14 | 17(15+2) | 0.055 | 91.6 |
| D5 | 17(15+2) | 0.189 | 71.3 |
| D6 | 17(5/10+2) | 0.155 | 76.4 |
| D7 | 100 | 0.065 | 90.1 |
| D8 | 17(15+2) | 0.045 | 93.2 |
| Zn2+ | 2 | 0.177 | 73.1 |
| Blank | - | 0.658 | - |
The corrosion inhibiter S1-S14 that be can be seen that from the data in table 4 according to prepared by the present invention is formed after being compounded with zinc salt
Composite corrosion inhibitor P1-P14 be applied to suppress aqueous corrosion there is preferable remission effect to corrosion of carbon steel, its corrosion mitigating effect is excellent
In using aliphatic hydroxyl carboxylic acid or its salt with formed after zinc salt compounding composite corrosion inhibitor (D5), better than using aspartic acid
Compounded with water-soluble inorganic zinc salt and to form composite corrosion inhibitor (D6), better than existing non-phosphate inhibitor (D7) and can reached
The level of the even more than existing corrosion inhibition containing phosphor corrosion inhibitor (D8).
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 the end points of disclosed scope and any value are not limited to the accurate model herein
Enclose or be worth, these scopes or value should be understood to comprising the value close to these scopes or value.For number range, Ge Gefan
Between the endpoint value enclosed, between the endpoint value of each scope and single point value, and individually can group each other between point value
Close and obtain one or more new number ranges, these number ranges should be considered as specific open herein.
It should be further stated that each particular technique feature described in above-mentioned embodiment, not
In the case of contradiction, it can be combined by any suitable means.In order to avoid unnecessary repetition, the present invention is to various
Possible combination 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 (18)
1. a kind of corrosion inhibiter, it is characterised in that the corrosion inhibiter contains compound and/or its salt and such as following formula as shown in following formula I
The condensation reaction products of compound shown in II,
In the Formulas I, R1For H or OH, R2For H or COOH, R3For COOH, CH2- COOH or
In the formula II, R4For H, C1-C4Alkyl, (CH2)n-COOH、(CH2)4-NH2、Or
CH2- OH, wherein n and m are each independently selected from 1 and 2.
2. corrosion inhibiter according to claim 1, wherein, the molecular weight distribution of the condensation reaction products is in 200-1000 models
In enclosing.
3. corrosion inhibiter according to claim 1, wherein, compound shown in the formula II and compound shown in the Formulas I and
The mol ratio of its salt is (0.5-8)：1, be preferably (1-4)：1.
4. corrosion inhibiter according to claim 1, wherein, the corrosion inhibiter also contains water, and the solid content of the corrosion inhibiter
For 25-55 weight %.
5. corrosion inhibiter according to claim 1, wherein, compound shown in Formulas I be gluconic acid, citric acid, tartaric acid and
One or more in malic acid；The salt of compound shown in Formulas I is sodium salt and/or sylvite, preferably sodium gluconate and/or Portugal
Grape saccharic acid potassium.
6. corrosion inhibiter according to claim 1, wherein, compound shown in formula II be glycine, alanine, aspartic acid,
One or more in serine, threonine, leucine, asparagine, glutamic acid and lysine, preferably aspartic acid.
7. a kind of preparation method of corrosion inhibiter, it is characterised in that the preparation method includes：
Under the conditions of condensation reaction, in the presence of a catalyst, aliphatic hydroxyl carboxylic acid and/or its salt are connect in water with amino acid
Touch, form the corrosion inhibiter；Wherein, the aliphatic hydroxyl carboxylic acid has the structure as shown in following formula I；The amino acid has such as
Structure shown in following formula II,
In the Formulas I, R1For H or OH, R2For H or COOH, R3For COOH, CH2- COOH or
In the formula II, R4For H, C1-C4Alkyl, (CH2)n-COOH、(CH2)4-NH2、Or
CH2- OH, wherein n and m are each independently selected from 1 and 2.
8. preparation method according to claim 7, wherein, the amino acid and aliphatic hydroxyl carboxylic acid and its mole of salt
Than for (0.5-8)：1, be preferably (1-4)：1.
9. preparation method according to claim 7, the catalyst is selected from sulfuric acid and/or nitric acid, it is preferable that the catalysis
Agent is using the mol ratio of pH meter and the aliphatic hydroxyl carboxylic acid and its salt as (0.4-6)：1, be preferably (1.6-3)：1.
10. preparation method according to claim 7, wherein, the condensation reaction condition includes：It is described contact be enough by
Water is carried out at a temperature of steaming, and is preferably placed in the container for carrying out the contact in the heating bath that temperature is 100-180 DEG C, described
The time of contact is 2-10 hours.
11. preparation method according to claim 7, wherein, the aliphatic hydroxyl carboxylic acid be gluconic acid, citric acid,
One or more in tartaric acid and malic acid, the salt of the aliphatic hydroxyl carboxylic acid are sodium salt and/or sylvite, preferred aliphat
The salt of hydroxycarboxylic acid is sodium gluconate and/or K-IAO.
12. preparation method according to claim 7, wherein, the amino acid is glycine, alanine, aspartic acid, silk
One or more in propylhomoserin, threonine, leucine, asparagine, glutamic acid and lysine, preferably described amino acid are asparagus fern
Propylhomoserin.
A kind of 13. corrosion inhibiter prepared by method as described in any one in claim 7 to 12.
14. a kind of composite corrosion inhibitor, it is characterised in that the composite corrosion inhibitor contains corrosion inhibiter and water-soluble inorganic zinc
Salt, the corrosion inhibiter are the corrosion inhibiter described in any one in claim 1 to 6 and 13.
15. composite corrosion inhibitor according to claim 14, wherein, the corrosion inhibiter in terms of its dry weight with the water solubility
The weight ratio that inorganic zinc salt is counted using Zn-ef ficiency is 100：(5-25), preferably 100：(7.5-20).
16. composite corrosion inhibitor according to claim 14, wherein, the water-soluble inorganic zinc salt be zinc sulfate and/or
Zinc nitrate.
17. the corrosion inhibiter in a kind of claim 1 to 6 and 13 described in any one, or in claim 14 to 16 it is any one
Application of the composite corrosion inhibitor in aqueous corrosion is suppressed described in；
Preferably, the corrosion inhibiter is using dosage of its total solids in water as 10-20mg/L, the composite corrosion inhibitor with
Wherein dosage of the total solids of corrosion inhibiter in water is 10-20mg/L.
A kind of 18. processing method of recirculated water, it is characterised in that this method be included in recirculated water add claim 1 to 6 and
Corrosion inhibiter in 13 described in any one, or the composite corrosion inhibitor in claim 14 to 16 described in any one；
Preferably, the corrosion inhibiter is using dosage of its total solids in water as 10-20mg/L, the composite corrosion inhibitor with
Wherein dosage of the total solids of corrosion inhibiter in water is 10-20mg/L.
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| CN110963583A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof |
| CN110963584A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Phosphorus-free composite corrosion inhibitor suitable for natural pH operation and application thereof |
| CN110963586A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Phosphorus-free composite corrosion inhibitor suitable for low-hardness water and application thereof |
| CN110963584B (en) * | 2018-09-28 | 2021-07-30 | 中国石油化工股份有限公司 | Phosphorus-free composite corrosion inhibitor suitable for natural pH operation and application thereof |
| CN110963583B (en) * | 2018-09-28 | 2021-08-03 | 中国石油化工股份有限公司 | Phosphorus-free composite corrosion inhibitor suitable for high-hardness water and application thereof |
| CN111039424A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor suitable for low-hardness water and application thereof |
| CN111039425A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor suitable for natural pH operation and application thereof |
| CN111039422A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor suitable for high-hardness water and application thereof |
| CN111039424B (en) * | 2018-10-12 | 2021-07-30 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor suitable for low-hardness water and application thereof |
| CN111039422B (en) * | 2018-10-12 | 2021-07-30 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor suitable for high-hardness water and application thereof |
| CN111039425B (en) * | 2018-10-12 | 2021-08-03 | 中国石油化工股份有限公司 | Composite scale and corrosion inhibitor suitable for natural pH operation and application thereof |
| CN109665634A (en) * | 2019-01-30 | 2019-04-23 | 上海电力学院 | A kind of macromolecule anti-incrustation corrosion inhibitor and its preparation method and application |
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