CN110066033A - Low-phosphorus corrosion and scale inhibitor composition and low-phosphorus corrosion and scale inhibitor and its application - Google Patents
Low-phosphorus corrosion and scale inhibitor composition and low-phosphorus corrosion and scale inhibitor and its application Download PDFInfo
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- CN110066033A CN110066033A CN201810065296.3A CN201810065296A CN110066033A CN 110066033 A CN110066033 A CN 110066033A CN 201810065296 A CN201810065296 A CN 201810065296A CN 110066033 A CN110066033 A CN 110066033A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
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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
- C02F5/14—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 phosphorus
- C02F5/145—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 phosphorus combined with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/173—Macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
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Abstract
The present invention relates to corrosion inhibiting and descaling agent fields, disclose a kind of low-phosphorus corrosion and scale inhibitor composition, wherein the composition contains polymer A, polymer B, organic phosphine compound, without phosphorus organic acid and/or without phosphorus acylate and water-soluble inorganic zinc salt；The polymer A is the copolymer of maleic anhydride and allyloxy polyoxyethylene maleic acid monoester, and the polymer B is no-phosphate corrosion polymer；The weight ratio of the polymer A, polymer B, organic phosphine compound, without phosphorus organic acid and/or without phosphorus acylate and water-soluble inorganic zinc salt is 1:(0.25-5): (0.08-1.67): (0.025-1): (0.05-1.26).The present invention also provides a kind of low-phosphorus corrosion and scale inhibitor and its applications.Low-phosphorus corrosion and scale inhibitor composition provided by the invention effectively reduces the dosage of corrosion inhibiter, and cost is greatly saved.
Description
Technical field
The present invention relates to a kind of low-phosphorus corrosion and scale inhibitor composition and low-phosphorus corrosion and scale inhibitor and its applications.
Background technique
Corrosion-mitigation scale-inhibition agent prescription used in China's cold water process is substantially based on phosphorus line formulation, although from performance
Substantially can reach requirement, but phosphorus line formulation still has deficiency: phosphorus system water treatment agent exists in use easily to be formed
The hidden danger of phosphoric acid salt crust influences heat transfer effect when water cooler longtime running；Phosphorus line formulation promotes microbial reproduction in recirculated water,
Consume a large amount of fungicide；The discharge of a large amount of phosphorus easily leads to the eutrophication of receiving water body.So developing using low-phosphorous or without phosphorus
Corrosion-mitigation scale-inhibition agent prescription has great importance to cold water process.
Corrosion inhibiting and descaling agent compound prescription is mainly reflected in resistance calcium carbonate scale, resistance phosphorus dirt and resistance zinc to the scale-inhibiting properties of recirculated water
Three aspect of dirt.With gradually popularizing for reusing sewage, a certain amount of phosphorus is inevitably contained in recirculated water, therefore even if use
Without phosphorus formula, without phosphorus formula should also have certain resistance phosphorus dirt ability.The antisludging agent single dose of low-phosphorus corrosion and scale inhibitor compound prescription
The main water-soluble polymer using synthesis, however the scale-inhibiting properties difference of different water soluble polymers is larger.Polyacrylic acid
(PAA), maleic acid-acrylic acid copolymer (MA-AA), hydrolysis of polymaleic anhydride (HPMA), poly-epoxy succinic acid (PESA), poly- day
The resistance calcium carbonate scale ability such as aspartic acid (PASP), phosphono based polycarboxylic acid (POCA) and copolymer of phosphono carboxylic acid (PCA) is strong, hinders phosphorus
Dirt and resistance zinc dirt ability are weak；Acrylic acid-acrylic ester analog copolymer, acrylic acid and hydroxypropyl acrylate copolymer (AA-HPA, T-
Etc. 225) resistance calcium carbonate scale, resistance phosphorus dirt and resistance zinc dirt ability are relatively strong；Acrylic acid-acrylic ester-co-polymer of sulfonate, propylene
The resistance such as acid and 2- acrylamide-2-methyl propane sulfonic copolymer (AA-AMPS) calcium carbonate scale, resistance phosphorus dirt and resistance zinc dirt ability are equal
By force；Allyloxy polyethoxy co-polymer of sulfonate (AA-APES), acrylic acid and 3- allyloxy -2- hydroxy-propanesulfonic acid are copolymerized
The resistance phosphorus dirt such as object (AA-AHPSE) and resistance zinc dirt ability are strong, it is weak to hinder calcium carbonate scale ability.
In the water-soluble polymer of synthesis, hydrolysis of polymaleic anhydride (HPMA), poly-epoxy succinic acid (PESA), poly- asparagus fern ammonia
Sour (PASP), phosphono based polycarboxylic acid (POCA) and copolymer of phosphono carboxylic acid (PCA) etc. have certain corrosion inhibiting ability, and poly- third
Olefin(e) acid (PAA), maleic acid-acrylic acid copolymer (MA-AA), acrylic acid-acrylic ester analog copolymer, acrylic acid and acrylic acid hydroxyl
Methacrylate-trimethoxysilyl propylmethacrylate copolymer (AA-HPA, T-225), acrylic acid-acrylic ester-co-polymer of sulfonate, acrylic acid and 2- acrylamide -2- first
Base sulphonic acid copolymer (AA-AMPS), allyloxy polyethoxy co-polymer of sulfonate (AA-APES), acrylic acid and 3- allyl
Oxygroup -2- hydroxy-propanesulfonic acid copolymer (AA-AHPSE) etc. is not only unable to inhibition, promotes corrosion instead.
CN 102674570A discloses a kind of compound low-phosphorus corrosion and scale inhibitor and its application, compound low-phosphorus corrosion and scale inhibitor
It is made of corrosion inhibiting and descaling agent A and corrosion inhibiting and descaling agent B, corrosion inhibiting and descaling agent A is by 20-40 parts of poly-epoxy succinic acid (PESA), glucose
Sour sodium 20-40 parts, 20-60 parts of water compositions；Corrosion inhibiting and descaling agent B is by 10-25 parts of hydrolysis of polymaleic anhydride (HPMA), acrylic acid/2-
10-25 parts of acrylamide -2- methacrylic sulfonic acid copolymer (AA/AMPS), 2- phosphonobutane -1,2,4- tricarboxylic acids (PBTCA)
5-10 parts, 10-25 parts of zinc salt, 1-2 parts of fluorescent tracer, 13-64 parts of water compositions.
CN 103253777A discloses a kind of anti-incrustation corrosion inhibitor composition and anti-incrustation corrosion inhibitor and its application, the scale inhibition
Corrosion inhibiter composition contains cyclodextrin and/or cyclodextrine derivatives, homopolymer containing carboxylic acid group, soluble metallic salt, contains sulfonic acid
Base co-polymer and the hydroxycarboxylic acid selectively contained, the weight ratio of each component are 1:0.2-20:0.04-15:0.2-30:0-20.
Carboxylic acid group's homopolymer is selected from polyacrylic acid (PAA), hydrolysis of polymaleic anhydride (HPMA), poly-epoxy succinic acid (PESA), poly- asparagus fern
Propylhomoserin (PASP), base co-polymer containing sulfonic acid are the carbonyl alkene of carbon atom number 3-4 and the copolymer of olefin containing sulfonic acid.
Contain acrylic acid/2- acrylamide -2- methyl-prop in compound low-phosphorus corrosion and scale inhibitor disclosed in CN 102674570A
Alkene sulfonic acid copolymer (AA/AMPS).It is former that anti-incrustation corrosion inhibitor composition disclosed in CN 103253777A contains polyacrylic acid, carbon
The carbonyl alkene of subnumber 3-4 and the base co-polymer containing sulfonic acid of olefin containing sulfonic acid.These substances can promote corrosion, in order to offset
The increased etching extent of these substances, it is necessary to increase inhibiter consumption in formula, use cost is caused to increase.
Summary of the invention
The purpose of the present invention is to provide a kind of low-phosphorus corrosion and scale inhibitor composition and low-phosphorus corrosion and scale inhibitor and its applications.
To achieve the goals above, according to the first aspect of the invention, the present invention provides a kind of low-phosphorus corrosion and scale inhibitors
Composition, wherein the composition contains polymer A, polymer B, organic phosphine compound, without phosphorus organic acid and/or without phosphorus has
Machine hydrochlorate and water-soluble inorganic zinc salt；The polymer A is maleic anhydride and allyloxy polyoxyethylene maleic acid monoester
Copolymer, the polymer B are no-phosphate corrosion polymer；It is the polymer A, polymer B, organic phosphine compound, without phosphorus organic
The weight ratio of sour and/or without phosphorus acylate and water-soluble inorganic zinc salt is 1:(0.25-5): (0.08-1.67): (0.025-
1):(0.05-1.26)。
According to the second aspect of the invention, the present invention provides a kind of low-phosphorus corrosion and scale inhibitor, the low-phosphorus corrosion scale inhibitions
Agent contains low-phosphorus corrosion and scale inhibitor composition and water, wherein the low-phosphorus corrosion and scale inhibitor composition is of the present invention low
Phosphorus corrosion inhibiting and descaling agent composition.
According to the third aspect of the invention we, the present invention provides the low-phosphorus corrosion and scale inhibitors in processing cycle cooling water
Application.
Due to the inventors found that polymer A (maleic anhydride and allyloxy polyoxyethylene maleic acid monoester
Copolymer) there is corrosion inhibition, combination can be effectively reduced under the premise of not influencing treatment effect in formula according to the invention
The dosage of corrosion inhibiter in object is saved greatly cost, and polymer A, polymer B, organic phosphine in formula of the invention
Object, without phosphorus organic acid and/or without phosphorus acylate, water-soluble inorganic zinc salt are closed in the presence of synergistic effect, reduces making for each single dose
Dosage reduces operating cost.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
It should be understood that the specific embodiments described herein are merely illustrative of the invention, it is not used to
The limitation present invention.
In the present invention, "at least one" refers to one or more kinds of mixtures.
The present invention provides a kind of low-phosphorus corrosion and scale inhibitor compositions, wherein the composition contains polymer A, polymerization
Object B, organic phosphine compound, without phosphorus organic acid and/or without phosphorus acylate and water-soluble zinc salt.Wherein, the polymer A is
The copolymer (MA-APEM) of maleic anhydride and allyloxy polyoxyethylene maleic acid monoester, the polymer B are poly- for no-phosphate corrosion
Close object；The polymer A, polymer B, organic phosphine compound, without phosphorus organic acid and/or without phosphorus acylate and water-soluble inorganic
The weight ratio of zinc is 1:(0.25-5): (0.08-1.67): (0.025-1): (0.05-1.26).
According to the present invention, the polymer A, polymer B, organic under preferable case in order to further increase corrosion mitigating effect
The weight ratio of phosphorus compound, without phosphorus organic acid and/or without phosphorus acylate and water-soluble inorganic zinc salt is 1:(0.6-2.4):
(0.2-0.8):(0.09-0.36):(0.13-0.5)。
According to the present invention, in order to further increase corrosion mitigating effect, under preferable case, the weight average molecular weight of the polymer A
For 1000-20000, more preferably 2000-10000.
In the present invention, the copolymer of the polymer A, i.e. maleic anhydride and allyloxy polyoxyethylene maleic acid monoester can
With by being prepared, in the specific embodiment of the present invention, the polymer A is preferably prepared in accordance with the following steps:
It is made using maleic anhydride (MA), allyloxy polyoxyethylene ether as raw material by being esterified and polymerizeing two-step reaction, tool
Body the following steps are included:
(1) esterification: under enzymatic synthesis condition, maleic anhydride is mixed with allyloxy polyoxyethylene ether, is esterified
Reaction, obtains allyloxy polyoxyethylene maleic acid monoester (APEM).The esterification condition generally comprise reaction temperature and
Reaction time, wherein set out for the angle that balance promotes esterification and improves reaction efficiency, the reaction temperature can be with
It is 70-120 DEG C, more preferably 80-100 DEG C, the reaction time can be 1-6h.Maleic anhydride and allyloxy polyoxyethylene ether
The ratio between amount of substance is preferably 1:0.9-1.1.
(2) polymerization reaction: under the polymerization conditions, in maleic anhydride (MA) solution, by the alkene of initiator and preparation
Propoxyl group polyoxyethylene maleic acid monoester (APEM) contact carries out polymerization reaction, obtains maleic anhydride and allyloxy polyoxyethylene
The copolymer (abbreviation MA-APEM copolymer) of maleic acid monoester, may be used as corrosion inhibiter.The specific way of contact can be with are as follows: will
Initiator and the allyloxy polyoxyethylene maleic acid monoester (APEM) of step (1) preparation instill (preferably same separately or together
When instill) carry out polymerization reaction in maleic anhydride (MA) solution.The polymeric reaction condition generally comprises reaction temperature and reaction
Time, wherein set out for the angle that balance promotes polymerization reaction and improves reaction efficiency, the reaction temperature is preferably
75-100 DEG C, the reaction time is preferably 2-5h.
In the present invention, in esterification stage, the preferably described allyloxy polyoxyethylene ether weight average molecular weight is 230-
2500, i.e., vinethene repetitive unit is 4-55, it is further preferred that the allyloxy polyoxyethylene ether weight average molecular weight is 320-
1100, i.e. vinethene repetitive unit is 6-24.
In the present invention, in polymerization stage, the quality proportioning of MA and APEM can be 5:95-95:5, preferably 10:
90-75:25, initiator are preferably one of ammonium persulfate, sodium peroxydisulfate, potassium peroxydisulfate or a variety of, the additive amount of initiator
(quality) is preferably the 2-12% of MA Yu APEM quality sum, more preferably 3-8%, specifically can be according to required copolymer
Weight average molecular weight is selected.
In the present invention, the quality sum of preferably MA, APEM and initiator account for the 10-50% of solution gross mass, more preferably
20-40%.
The copolymer of maleic anhydride used in the embodiment of the present invention and allyloxy polyoxyethylene maleic acid monoester, makes
Use allyloxy polyoxyethylene ether that maleic anhydride (MA) and weight average molecular weight are 500 as esterification raw material, reaction temperature
It is 85 DEG C, reaction time 4h, esterification has obtained allyloxy polyoxyethylene maleic acid monoester (APEM)；By quality proportioning
Polymerization reaction is carried out in the presence of initiator for the APEM and MA of 5:95-95:5, needs to adjust according to different weight average molecular weight
Polymeric reaction condition and initiator amount, obtain the present invention claims preferred weight average molecular weight MA-APEM copolymer.
According to the present invention, optional wider range of the type of the polymer B, non-phosphate inhibitor polymer are used equally for this
Invention, in order to further increase corrosion mitigating effect, for the present invention, the preferred polymer B be selected from poly-aspartate (PASP),
At least one of poly-epoxy succinic acid (PESA) and hydrolysis of polymaleic anhydride (HPMA).
According to the present invention, in order to further increase corrosion mitigating effect, the organic phosphorus compound is selected from 2- hydroxy phosphinylidyne base second
At least one of sour (HPAA), phosphono based polycarboxylic acid (POCA) and copolymer of phosphono carboxylic acid (PCA).
According to the present invention, optional wider range of the type of the without phosphorus organic acid, in order to further increase corrosion mitigating effect,
For the present invention, it is different anti-bad that the without phosphorus organic acid is preferably selected from ascorbic acid, hydroascorbic acid, arabo-ascorbic acid and dehydrogenation
At least one of hematic acid.Optional wider range of the type of the without phosphorus acylate, preferably gluconate, such as can
Think in sodium gluconate, K-IAO, maltonic acid sodium, maltonic acid potassium, zinc gluconate and manganese gluconate
At least one.Wherein, most preferably, the without phosphorus organic acid and/or without phosphorus acylate are without phosphorus organic acid, more preferably anti-
At least one of bad hematic acid, hydroascorbic acid, arabo-ascorbic acid and dehydrogenation arabo-ascorbic acid.
In the present invention, the water-soluble inorganic zinc salt can be various water-soluble nothings conventional use of in water treatment agent field
Machine zinc salt, especially preferably selected from one of zinc chloride, zinc sulfate and zinc nitrate or a variety of, particularly preferably zinc sulfate and/
Or zinc chloride.In the present invention, it is big that the water-soluble inorganic zinc salt, which refers generally to solubility (20 DEG C, 1 atmospheric pressure under) in water,
In the inorganic zinc salt of 1 weight %.
The present invention provides a kind of low-phosphorus corrosion and scale inhibitor, the low-phosphorus corrosion and scale inhibitor contains low-phosphorus corrosion and scale inhibitor group
Object and water are closed, the low-phosphorus corrosion and scale inhibitor composition is low-phosphorus corrosion and scale inhibitor composition of the present invention.
Low-phosphorus corrosion and scale inhibitor according to the present invention, it is preferable that described on the basis of the total amount of the low-phosphorus corrosion and scale inhibitor
The content of low-phosphorus corrosion and scale inhibitor composition is 25-85 weight %, preferably 30-80 weight %, more preferably 40-72 weight
Measure %；The content of water is 15-75 weight %, preferably 20-70 weight %, more preferably 28-60 weight %.
Low-phosphorus corrosion and scale inhibitor according to the present invention, it is preferable that on the basis of the total amount of the low-phosphorus corrosion and scale inhibitor, polymerization
The content of object A is 5-40 weight %, more preferably 10-30 weight %；The content of polymer B is 12-35 weight %, more preferably
18-30 weight %；The content of organic phosphine compound is 4-12 weight %, more preferably 6-10 weight %.Without phosphorus organic acid and/or
The content of without phosphorus acylate is 2-5 weight %, more preferably 2.7-4.5 weight %；The content of water-soluble inorganic zinc salt is 3-7
Weight %, more preferably 3.9-6.3 weight %, remaining is water.
Low-phosphorus corrosion and scale inhibitor according to the present invention, it is preferable that on the basis of the total amount of the low-phosphorus corrosion and scale inhibitor, phosphoric acid
The content of root is lower than 4 weight %.
The present invention provides application of the low-phosphorus corrosion and scale inhibitor of the present invention in processing cycle cooling water.
Application according to the present invention, preferably with respect to every liter of recirculated cooling water, the dosage of low-phosphorus corrosion and scale inhibitor is 70-
140mg, more preferably 90-110mg.
Below with reference to embodiment, the present invention will be described in detail, but the present invention is not limited to this.
Various raw materials used in embodiment are commercially available.
The detection method of the corrosion inhibition of corrosion inhibiting and descaling agent and scale-inhibiting properties is referring in the embodiment of the present invention and comparative example
What production department, petrochemical industry parent company, state and development division were write, and " cooling water analysis and test method " (1993, Anqing petroleum
Work head factory information centre publish) in 401,402,403 methods and 404 methods.Wherein, low-phosphorous relative to every liter of Beijing tap water
The dosage of corrosion inhibiting and descaling agent is 100mg.Test water used is Beijing tap water in the embodiment of the present invention and comparative example, and water quality is shown in Table
1, corrosion rate and scale inhibition performance are shown in Table 2.
The 1 main water quality of Beijing tap water of table
In the present invention, the definition of average corrosion rate is the inhibition efficiency of corrosion inhibiting and descaling agent, the calculating of average corrosion rate
Formula are as follows:
In formula: F-corrosion rate, mm/a；
C-computational constant (8.76 × 107)；
△ W-test specimen corrosion weight loss, g；
A-test specimen area, cm2；
T-corrosion test time, h；
ρ-material for test density, kg/dm3。
Resistance calcium carbonate scale rate is defined as the resistance calcium carbonate scale efficiency of corrosion inhibiting and descaling agent, hinders the calculation formula of calcium carbonate scale rate
Are as follows:
In formula: N-cycles of concentration
Ca2+ 0The Ca surveyed before the test of-test solution2+Mass concentration, mg/L；
Ca2+ 1The test solution of-adding medicine, the Ca after test2+Mass concentration, mg/L；
Ca2+ 2- not adding medicine test solution (blank) test after Ca2+Mass concentration, mg/L.
Resistance phosphorus dirt rate is defined as the resistance phosphorus dirt efficiency of corrosion inhibiting and descaling agent, hinders the calculation formula of phosphorus dirt rate are as follows:
In formula:It is surveyed before the test of-test solutionMass concentration, mg/L；
After the test of-adding medicine test solutionMass concentration, mg/L；
- not adding medicine test solution (blank) test afterMass concentration, mg/L.
Resistance zinc dirt rate (also referred to as steady zinc rate) is defined as the resistance zinc dirt efficiency of corrosion inhibiting and descaling agent, hinders the calculation formula of zinc dirt rate
Are as follows:
In formula:The Zn measured before the test of-test solution2+Mass concentration, mg/L；
The Zn measured after the test of-adding medicine test solution2+Mass concentration, mg/L.
- the Zn that adding medicine test solution (blank) does not measure after testing2+Mass concentration, mg/L.
Embodiment 1
It weighs 3.9g zinc chloride to be placed in 250mL beaker, addition 39.4g deionized water, after stirring and dissolving, adds 30g
MA-APEM (weight average molecular weight 2000), 18g HPMA (article number LH-10), 6g HPAA and 2.7g ascorbic acid, stir evenly,
Corrosion inhibiting and descaling agent is obtained, the content of phosphate radical is 1.5 weight %.
Embodiment 2
It weighs 6.3g zinc sulfate to be placed in 250mL beaker, addition 29.2g deionized water, after stirring and dissolving, adds 20g
MA-APEM (weight average molecular weight 10000), 30g PASP (article number LH-157), 10g POCA (article number LH-164) and 4.5g
Hydroascorbic acid stirs evenly, and obtains corrosion inhibiting and descaling agent, and the content of phosphate radical is 0.7 weight %.
Embodiment 3
It weighs 5g zinc nitrate to be placed in 250mL beaker, addition 49.4g deionized water, after stirring and dissolving, adds 10g
MA-APEM (weight average molecular weight 5500), 24g PESA (article number LH-158), 8g HPAA and 3.6g arabo-ascorbic acid, stirring are equal
It is even, corrosion inhibiting and descaling agent is obtained, the content of phosphate radical is 2.0 weight %.
Embodiment 4
It weighs 3.2g zinc chloride to be placed in 250mL beaker, addition 38.8g deionized water, after stirring and dissolving, adds 40g
MA-APEM (weight average molecular weight 1500), 12g PESA (article number LH-158), 4g POCA (article number LH-164) and 2g are anti-bad
Hematic acid stirs evenly, and obtains corrosion inhibiting and descaling agent, and the content of phosphate radical is 0.3 weight %.
Embodiment 5
It weighs 5g zinc sulfate to be placed in 250mL beaker, addition 58.5g deionized water, after stirring and dissolving, adds 5g MA-
APEM (weight average molecular weight 15000), 20g PASP (article number LH-157), 7.5g HPAA and 4g arabo-ascorbic acid, stirring are equal
It is even, corrosion inhibiting and descaling agent is obtained, the content of phosphate radical is 1.9 weight %.
Comparative example 1
Except with 30g MA-APEM in 30g AA-AMPS alternate embodiment 1, remaining ingredient and dosage are constant, inhibition resistance is obtained
Dirty agent, the content of phosphate radical are 1.5 weight %.
Comparative example 2
Except with 30g MA-APEM in 30g MA-APES alternate embodiment 1, remaining ingredient and dosage are constant, inhibition resistance is obtained
Dirty agent, the content of phosphate radical are 1.5 weight %.
Comparative example 3
On the basis of comparative example 1,3.9g zinc chloride, 18g HPMA, 6g HPAA and 2.7g ascorbic acid increase separately to
12g, 36g, 12g and 8g, obtain corrosion inhibiting and descaling agent, and the content of phosphate radical is 3.65 weight %.
Corrosion inhibition is carried out to the resulting corrosion inhibiting and descaling agent of embodiment 1-5 and comparative example 1-3 respectively and scale-inhibiting properties carry out
Evaluation.As a result such as table 2.
Table 2
As shown in Table 2, corrosion inhibiting and descaling agent according to the invention is formulated, in the premise for guaranteeing scale inhibition effect
Under, corrosion rate substantially reduces, and relative to comparative example 3, if according to the corrosion inhibiting and descaling agent of the formula of the prior art in order to obtain
Almost the same corrosion mitigating effect, needs to greatly improve the dosage of corrosion inhibiter with the present invention.It can be seen that low-phosphorus corrosion of the invention
Scale inhibitor composition effectively reduces the dosage of corrosion inhibiter, is saved greatly cost.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (13)
1. a kind of low-phosphorus corrosion and scale inhibitor composition, which is characterized in that the composition contains polymer A, polymer B, organic
Phosphine compound, without phosphorus organic acid and/or without phosphorus acylate and water-soluble inorganic zinc salt；The polymer A is maleic anhydride
With the copolymer of allyloxy polyoxyethylene maleic acid monoester, the polymer B is no-phosphate corrosion polymer；The polymer A,
The weight ratio of polymer B, organic phosphine compound, without phosphorus organic acid and/or without phosphorus acylate and water-soluble inorganic zinc salt is 1:
(0.25-5):(0.08-1.67):(0.025-1):(0.05-1.26)。
2. composition according to claim 1, wherein the polymer A, polymer B, organic phosphine compound, without phosphorus have
The weight ratio of machine acid and/or without phosphorus acylate and water-soluble inorganic zinc salt is 1:(0.6-2.4): (0.2-0.8): (0.09-
0.36):(0.13-0.5)。
3. composition according to claim 1, wherein the weight average molecular weight of the polymer A is 1000-20000, preferably
For 2000-10000.
4. composition described in any one of -3 according to claim 1, wherein the polymer B is selected from poly-aspartate, gathers
At least one of Epoxysuccinic acid and hydrolysis of polymaleic anhydride.
5. composition described in any one of -3 according to claim 1, wherein the organic phosphine compound is selected from 2- hydroxyl phosphine
At least one of acyl acetic acid, phosphono based polycarboxylic acid and copolymer of phosphono carboxylic acid.
6. composition described in any one of -3 according to claim 1, wherein the without phosphorus organic acid be selected from ascorbic acid,
At least one of hydroascorbic acid, arabo-ascorbic acid and dehydrogenation arabo-ascorbic acid, the without phosphorus acylate are selected from grape
At least one in sodium saccharate, K-IAO, maltonic acid sodium, maltonic acid potassium, zinc gluconate and manganese gluconate
Kind；It is preferred that the without phosphorus organic acid and/or without phosphorus acylate are without phosphorus organic acid.
7. composition described in any one of -3 according to claim 1, wherein the water-soluble inorganic zinc salt is selected from chlorination
At least one of zinc, zinc sulfate and zinc nitrate.
8. a kind of low-phosphorus corrosion and scale inhibitor, the low-phosphorus corrosion and scale inhibitor contains low-phosphorus corrosion and scale inhibitor composition and water, special
Sign is that the low-phosphorus corrosion and scale inhibitor composition is low-phosphorus corrosion and scale inhibitor group described in any one of claim 1-7
Close object.
9. low-phosphorus corrosion and scale inhibitor according to claim 8, wherein using the total amount of the low-phosphorus corrosion and scale inhibitor as base
Standard, the content of the low-phosphorus corrosion and scale inhibitor composition are 25-85 weight %, preferably 30-80 weight %, more preferably 40-
72 weight %；The content of water is 15-75 weight %, preferably 20-70 weight %, more preferably 28-60 weight %.
10. low-phosphorus corrosion and scale inhibitor according to claim 8 or claim 9, wherein the total amount with the low-phosphorus corrosion and scale inhibitor is
Benchmark, the content of polymer A are 5-40 weight %, and the content of polymer B is 12-35 weight %, the content of organic phosphine compound
For 4-12 weight %, the content of without phosphorus organic acid and/or without phosphorus acylate is 2-5 weight %, and water-soluble inorganic zinc salt contains
Amount is 3-7 weight %, remaining is water；
It is preferred that the content of polymer A is 10-30 weight %, polymer B on the basis of the total amount of the low-phosphorus corrosion and scale inhibitor
Content be 18-30 weight %, the content of organic phosphine compound is 6-10 weight %, without phosphorus organic acid and/or without phosphorus organic acid
The content of salt is 2.7-4.5 weight %, and the content of water-soluble inorganic zinc salt is 3.9-6.3 weight %, remaining is water.
11. low-phosphorus corrosion and scale inhibitor according to claim 8 or claim 9, wherein the total amount with the low-phosphorus corrosion and scale inhibitor is
The content of benchmark, phosphate radical is lower than 4 weight %.
12. application of the low-phosphorus corrosion and scale inhibitor in processing cycle cooling water described in any one of claim 8-11.
13. application according to claim 12, wherein relative to every liter of recirculated cooling water, the use of low-phosphorus corrosion and scale inhibitor
Amount is 70-140mg, preferably 90-110mg.
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