CN106082457B - Phosphate-free corrosion inhibition antisludging agent and application suitable for middle soft and strong corrosive water quality - Google Patents
Phosphate-free corrosion inhibition antisludging agent and application suitable for middle soft and strong corrosive water quality Download PDFInfo
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- CN106082457B CN106082457B CN201610654172.XA CN201610654172A CN106082457B CN 106082457 B CN106082457 B CN 106082457B CN 201610654172 A CN201610654172 A CN 201610654172A CN 106082457 B CN106082457 B CN 106082457B
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- phosphate
- corrosion inhibition
- antisludging agent
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
- C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
- C02F5/105—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances combined with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- 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
- C02F5/125—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 combined with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/08—Corrosion inhibition
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/22—Eliminating or preventing deposits, scale removal, scale prevention
Abstract
The present invention relates to a kind of phosphate-free corrosion inhibition antisludging agent and its application suitable for middle soft and strong corrosive water quality, which is consisted of the following components in percentage by weight: terpolymer 15~30%, hydrolyzed polymaleic anhydride 12~20%, sodium gluconate 0.1~10%, aliphatic alcohol polyethenoxy alkyl ether-carboxyl-Sulfo propionic acid ester copolymer 15~40% containing AMPS, pH adjusting agent 0.1~3%, zinc salt 0.1~12%, benzotriazole 0.1~5.0%, water soluble inert fluorescent tracer 0.5~5.0%, deionized water 15~40%.Compared with prior art, the present invention solves general phosphate-free corrosion inhibition antisludging agent and is difficult to take into account the defect of inhibition, scale effect in circulation concentration process.The phosphate-free corrosion inhibition antisludging agent function admirable, stability is good, has general applicability in middle soft and strong corrosive water quality, this product has the characteristics that without phosphorus, environment-friendly high-efficiency.
Description
Technical field
The present invention relates to a kind of phosphate-free corrosion inhibition antisludging agents suitable for industrial circulating cooling water system, more particularly, to one kind
Phosphate-free corrosion inhibition antisludging agent and application suitable for middle soft and strong corrosive water quality.
Background technique
In order to cooperate national economy Transformation Development and protect resource environment, National Environmental Protection Agency increases environment monitoring power
Degree, wherein the prevention and treatment, monitoring of water pollution are the most important things.On the one hand government encourages enterprise excellent using new and high technology, performance scientific research
Gesture realizes technology shifts upgrading, saves water effective and reasonablely and water conservation is not contaminated, while environmental protection administration increases
To environmentally friendly illegal investigation, punishment dynamics, manufacturing enterprise is strict with water terminal sewerage and reaches local environment protection emission
It is required that.
The use of phosphorus system medicament leads to water to a large amount of phosphorus-containing compound is brought in industrial discharge water in Treatment of Industrial Water
The eutrophication of matter accelerates microorganism and the growth of tongue fur algae of water system, causes the generation of " red tide " phenomenon.Present many countries
Forbid phosphorus discharge or the measure of limiting emission with regional take in succession.China has also formulated stringent standard to the discharge of phosphorus,
It is provided according to " GB 8979-1996 integrated wastewater discharge standard ", all pollutant discharging unit's first discharge standard total phosphorus≤0.5mg/l,
Secondary discharge standard is 1.0mg/l, therefore in Treatment of Industrial Water, and the water treatment agent of non-phosphate environment-friendly type obtains pole both domestic and external
Big to pay attention to, correlative study also gradually increases.For circulation, studying more nonphosphorus, inorganic corrosion inhibiter mainly has molybdic acid
Salt, tungstates, silicate, nitrate, borate and rare earth compound etc., the wherein rust inhibition of silicate, nitrate, borate
Can be poor, and molybdate, tungstates and rare earth compound it is on the high side.For this purpose, people endeavour to develop it is functional,
Inexpensively, nontoxic phosphate-free corrosion inhibition antisludging agent.
Study at present more without phosphorus organic inhibitor mainly include organic amine, imidazolines, aminocarboxylic acids and
Thiocarboxylic acid class, and phosphate-free corrosion inhibition antisludging agent poly-aspartate and poly-epoxy succinic acid with biodegradability.
The medicaments such as organic amine, imidazolines are mainly to prevent based on corrosion, since its corrosion inhibition does not protrude, and
Substantially do not have a scale inhibition function, practical application it is seldom.Aminocarboxylic acids and thiocarboxylic acid class, mainly as corrosion inhibiting and descaling agent
Compound ingredient use, cooperate with other dosage components and complete corrosion-mitigation scale-inhibition and act on, especially cooperateed with zinc salt
Can just have certain corrosion inhibition, it is more loose in the protective film that metal surface is formed due to the defect of zinc salt itself, especially
It is under middle soft water quality and its strong corrosive condition of water quality, the protective film that zinc salt is formed cannot prevent metal surface shape
At point corrosion, it is existing that such compounding corrosion inhibiting and descaling agent is difficult to the spot corrosion for inhibiting metal material, particularly carbon steel material to be easy to appear
As being subject to certain restrictions in actual use.Aspartic acid and Epoxysuccinic acid are used mainly as antisludging agent, are had good
Biological degradability, be newly into developing representative Phosphateless environmentally friendly antisludging agent, but which are mainly applied to inclined fouling tendency water
Matter, the scale effect of completion system is cooperateed with other medicine components, and corrosion inhibition is poor.
Since phosphate-free water treatment agent research is later, it is successfully applied to the without phosphorus water treating corrosion and scale inhibitor of industrial application at present
It is of less types, be especially applicable in phosphate-free corrosion inhibition antisludging agent that the various complicated water quality systems of industrial circulating water system use it is few again
It is few.But with the development of without phosphorus water treatment technology, the use of the corrosion inhibiting and descaling agent based on phosphorus system will be environmentally protective nothing
Phosphorus water treatment agent is substituted, and the exploitation of environmentally protective water treatment agent will be future thrust.
It is the typical extremely low hardness in south, low alkaline soft water water quality and other middle softs, basicity water for water quality type
The open type circulation of matter, the corrosion tendency of water is very strong, water quality operation or from low dense under low loading conditions for a long time
Demagnification rate transits to during day-to-day operation, and the corrosion control of system is the difficult point of without phosphorus reagent combination control.In existing industry
In technology on circulating cooling water treatment, due to technology, cost etc., answered for the reality of the phosphate-free corrosion inhibition antisludging agent of soft water system
It is less, main reason is that, on the one hand the concentration of without phosphorus reagent combination can pass through detection not as good as phosphorus system medicament in water body
Total phosphorus controls, and copolymer or homopolymer ingredient are difficult to detect by general spectrophotometric analysis means；On the other hand logical
Normal phosphate-free corrosion inhibition antisludging agent is mainly compounded by dirt dispersion agent with zinc salt, and dirt dispersion agent ingredient is in addition to requiring
Outside good antiscaling dispersion function, suitable for high concentration ratio or high rigidity, in the inclined fouling tendency water quality of basicity, assist zinc
Salt shows to form adsorbed film, inhibition corrosion of metal in metal material.
According to the mechanism that zinc salt forms a film, usual zinc salt shows that the protective film to be formed is more loose in metal material, due to not
Fine and close phosphorus zinc deposition film can be formed, therefore the adsorbed film based on zinc salt easily causes the spot corrosion of equipment, metal material is once
Spot corrosion is formed, can equally generate biggish harm, particular for the water quality of severe corrosive, prolonged spot corrosion state to equipment
It cannot be effectively controlled, may cause the uncontrollable corrosion failure of equipment, generate direct economic loss, provided according to document
Material is controlled without a kind of phosphate-free corrosion inhibition antisludging agent for the point corrosion of circulation on the market at present.
The technology according to existing for the water quality characteristic and without phosphorus medicament at present of middle soft and strong corrosive water quality system lacks
It falls into, objectively requires to develop that a kind of corrosion and scale inhibition performance is excellent, can be realized stability contorting, and have more spot corrosion specific aim
Phosphate-free corrosion inhibition antisludging agent formula.For the processing of strong corrosive water quality, Chinese invention patent (notification number: CN102092863A)
On June 15th, 2011 disclose it is a kind of " for the phosphate-free corrosion inhibition antisludging agent of strong corrosive water treatment and its application and its
Use the detection method of concentration ", technical solution include by weight percentage, it is composed of the following components: poly-epoxy succinic acid
20~60%, S- carboxyethyl sulfosuccinic acid 5.5~25%, chain alkyl polyetheramides 5~43%, containing the quarternary copolymerized of AMPS
Object 10~35%, benzotriazole 0.2~1%, water soluble fluorescence compound 0.5~5%, pH value adjustment agent 1.5~3%, zinc
Salt 0~15%, deionized water 10~40%.Wherein, the quadripolymer containing AMPS is with sulfonic group, carboxylic acid group, hydroxyl
The without phosphorus copolymer of base and ehter bond functional group.The water soluble fluorescence compound is that maximum excitation wavelength is 390nm, emission maximum
Wavelength is the water soluble fluorescence compound of 530nm.The pH adjusting agent is sodium hydroxide, potassium hydroxide, sulfuric acid or nitric acid.
The zinc salt is zinc chloride or zinc sulfate.
Foregoing invention patent is used for by detection technique of fluorescence although can be quickly detected from industrial circulating cooling water
The use concentration of the phosphate-free corrosion inhibition antisludging agent of strong corrosive water treatment is emphasized quickly detect phosphate-free corrosion inhibition antisludging agent
Using concentration, convenient for the control of drug concentration, but according to the property of fluorescent chemicals, it is placed in when general fluorescent chemicals
When industrial circulating cooling water system, it is possible to so that fluorescence signal is generated 10% or more signal intensity, that is, lead to analysis detection knot
The deviation of fruit makes the concentration of actually possessing of phosphate-free corrosion inhibition antisludging agent generate larger deviation, is likely to result in medicine in practical applications
The lag of agent control, directly affects the performance of the comprehensive performance of phosphate-free corrosion inhibition antisludging agent.
In addition to this, the technical solution of foregoing invention patent, since its formula is mainly the mixture of polymer and zinc salt,
Therefore in the corrosion control application of strong corrosive water quality system, due to being formulated property itself, can not well inhibit to corrode
Property water quality system point corrosion, to still be difficult to well solve the problems, such as the corrosion control of corrosive water plastidome.
Summary of the invention
The object of the invention is in order to overcome technological deficiency existing for existing phosphate-free corrosion inhibition antisludging agent and provide one
The phosphate-free corrosion inhibition antisludging agent and application of soft and strong corrosive water quality in kind.Phosphate-free corrosion inhibition antisludging agent of the invention can be effective
The etching problem of soft, low alkalinity and strong corrosive water quality system in control effectively inhibits the point of corrosive water plastidome
Etching problem.
The purpose of the present invention can be achieved through the following technical solutions:
Suitable for the phosphate-free corrosion inhibition antisludging agent of middle soft and strong corrosive water quality, the phosphate-free corrosion inhibition antisludging agent is by following heavy
The group of amount percentage is grouped as:
It is further preferred that the phosphate-free corrosion inhibition antisludging agent consists of the following components in percentage by weight:
Preferably, the terpolymer containing AMPS be containing carboxylic acid group, sulfonic group, acrylate copolymer.
Preferably, aliphatic alcohol polyethenoxy alkyl ether-carboxyl-Sulfo propionic acid ester copolymer is C14~C18 fat
- 1 Sulfo propionic acid ester of alcohol polyoxyethylene alkyl ether 3- carboxyl.
Preferably, the pH adjusting agent is sodium hydroxide, sulfuric acid or nitric acid.
Preferably, the zinc salt is zinc chloride or zinc sulfate.
Preferably, it is 365nm that the water soluble inert fluorescent tracer, which is maximum excitation wavelength, and maximum emission wavelength is
The water soluble inert fluorescent chemicals of 400nm, the water soluble fluorescence compound are preferably 1,3,6,8- pyrene tetrasulfonic acid tetrasodium salts.
When the phosphate-free corrosion inhibition antisludging agent is used for middle soft and strong corrosive water treatment, in middle soft and strong corruption
Use concentration in the industrial circulating cooling water of corrosion water quality is 60~200mg/L.
PH value of the phosphate-free corrosion inhibition antisludging agent in the aqueous solution that weight percent is 1% is 1.5~4.5.
Use of the phosphate-free corrosion inhibition antisludging agent in the industrial circulating cooling water of middle soft and strong corrosive water quality
Detection method includes the following steps for concentration:
1) apparatus selection: selection fluorescence mode carries out using Concentration Testing；
2) starting/termination wavelength parameter of fluorescent exciting, starting/termination of fluorescence emission wavelengths parameter setting: are set
Wavelength parameter, default value may be selected in other；
3) it measurement standard sample and establishes regression curve: the without phosphorus slow of middle soft and strong corrosive water treatment will be used for
Erosion antisludging agent is configured to standard solution according to various concentration gradient respectively, makes function using the standard regression curvilinear equation of instrument
Can, then the corresponding fluorescent value of each standard solution of sequentially determining passes through after the fluorescent value measurement for completing standard sample concentration
The computing function of instrument establishes the concentration of standard sample and the regression curve equation of fluorescent value, and the standard regression of generation is bent
Line equation is stored in instrument；
4) in industrial circulating cooling water phosphate-free corrosion inhibition antisludging agent concentration measurement: after the regression curve for obtaining standard sample
Water sample Jing Guo filtration treatment is placed in sample to be tested pond by the fluorescent value and concentration that can measure sample, by detect to
The fluorescent value of sample directly reads the concentration value of the phosphate-free corrosion inhibition antisludging agent of water sample to be measured from instrument.
There is good synergistic function between medicament each component of the invention, form absorption-deposition covering-cathode control
The Synergistic Effect of Corrosion Inhibition mode of system, so that medicament has excellent corrosion inhibition.
The ability of medicine component carboxylate, sulfonate with excellent stabilization zinc salt of the invention, while it has well
Complexing solubilising, distortion of lattice and electrostatic repulsion effect.It can be with the Ca in aqueous solution2+、Mg2Ion forms stable complexing
Object, while can also be with established CaCO3Ca in crystal2+Ion generates distortion of lattice effect, and this effect is so that CaCO3It is small
Crystal with other CaCO3It is difficult in microcrystal collision process by stringent lattice arrangement sequential arrangement, so it is not easily generated
CaCO3Big crystal, that is, inhibit scale forming matter generation, have good scale-inhibiting properties.
- 1 Sulfo propionic acid ester of medicament constituent aliphatic alcohol polyethenoxy alkyl ether 3- carboxyl of the invention and ternary are total
The non-ionic acrylate ingredient of polymers has excellent absorption, deposition covering effect, can cover well around spot corrosion source,
The electronics transfer for inhibiting galvanic interaction process, to block the progress of corrosion process.The greatly hair of inhibition point corrosion phenomenon
It is raw.
Medicine component of the invention is not phosphorous, and zinc salt content is very low, therefore avoids the richness that discharge water body may cause
Nutrient laden problem is conducive to the protection of environment.
The stability of medicine component of the invention is good, and general fungicide type, such as chlorine type, bromine type, organic sulfur type, season
The oxidizing bactericides such as ammonium salt, non oxidizing bactericide good compatibility, have the function of preferable inoxidizability.
Reagent combination of the invention may be implemented steady due to introducing inert fluorescent tracer and mating online fluorescent tracing instrument
Determine on-line checking and the control of water Chinese medicine concentration, solve the problems, such as that general without phosphorus medicament and fluorescent tracing can not be detected accurately,
Ensure the application effect of water treatment technology, for water quality management it is convenient, technical guarantee is efficiently provided.
The present invention be suitable for middle soft water quality and strong corrosive water quality or in low concentration rate circulation, medicament
Residence time is long, saves the usage amount of medicament, reduces wastewater discharge, is conducive to water-saving, emission reduction.
Medicament of the present invention ingredient is without phosphorus, uses in circulation, can well inhibit the growth of bacterium, algae, saves
The use of bulk sterilization agent reduces the composite chemical processing cost of circulation.
Reagent combination water quality use scope of the invention is extensive, is particularly suitable for southern soft water water system, ChangJiang River and east
In the typicalness such as northern Songhua River System soft, low alkalinity be supplement water industrial circulating cooling water system in, can be effectively
The heavy corrosion and scale problems for solving equipment and pipeline in water system, can especially prevent the spot corrosion phenomenon of equipment material
It generates, the recirculating cooling water system with every profession and trades such as petrochemical industry, chemical fertilizer, electric power, coal chemical industries can be applied.
The present invention uses inert fluorescent tracer, in industrial water system, it is ensured that the fluorescence signal of fluorescent chemicals
Variation is no more than 10%.Here 'inertia' refers to inert fluorescent tracer in industrial circulating cooling water system, not by water
Other compounds in system, microbial activity, concentration of sterilant and other factors significantly affect.In practical applications, this hair
The bright inert fluorescent tracer used has good inoxidizability, has with the use concentration of phosphate-free corrosion inhibition antisludging agent good
Correlation can accurately detect the use concentration of medicament.
The phosphate-free corrosion inhibition antisludging agent formula of the invention dirt dispersion agent excellent in addition to service performance, the glucose in configuration
Sour sodium, hydroxyl, carboxyl and zinc salt have good synergistic effect, the generation of the good control system corrosion of energy.Meanwhile formula group
- 1 Sulfo propionic acid ester of aliphatic alcohol polyethenoxy alkyl ether 3- carboxyl and non-ionic acrylate group in point, can be in industry water
The covering to micro cell reaction process positive and negative electrode is formed in system can well inhibit micro- during the synergistic effect with zinc salt
The electronic transfer process of cell reaction, it is suppressed that the generation of corrosion current, to eliminate the point corrosion of system material.
Compared with prior art, the detection means of phosphate-free corrosion inhibition antisludging agent of the invention is more stable, comprehensive corrosion inhibiting and descaling agent
Superior performance, and the point corrosion that soft and strong corrosive water quality system are easy to produce in capable of well solving, and medicament stops
Stay the time long, it is low using concentration, the corrosion failure phenomenon of equipment can be effectively reduced, the whole service life of equipment is improved.
Specific embodiment
Suitable for the phosphate-free corrosion inhibition antisludging agent of middle soft and strong corrosive water quality, the phosphate-free corrosion inhibition antisludging agent is by following heavy
The group of amount percentage is grouped as:
Wherein, the terpolymer containing AMPS be containing carboxylic acid group, sulfonic group, acrylate copolymer.
Wherein, aliphatic alcohol polyethenoxy alkyl ether-carboxyl-Sulfo propionic acid ester copolymer is C14~C18 fatty alcohol
- 1 Sulfo propionic acid ester of polyoxyethylene alkyl ether 3- carboxyl.
Wherein, the pH adjusting agent is sodium hydroxide, sulfuric acid or nitric acid.
Wherein, the zinc salt is zinc chloride or zinc sulfate.
Wherein, it is 365nm that the water soluble inert fluorescent tracer, which is maximum excitation wavelength, and maximum emission wavelength is
The water soluble inert fluorescent chemicals of 400nm, the water soluble fluorescence compound are preferably 1,3,6,8- pyrene tetrasulfonic acid tetrasodium salts.
When the phosphate-free corrosion inhibition antisludging agent is used for middle soft and strong corrosive water treatment, in middle soft and strong corruption
Use concentration in the industrial circulating cooling water of corrosion water quality is 60~200mg/L.The phosphate-free corrosion inhibition antisludging agent is in weight
The pH value in aqueous solution that percentage is 1% is 1.5~4.5.
Use of the phosphate-free corrosion inhibition antisludging agent in the industrial circulating cooling water of middle soft and strong corrosive water quality
Detection method includes the following steps for concentration:
1) apparatus selection: selection fluorescence mode carries out using Concentration Testing；
2) starting/termination wavelength parameter of fluorescent exciting, starting/termination of fluorescence emission wavelengths parameter setting: are set
Wavelength parameter, default value may be selected in other；
3) it measurement standard sample and establishes regression curve: the without phosphorus slow of middle soft and strong corrosive water treatment will be used for
Erosion antisludging agent is configured to standard solution according to various concentration gradient respectively, makes function using the standard regression curvilinear equation of instrument
Can, then the corresponding fluorescent value of each standard solution of sequentially determining passes through after the fluorescent value measurement for completing standard sample concentration
The computing function of instrument establishes the concentration of standard sample and the regression curve equation of fluorescent value, and the standard regression of generation is bent
Line equation is stored in instrument；
4) in industrial circulating cooling water phosphate-free corrosion inhibition antisludging agent concentration measurement: after the regression curve for obtaining standard sample
Water sample Jing Guo filtration treatment is placed in sample to be tested pond by the fluorescent value and concentration that can measure sample, by detect to
The fluorescent value of sample directly reads the concentration value of the phosphate-free corrosion inhibition antisludging agent of water sample to be measured from instrument.
The present invention is described in detail combined with specific embodiments below.
Embodiment 1:
For Hainan petro-chemical corporation circulation, a kind of phosphate-free corrosion inhibition antisludging agent suitable for strong corrosive water quality,
The corrosion inhibiting and descaling agent consists of the following components in percentage by weight:
Terpolymer containing AMPS: 18%；
Hydrolyzed polymaleic anhydride: 9.5%；
Sodium gluconate: 7.5%；
- 1 Sulfo propionic acid ester of aliphatic alcohol polyethenoxy alkyl ether 3- carboxyl: 28%；
Sulfuric acid or nitric acid: 1.0%；
Zinc salt: 10%；
Benzotriazole: 1.0%；
Water soluble inert fluorescent chemicals: 1.0%；
Deionized water: 24%.
This kind is suitable for the phosphate-free corrosion inhibition antisludging agent of strong corrosive water quality, is added according to the concentration of 120mg/l to be processed
Industrial water in.Industrial water raw water quality: pH value 6.74, turbidity 3.8NTU, conductivity 225uS/cm, total dissolubility are solid
151mg/L, M- basicity are (with CaCO3Meter) 57.2mg/L, total hardness is (with CaCO3Meter) 81mg/L, Ca2+(with CaCO3Meter) 45mg/
L, SO4 2-12.1mg/L Cl-39mg/L, total iron 0.05mg/L, SiO27.6mg/L, total phosphorus 0.12mg/L, CODMn 3mg/l。
The phosphate-free corrosion inhibition antisludging agent is applied to circulation, and concentration rate transits to 6.0 times from 1.2, system fluorescent value
Control 110~120, zinc ion control 1.5~2.0mg/l.When concentration rate continuously rises to 6.0 times, carbon steel corrosion inhibition rate is rotten
Erosion rate is 0.04mm/a, is lower than the carbon steel material of " GB50050-2007 Code for design of industrial recirculating cooling water treatment " prescribed requirement
Rate of corrosion < 0.075mm/a requirement.Corrosion of Stainless Steel rate 0.002mm/a, corrosion of copper alloy rate 0.003mm/a, lower than " design rule
Model " copper alloy and Corrosion of Stainless Steel rate are less than the requirement of 0.005mm/a.Test tube inner surface does not have obvious point corrosion to generate, dirty
Dirty thermal resistance 1.7 × 10-4㎡ K/W is less than " design specification " requires 3.44 × 10-4㎡K/W。
Embodiment 2
It is a kind of suitable for middle soft, basicity Corrosive water quality for Sichuan Gas Purification Factory circulation
Phosphate-free corrosion inhibition antisludging agent, the phosphate-free corrosion inhibition antisludging agent are formed by following weight percent:
Terpolymer containing AMPS: 28%；
Hydrolyzed polymaleic anhydride: 16%；
- 1 Sulfo propionic acid ester of aliphatic alcohol polyethenoxy alkyl ether 3- carboxyl: 18%；
Sulfuric acid or nitric acid: 2.0%；
Zinc salt: 8%；
Benzotriazole: 1.0%；
Water soluble inert fluorescent chemicals: 1.0%；
Deionized water: 26%.
With prepared phosphate-free corrosion inhibition antisludging agent solution, industrial water to be processed is added to according to the concentration of 150mg/l
In.
Above-mentioned industrial water raw water quality: pH 7.90, turbidity 1.0NTU, 300 μ s/cm of conductivity, total dissolved solid
201mg/L, M- basicity are (with CaCO3Meter) 105mg/L, total hardness is (with CaCO3Meter) 162mg/L, calcium hardness is (with CaCO3Meter)
125mg/L, Cl-22mg/L, Fe 0.04mg/L, SO4 2-18mg/L, SiO27.8mg/L, COD 1.6mg/L.
Applied to the single system commerical test of Gas Purification Factory (petroleum chemical enterprise) circulation, concentration process raw water
4.7 times are gradually risen up to, system fluorescent value 140~155 test period 60 days, controls 0.8~1.5mg/l of zinc ion.
According to field monitoring data, carbon steel average corrosion rate is less than 0.01mm/a, reaches plant area's control Con trolling index
0.03mm/a requirement, and it is significantly less than the 0.075mm/a skill of " GB50050-2007 Code for design of industrial recirculating cooling water treatment "
Art requirement.Test tube inner surface is smooth, no point corrosion.Dirtiness resistance 0.299 × 10-4㎡ K/W is less than " design specification " requirement
3.44×10-4㎡K/W.The rate average out to 3.7mg/cm2. month is adhered to, the code requirement 15mg/cm2. month is less than.Copper alloy is average
Rate of corrosion 0.002mm/a is less than code requirement 0.005mm/a.
Embodiment 3
It is pressed for Jilin petroleum chemical enterprise circulation using the phosphate-free corrosion inhibition antisludging agent formula of strong corrosive water quality
It is formed according to following weight percent:
Terpolymer containing AMPS: 18%；
Hydrolyzed polymaleic anhydride: 12%；
Sodium gluconate: 6%；
- 1 Sulfo propionic acid ester of aliphatic alcohol polyethenoxy alkyl ether 3- carboxyl: 26%；
Sulfuric acid or nitric acid: 1.0%；
Zinc salt: 10%；
Water soluble inert fluorescent chemicals: 0.5%；
Deionized water: 26.5%.
With prepared phosphate-free corrosion inhibition antisludging agent solution, industrial water to be processed is added to according to the concentration of 120mg/l
In.
Above-mentioned industrial water raw water quality: pH7.38, conductivity 160us/cm, total hardness (calcium carbonate) 75mg/L, calcium
Hardness (calcium carbonate) 40mg/L, M- basicity (calcium carbonate) 50mg/L, chloride ion 27mg/L, total iron 0.3mg/L, silica
8mg/L, sulfate ion 24.5mg/L, turbidity 3.0NTU.
The phosphate-free corrosion inhibition antisludging agent is applied to be gradually risen up to Ethylene in Petrochemical Enterprises factory circulation, concentration process raw water
7.0 times, system fluorescent value 60~80 controls 1.0~2.0mg/l of zinc ion.According to field monitoring data, carbon steel average corrosion speed
Rate is less than 0.03mm/a, and stainless steel average corrosion rate is less than 0.002mm/a, is respectively smaller than " Code for design of industrial recirculating cooling water "
It is required that corrosion of carbon steel rate be less than 0.075mm/a, Corrosion of Stainless Steel rate be less than 0.005mm/a.Lacing film shows existing without obvious spot corrosion
As.Dirtiness resistance 1.3 × 10-4 ㎡ K/W is less than 3.44 × 10-4 of code requirement ㎡ K/W.
Embodiment 4
A kind of phosphate-free corrosion inhibition antisludging agent suitable for middle soft and strong corrosive water quality, the phosphate-free corrosion inhibition antisludging agent by with
The group of lower weight percent is grouped as: containing carboxylic acid group, sulfonic group, acrylate copolymer: 15%, hydrolyzed polymaleic anhydride:
20%, sodium gluconate: 10%, -1 Sulfo propionic acid ester of C14~C18 aliphatic alcohol polyethenoxy alkyl ether 3- carboxyl: 15%, pH tune
Save agent (sodium hydroxide and sulfuric acid): 3%, zinc salt (zinc chloride): 12%, benzotriazole: 5.0%, water soluble inert fluorescence shows
Track agent (1,3,6,8- pyrene tetrasulfonic acid tetrasodium salt): 5.0%, deionized water: 15%.
Embodiment 5
A kind of phosphate-free corrosion inhibition antisludging agent suitable for middle soft and strong corrosive water quality, the phosphate-free corrosion inhibition antisludging agent by with
The group of lower weight percent is grouped as: containing carboxylic acid group, sulfonic group, acrylate copolymer: 19%, hydrolyzed polymaleic anhydride:
12%, sodium gluconate: 5.0%, -1 Sulfo propionic acid ester of C14~C18 aliphatic alcohol polyethenoxy alkyl ether 3- carboxyl: 30%, pH
Regulator (nitric acid): 1%, zinc salt (zinc sulfate): 6%, benzotriazole: 2.0%, water soluble inert fluorescent tracer (1,3,
6,8- pyrene tetrasulfonic acid tetrasodium salt): 0.5%, deionized water: 24.5%.
Embodiment 6
A kind of phosphate-free corrosion inhibition antisludging agent suitable for middle soft and strong corrosive water quality, the phosphate-free corrosion inhibition antisludging agent by with
The group of lower weight percent is grouped as: containing carboxylic acid group, sulfonic group, acrylate copolymer: 30%, hydrolyzed polymaleic anhydride:
15%, sodium gluconate: 0.1%, -1 Sulfo propionic acid ester of C14~C18 aliphatic alcohol polyethenoxy alkyl ether 3- carboxyl: 19.6%,
PH adjusting agent (nitric acid): 0.1%, zinc salt (zinc chloride): 0.1%, benzotriazole: 0.1%, water soluble inert fluorescent tracer
(1,3,6,8- pyrene tetrasulfonic acid tetrasodium salt): 2.0%, deionized water: 33%.
Embodiment 7
A kind of phosphate-free corrosion inhibition antisludging agent suitable for middle soft and strong corrosive water quality, the phosphate-free corrosion inhibition antisludging agent by with
The group of lower weight percent is grouped as: containing carboxylic acid group, sulfonic group, acrylate copolymer: 15%, hydrolyzed polymaleic anhydride:
13%, sodium gluconate: 1%, -1 Sulfo propionic acid ester of C14~C18 aliphatic alcohol polyethenoxy alkyl ether 3- carboxyl: 18%, pH tune
It saves agent (sulfuric acid): 1%, zinc salt (zinc chloride): 8%, benzotriazole: 3%, water soluble inert fluorescent tracer (1,3,6,8-
Pyrene tetrasulfonic acid tetrasodium salt): 1%, deionized water: 40%.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (9)
1. being suitable for the phosphate-free corrosion inhibition antisludging agent of middle soft and strong corrosive water quality, which is characterized in that the no-phosphate corrosion scale inhibition
Agent consists of the following components in percentage by weight:
Terpolymer containing AMPS be containing carboxylic acid group, sulfonic group, acrylate copolymer；
The water soluble inert fluorescent tracer is that maximum excitation wavelength is 365nm, and maximum emission wavelength is the water-soluble of 400nm
Property inert fluorescent compound.
2. the phosphate-free corrosion inhibition antisludging agent according to claim 1 suitable for middle soft and strong corrosive water quality, feature
It is, which consists of the following components in percentage by weight:
3. the phosphate-free corrosion inhibition antisludging agent according to claim 1 or 2 suitable for middle soft and strong corrosive water quality, special
Sign is that the aliphatic alcohol polyethenoxy alkyl ether-carboxyl-Sulfo propionic acid ester copolymer is C14~C18 fatty alcohol polyoxy second
- 1 Sulfo propionic acid ester of allylic alkylation ether 3- carboxyl.
4. the phosphate-free corrosion inhibition antisludging agent according to claim 1 or 2 suitable for middle soft and strong corrosive water quality, special
Sign is that the pH adjusting agent is sodium hydroxide, sulfuric acid or nitric acid.
5. the phosphate-free corrosion inhibition antisludging agent according to claim 1 or 2 suitable for middle soft and strong corrosive water quality, special
Sign is that the zinc salt is zinc chloride or zinc sulfate.
6. the phosphate-free corrosion inhibition antisludging agent according to claim 1 or 2 suitable for middle soft and strong corrosive water quality, special
Sign is that the water soluble inert fluorescent chemicals are 1,3,6,8- pyrene tetrasulfonic acid tetrasodium salts.
7. it is suitable for the application of the phosphate-free corrosion inhibition antisludging agent of middle soft and strong corrosive water quality as claimed in claim 1 or 2,
It is characterized in that, when the phosphate-free corrosion inhibition antisludging agent is used for middle soft and strong corrosive water treatment, in middle soft and
Use concentration in the industrial circulating cooling water of strong corrosive water quality is 60~200mg/L.
8. the application of the phosphate-free corrosion inhibition antisludging agent according to claim 7 suitable for middle soft and strong corrosive water quality,
It is characterized in that, pH value of the phosphate-free corrosion inhibition antisludging agent in the aqueous solution that weight percent is 1% is 1.5~4.5.
9. the application of the phosphate-free corrosion inhibition antisludging agent according to claim 7 suitable for middle soft and strong corrosive water quality,
It is characterized in that, the phosphate-free corrosion inhibition antisludging agent makes in the industrial circulating cooling water of middle soft and strong corrosive water quality
With concentration, detection method includes the following steps:
1) apparatus selection: selection fluorescence mode carries out using Concentration Testing；
2) starting/termination wavelength parameter of fluorescent exciting, starting/termination wavelength of fluorescence emission wavelengths parameter setting: are set
Parameter, default value may be selected in other；
3) it measurement standard sample and establishes regression curve: the no-phosphate corrosion resistance of middle soft and strong corrosive water treatment will be used for
Dirty agent is configured to standard solution according to various concentration gradient respectively, makes function using the standard regression curvilinear equation of instrument, according to
It is secondary to measure the corresponding fluorescent value of each standard solution, after the fluorescent value measurement for completing standard sample concentration, then pass through instrument
Computing function, establish the concentration of standard sample and the regression curve equation of fluorescent value, and by the standard regression curve side of generation
Journey is stored in instrument；
4) in industrial circulating cooling water phosphate-free corrosion inhibition antisludging agent concentration measurement: obtaining can after the regression curve of standard sample
To measure the fluorescent value and concentration of sample, the water sample Jing Guo filtration treatment is placed in sample to be tested pond, by detecting to test sample
The fluorescent value of product directly reads the concentration value of the phosphate-free corrosion inhibition antisludging agent of water sample to be measured from instrument.
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| CN106517611A (en) * | 2016-12-30 | 2017-03-22 | 薛方勤 | Reclaimed water reutilization method for circulating water system |
| CN110201550B (en) * | 2019-06-24 | 2021-10-22 | 营口科林膜技术工程服务有限公司 | Corrosion and scale inhibitor for reverse osmosis membrane |
| CN112978944A (en) * | 2021-02-26 | 2021-06-18 | 常州大学 | Fluorescent tracing type non-phosphorus corrosion and scale inhibitor PESA-X and preparation method and application thereof |
| CN113003739B (en) * | 2021-04-23 | 2023-01-10 | 天津市中海水处理科技有限公司 | Ternary sulfonic acid polymer scale inhibitor containing fluorescent group and preparation method thereof |
| CN115432831A (en) * | 2022-09-21 | 2022-12-06 | 岳阳隆兴实业有限公司 | Non-phosphorus scale and corrosion inhibitor |
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| CN102815796A (en) * | 2011-06-10 | 2012-12-12 | 中国石油化工股份有限公司 | Composite phosphorus-free corrosion and scale inhibitor and its application |
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| CN102092863A (en) * | 2010-11-22 | 2011-06-15 | 茂名众和国颂精细化工有限公司 | Phosphorus-free corrosion and scale inhibitor for treating strong corrosive water and use concentration detection method thereof |
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| CN105623865A (en) * | 2014-10-31 | 2016-06-01 | 张媛媛 | Brightener for household electrical appliance |
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