CN101781028A - High-efficiency low-phosphorous corrosion and scale inhibition dispersant as well as preparation method and application thereof - Google Patents

High-efficiency low-phosphorous corrosion and scale inhibition dispersant as well as preparation method and application thereof Download PDF

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CN101781028A
CN101781028A CN201010107044A CN201010107044A CN101781028A CN 101781028 A CN101781028 A CN 101781028A CN 201010107044 A CN201010107044 A CN 201010107044A CN 201010107044 A CN201010107044 A CN 201010107044A CN 101781028 A CN101781028 A CN 101781028A
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water
dispersion agent
efficient low
dirt dispersion
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CN101781028B (en
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马俊
曾玉
孙轶民
唐明辉
李芝勇
严莲荷
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Industrial And Technological University Kaiyuan Environmental Protection Technology Anhui Co ltd
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Kaiyuan Chemical Co Ltd Nanjing University Of Technology
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Abstract

The invention relates to a high-efficiency low-phosphorous corrosion and scale inhibition dispersant as well as a preparation method and application thereof, which belong to the technical field of environmental protection. The low-phosphorous corrosion and scale inhibition dispersants of different formulas are prepared by compounding with a corrosion inhibitor, a scale inhibitor, a stabilizer, a fluorescent tracer and deionized water according to different water quality of water sources; the adding concentration of the dispersant in circulating water is 50-80mg/L relative to the added water amount, and the adding concentration is 3-4mg/L relative to fluorescence intensity; the dispersant can be widely applied to the water quality of the circulating water of which the hardness plus the alkalinity is smaller than 1100mg/L, the chloride ion concentration is smaller than 1000mg/L, the pH value is 6.8-9.5 and the turbidity is smaller than 20NTYU; and the dispersant is particularly suitable for more than 5 times of high concentration multiple operation of the circulating water of the water quality of the water sources in the middle and lower reaches of Changjiang River, the scale and corrosion inhibition performance can satisfy the specified requirement on a GB 50050-2007 industrial circulating water design criterion; and the dispersant has the advantages of low phosphorous content, environmental protection, strong chlorine resistance, applicability to automatic dosing control, convenient use and the like.

Description

Efficient low-phosphorus corrosion dirt dispersion agent and its production and application
Technical field: the invention belongs to environmental protection technical field, relate to a kind of efficient low-phosphorus dirt dispersion agent of cycle of treatment water coolant and customize production technique and complete-set applied technology.
Background technology: developed country has reached 80%-90% on the repeat usage of process water, and the concentration rate of water has reached 6-8 doubly.And the utilization ratio of China's water is on average less than 50%, and the concentration rate overwhelming majority of recirculated cooling water is in 2-3 level doubly, and from energy-saving and water-saving, this is undoubtedly the huge waste of resource.For the conserve water resource need provide the repeating utilization factor of water, and in the recycling process of water, can produce problems such as fouling, burn into bacterium algae and foundry loam breeding, once must add a certain amount of water quality stabilizer, as anti-incrustation corrosion inhibitor, Biocidal algae-killing agent.And present domestic recirculated cooling water processing anti-incrustation corrosion inhibitor commonly used has poly-phosphate, phosphoric acid ester, organophosphate and acrylic copolymer etc.Wherein, the organic phosphate medicament efficiently have inhibition and scale inhibition dual-use function concurrently with it and be employed the most general, but because its phosphorus content height, have a large amount of phosphoric acid salt during blowdown and enter environment, easily cause the rich phosphorus of water system and form " red tide ", make anoxic in the water, influence the existence of aquatic organism.At present strict control (discharge of wastewater primary standard P<0.5mg/L, secondary standard P<1.0mg/L) have made to the discharging of phosphorus in China for this reason.Therefore,, particularly do not have phosphatization and handle, help reducing the nutrition source of bacterium in the recirculated water, microorganism, reduce the sterilant consumption from just the begin one's study low-phosphorous and no phosphatization treatment technology of water conditioner of the country of some prosperities of the early 1990s.
Summary of the invention: purpose of the present invention is exactly to propose under a kind of prerequisite that meets the environment protection emission requirement, the scale inhibitor preparation of the low-phosphorous prescription of cycle of treatment water coolant, and in industrial application, really can accomplish low-phosphorous, environmental protection, efficient, easily produce, easy to control.
Efficient low-phosphorus corrosion dirt dispersion agent of the present invention is to be benchmark with the mass percent, it consists of: 2%~12% Sunmorl N 60S, 1%~5% molybdenum or tungstate, 1%~2% thiazole, 3%~6% Zinc Chloride Anhydrous, 8%~18%2-phosphonate group-1,2,4-butane tricarboxylate, 5%~15% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multipolymer, 3%~6% dimethyl formamide and 3%~6% tracer agent, surplus is a deionized water.
The various materials that dispersion agent of the present invention adopted are well-known to those skilled in the art, also are the commercial goods, can obtain very easily.
A kind of efficient low-phosphorus corrosion dirt dispersion agent of the present invention is a kind of compound prescription preparation, and concrete proportioning need be according to the different proportionings of water quality different mining.
Dispersion agent usually of the present invention is by inhibiter, Scale inhibitors and the stablizer of different ratios, the formulation product that cooperates fluorescent tracer and deionized water to be composited again.Inhibiter comprises 2%~12% Sunmorl N 60S, 1%~5% molybdenum or tungstate, 1%~2% thiazole, 3%~6% Zinc Chloride Anhydrous, 8%~18%2-phosphonate group-1,2,4-butane tricarboxylate; Scale inhibitors comprises 5%~15% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multipolymer, 2%~12% Sunmorl N 60S and 8%~18%2-phosphonate group-1,2,4-butane tricarboxylate; Stablizer comprises 3%~6% dimethyl formamide.
Described thiazole is one or more in phenylpropyl alcohol thiazole or methyl phenylpropyl alcohol thiazole or the sulfydryl phenylpropyl alcohol thiazole.
Vinylformic acid-acrylate-co-polymer of sulfonate that described tracer agent is modified for the hydroxyl pyridine derivate.Generally be by one or more mixture and the hydroxyl pyridine derivate vinylformic acid-acrylate-co-polymer of sulfonate that the synthetic hydroxyl pyridine derivate that obtains is modified under catalyst action that contains in vinylformic acid, methacrylic acid, acrylamide, ester group, amino and the sulfonic acid group, it has fluorescence, water-soluble and dispersed, it with and each water conditioner good synergistic effect is arranged.
A kind of efficient low-phosphorus corrosion dirt dispersion agent physicochemical property of the present invention is:
Appearance colorless or faint yellow or brown liquid do not have precipitation
Density (20 ℃), g/cm 31.00~1.20
Total phosphate content is (with PO 4 3-Meter), %≤5.0
PH value (1% aqueous solution)≤6.0
Solids content, % 〉=25.0
Orthophosphoric acid salt is (with PO 4 3-Meter) content, %≤0.5
Phosphorous acid is (with PO 3 3-Meter) content, %≤0.5
Azole content, % 〉=0.8
The used raw material of a kind of efficient low-phosphorus corrosion dirt dispersion agent of the present invention all requires to meet the relevant product standard of country, and the proportioning metering is to measure by percentage to the quality.
The preparation method of dispersion agent of the present invention is: add deionized water in reactor, start agitator, stir on one side, add 1%~5% dimethyl formamide respectively by following order on one side, 5%~15%AA/AMPS multipolymer, 2%~12% Sunmorl N 60S, 1%~5% molybdenum (tungsten) hydrochlorate, 8%~18%PBTCA, 1%~2% methyl phenylpropyl alcohol thiazole, 3%~6% Zinc Chloride Anhydrous and 3%~6% tracer agent, after adding, supplies raw material deionized water to quantitative, stirring-filtration under the room temperature, cross the cleaner liquid packing and be product, churning time is preferably about 1 hour more than 0.1 hour.
A kind of efficient low-phosphorus corrosion dirt dispersion agent of the present invention is according to HG/T2024-91 " water treatment agent scale-inhibiting properties measuring method---Bubbling method " and Sinopec " water coolant analysis and test method ", GB/T18175-2000 " mensuration of water treatment agent corrosion inhibition---rotary hanging plate method " and HG/T2160-2008 " water coolant dynamic analog test method " carries out scale-inhibiting properties and the qualification test of corrosion inhibition quadrature determines that each monomer the best adds ratio in the prescription.
A kind of efficient low-phosphorus corrosion dirt dispersion agent of the present invention can be widely applicable for hardness and add basicity less than 1100mg/L, and chlorion is less than 1000mg/L, and pH6.8~9.5 are in the circulating water quality of turbidity less than 20NTYU; The recirculated water of particularly suitable middle and lower reach of Yangtze River source quality is the high concentration multiple operation more than 5 times.
A kind of efficient low-phosphorus corrosion dirt dispersion agent of the present invention adds concentration and counts 50~80mg/L by mending amount of flush water in recirculated water, add concentration 3~4mg/L in fluorescence intensity, controls phosphoric acid salt in the recirculated water (with PO 4 3-Meter) less than 1.5mg/L, for drug concentration of the present invention in the accurate Control Circulation water, add 3%~6% tracer agent in the medicament, variation by the fluorescence intensity in recirculated water, cooperate the control of fluorescent tracing Monitoring and Controlling instrument, can directly reflect the concentration of water treatment agent, be convenient to be implemented in the line automation dosing, improve the controllability of water treatment agent concentration monitoring stability and science, economic management greatly at recirculated water.
Low-phosphorous with other or the low-phosphorous formulation product of a kind of efficient low-phosphorus corrosion dirt dispersion agent of the present invention is compared has the following advantage: 1. applied widely, can be applicable to various source qualities widely, and only need regulate formula rate and get final product; 2. scale inhibition performance height, the Sunmorl N 60S of selecting for use among the present invention be because of containing a plurality of hydroxyls in the molecule, in the aqueous solution to Fe 3+, Cu 2+, Ca 2+Plasma has fabulous complex ability, and the many salts of these ionic are also had good deactivation.Therefore, it is used as scale inhibition, inhibiter in the present invention, also is used as dispersion agent simultaneously, and the AA/AMPS multipolymer of selecting for use among the present invention that has sulfonic acid group contains strong acid group (SO simultaneously 3H), the weak acid group (COOH), non-ionic group (C-O-R ,-C=O ,-OH), these functional groups are playing a part to have nothing in common with each other aspect the scale inhibition dispersion.The weak acid group has strong adsorption to the active part of difficulty soluble salt crystallite, thereby play the low dosage effect and suppress the crystallization generation, strong acid group is then keeping slight ion characteristic, thereby help difficulty soluble salt to dissociate, and non-ionic group has stronger adsorption to outstanding admittedly thing, and it is dispersed in the water.These groups in conjunction with producing synergistic effect, make medicament have good scale inhibition and dispersion performance through effectively.
The PBTCA that selects for use among the present invention contains a phosphino-(PO 3H 2) and three carboxyls (COOH), the phosphine carboxylic acid can effectively stop the deposition of carbonate, vitriol and zinc salt, therefore has excellent scale inhibition and corrosion inhibition, and high temperature resistant, and anti-chlorine decomposes, and phosphorus content is low, and is little to the influence of environment.Under the harsh condition of water quality of high temperature, high rigidity, high pH value, high concentration multiple, also can bring into play very strong scale effect especially; 3. corrosion inhibition is strong, selects for use inhibiter such as phosphine carboxylic acid PBTCA, Sunmorl N 60S, molybdenum (tungsten) hydrochlorate and methyl phenylpropyl alcohol thiazole can effectively prevent the corrosion of various material such as carbon steel, stainless steel, copper in the prescription; 4. the resisting chloride ion penetration corrosion can be strong, selected anti-chlorine factor thiazole compound in the prescription for use, and recirculated water resisting corrosion of chlorine ion performance can effectively be resisted 1100mg/L with the erosion of interior chlorion to metal; 5. can realize intelligent automatic dosing control, the fluorescent tracer that adds in the prescription cooperates fluorescence detection device to realize accurate dosing, control automatically.
In sum, a kind of efficient low-phosphorus corrosion dirt dispersion agent of the present invention is used for recirculated cooling water to be handled, corrosion and scale inhibition performance can satisfy GB 50050-2007 industrial circulating water design specifications specified requirement, it is wide to be suitable for the source quality scope, have low-phosphorous, environmental protection, chlorine resistance is strong, is applicable to advantages such as Automatic Dosing control is easy to use.
Embodiment:
1. embodiment 1:
Be applicable to 5 times of cycles of concentration the Changjiang river water system source quality efficient low-phosphorus corrosion dirt dispersion agent preparations and application
1. the present invention fills a prescription 1
Be fit to the preparation of the recirculated water efficient low-phosphorus corrosion dirt dispersion agent of the above source quality of five times of cycles of concentration of certain petroleum chemical enterprise: determine following prescription (mass percent): 1% dimethyl formamide, 10%AA/AMPS multipolymer, 10%PBTCA, 10% Sunmorl N 60S, 4% Sodium orthomolybdate, 1% methyl phenylpropyl alcohol thiazole, 3% Zinc Chloride Anhydrous and 3% fluorescent tracer composite dose according to orthogonal test.
2. product quality indicator
The outward appearance weak yellow liquid does not have precipitation
Density (20 ℃), g/cm 31.199
Total phosphate content is (with PO 4 3-Meter), %≤1.81
Orthophosphoric acid salt is (with PO 3 3-) content %≤0.01
Phosphite is (with PO 3 3-) content %≤0.02
PH value (1% aqueous solution)≤3.78
Solids content, % 〉=28.54
Zinc salt is (with Zn 2+Meter) content, % 〉=1.45
Azole content, % 〉=1.32
3. product rig-site utilization and effect
The product of present embodiment is used in certain heat power plant's two cover recirculated water, and heat power plant's electricity 1 follows the systemic circulation water yield: 35000m 3/ h possesses the water yield: 21000m 3, material is carbon steel, brass; Electricity 2 follows the systemic circulation water yield: 17500m 3/ h possesses the water yield: 10500m 3, material is carbon steel, brass.NJS-III type fluorescent tracing automatic medicament feeding system is adopted in dosing control, realizes adding the Automatic Detection and Control of projects such as dose, moisturizing, blowdown, pH, specific conductivity, turbidity.
Treatment effect is: the recirculated water concentration rate is greater than 5 times, total hardness 200~400mg/L, total alkalinity 200~400mg/l, chlorion is up to 300mg/l, carbon steel lacing film erosion rate is less than 0.0142mm/a, copper lacing film erosion rate is less than 0.0012mm/a, the dirt deposition rate is 1.003mcm only, and phosphonate is (with PO in the recirculated water 4 3-Meter) be controlled at 1~1.5mg/L, phosphate content in the sewer (in P) meets the requirement of one-level environment protection emission less than 0.5mg/L.
2. embodiment 2:
Be applicable to 8 times of cycles of concentration softs, low basicity source quality efficient low-phosphorus corrosion dirt dispersion agent preparation and application
1. the present invention fills a prescription 2
Be fit to the preparation of the recirculated water efficient low-phosphorus corrosion dirt dispersion agent of the above source quality of certain enterprise's circulating water system soft, low basicity octuple cycles of concentration: determine following prescription (mass percent): composite dose of 5% dimethyl formamide, 15%AA/AMPS multipolymer, 18%PBTCA, 12% Sunmorl N 60S, 1% Sodium orthomolybdate, 1% methyl phenylpropyl alcohol thiazole, 3% Zinc Chloride Anhydrous and 2% fluorescent tracer according to orthogonal test.
2. product quality indicator
The outward appearance brown liquid does not have precipitation
Density (20 ℃), g/cm 31.178
Total phosphate content is (with PO 4 3-Meter), %≤2.11
Orthophosphoric acid salt is (with PO 3 3-) content %≤0.02
Phosphite is (with PO 3 3-) content %≤0.03
PH value (1% aqueous solution)≤4.01
Solids content, % 〉=27.99
Zinc salt is (with Zn 2+Meter) content, % 〉=1.28
Azole content, % 〉=1.40
3. product rig-site utilization and effect
The product of present embodiment is used in certain recirculated water, the systemic circulation water yield: 5000m 3/ h possesses the water yield: 2000m 3, material is carbon steel, stainless steel.NJS-III type fluorescent tracing automatic medicament feeding system is adopted in dosing control, realizes adding the Automatic Detection and Control of projects such as dose, moisturizing, blowdown, pH, specific conductivity, turbidity.
Treatment effect is: the recirculated water concentration rate is greater than 8 times, total hardness is up to 750mg/L, basicity 150~250mg/l, chlorion is less than 300mg/l, carbon steel lacing film erosion rate is less than 0.0102mm/a, stainless steel lacing film erosion rate is less than 0.0001mm/a, and the dirt deposition rate is 1.123mcm only, and phosphonate is (with PO in the recirculated water 4 3-Meter) be controlled at 1~1.5mg/L, phosphate content in the sewer (in P) meets the requirement of one-level environment protection emission less than 0.5mg/L.
3. embodiment 3:
Be applicable to high chlorine root source quality efficient low-phosphorus water treatment formulation preparation and application
1. the present invention fills a prescription 3
Be fit to certain petrochemical industry and reclaim the doubly preparation of the recirculated water efficient low-phosphorus corrosion dirt dispersion agent of the above source quality of 5 times of cycles of concentration of high chlorine root sewage: determine following prescription (mass percent): composite dose of 3% dimethyl formamide, 10%AA/AMPS multipolymer, 15%PBTCA, 12% Sunmorl N 60S, 5% sodium wolframate, 2% methyl phenylpropyl alcohol thiazole, 3% Zinc Chloride Anhydrous and 2% fluorescent tracer according to orthogonal test.
2. product quality indicator
The outward appearance brown liquid does not have precipitation
Density (20 ℃), g/cm 31.188
Total phosphate content is (with PO 4 3-Meter), %≤2.03
Orthophosphoric acid salt is (with PO 3 3-) content %≤0.02
Phosphite is (with PO 3 3-) content %≤0.03
PH value (1% aqueous solution)≤4.54
Solids content, % 〉=30.11
Zinc salt is (with Zn 2+Meter) content, % 〉=1.40
Azole content, % 〉=1.98
3. product rig-site utilization and effect
The product of present embodiment is used in certain II of petrochemical refining type recirculated water, the oil refining II type systemic circulation water yield: 8000m 3/ h possesses the water yield: 7000m 3, material is carbon steel, stainless steel.NJS-III type fluorescent tracing automatic medicament feeding system is adopted in dosing control, realizes adding the Automatic Detection and Control of projects such as dose, moisturizing, blowdown, pH, specific conductivity, turbidity.
Treatment effect is: the recirculated water concentration rate is greater than 4 times, total hardness is up to 600mg/L, chlorion is less than 850mg/L, COD is less than 60mg/l, carbon steel lacing film erosion rate is less than 0.0412mm/a, stainless steel lacing film erosion rate is less than 0.0021mm/a, and the dirt deposition rate is 2.23mcm only, and phosphonate is (with PO in the recirculated water 4 3-Meter) be controlled at 1~1.5mg/L, phosphate content in the sewer (in P) meets the requirement of one-level environment protection emission less than 0.5mg/L.
4. embodiment 4:
Be applicable to high rigidity, high basicity source quality efficient low-phosphorus water treatment formulation preparation and application
1. the present invention fills a prescription 4
Be fit to the preparation of the recirculated water low-phosphorus corrosion dirt dispersion agent of the above source quality of certain fertilizer plant's high rigidity, 4 times of cycles of concentration of high basicity: determine following prescription (mass percent): composite dose of 3% dimethyl formamide, 15%AA/AMPS multipolymer, 18%PBTCA, 8% Sunmorl N 60S, 4% sodium wolframate, 1% methyl phenylpropyl alcohol thiazole, 3% Zinc Chloride Anhydrous and 3% fluorescent tracer according to orthogonal test.
2. product quality indicator
The outward appearance brown liquid does not have precipitation
Density (20 ℃), g/cm 31.178
Total phosphate content is (with PO 4 3-Meter), %≤2.23
Orthophosphoric acid salt is (with PO 3 3-) content %≤0.01
Phosphite is (with PO 3 3-) content %≤0.03
PH value (1% aqueous solution)≤3.98
Solids content, % 〉=28.11
Zinc salt is (with Zn 2+Meter) content, % 〉=1.40
Azole content, % 〉=0.98
3. product rig-site utilization and effect
The product of present embodiment is used in certain fertilizer plant's recirculated water, this fertilizer plant's systemic circulation water yield: 5000m 3/ h possesses the water yield: 1600m 3, material is a carbon steel.NJS-III type fluorescent tracing automatic medicament feeding system is adopted in dosing control, realizes adding the Automatic Detection and Control of projects such as dose, moisturizing, blowdown, pH, specific conductivity, turbidity.
Treatment effect is: the recirculated water concentration rate is greater than 4 times, total hardness 600mg/L, total alkalinity 500mg/l, chlorion is up to 700mg/L, carbon steel lacing film erosion rate is less than 0.0342mm/a, stainless steel lacing film erosion rate is less than 0.0022mm/a, and the dirt deposition rate is 2.58mcm only, and phosphate content in the sewer (in P) meets the requirement of one-level environment protection emission less than 0.5mg/L.

Claims (8)

1. efficient low-phosphorus corrosion dirt dispersion agent, it is characterized in that this dispersion agent is benchmark with the mass percent, it consists of: 2%~12% Sunmorl N 60S, 1%~5% molybdenum or tungstate, 1%~2% thiazole, 3%~6% Zinc Chloride Anhydrous, 8%~18%2-phosphonate group-1,2,4-butane tricarboxylate, 5%~15% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multipolymer, 3%~6% dimethyl formamide and 3%~6% tracer agent, surplus is a deionized water.
2. efficient low-phosphorus corrosion dirt dispersion agent as claimed in claim 1, it is characterized in that its physicochemical property is: following % is all mass percent
Appearance colorless or faint yellow or brown liquid do not have precipitation
Density (20 ℃), g/cm 31.00~1.20
Total phosphate content is (with PO 4 3-Meter), %≤5.0
PH value (1% aqueous solution)≤6.0
Solids content, % 〉=25.0
Orthophosphoric acid salt is (with PO 4 3-Meter) content, %≤0.5
Phosphorous acid is (with PO 3 3-Meter) content, %≤0.5
Azole content, % 〉=0.8
3. efficient low-phosphorus corrosion dirt dispersion agent as claimed in claim 1 is characterized in that thiazole is one or more in phenylpropyl alcohol thiazole or methyl phenylpropyl alcohol thiazole or the sulfydryl phenylpropyl alcohol thiazole.
4. efficient low-phosphorus corrosion dirt dispersion agent as claimed in claim 1 is characterized in that vinylformic acid-acrylate-co-polymer of sulfonate that tracer agent is modified for the hydroxyl pyridine derivate.
5. as claim 1 or 4 described efficient low-phosphorus corrosion dirt dispersion agents, it is characterized in that vinylformic acid-acrylate-co-polymer of sulfonate that tracer agent hydroxyl pyridine derivate is modified is to synthesize under catalyst action with the hydroxyl pyridine derivate and obtain by containing one or more mixture in vinylformic acid, methacrylic acid, acrylamide, ester group, amino and the sulfonic acid group, have fluorescence, water-soluble and dispersed, it with and each water conditioner good synergistic effect is arranged.
6. the preparation method of efficient low-phosphorus corrosion dirt dispersion agent as claimed in claim 1, it is characterized in that in reactor, adding deionized water, start agitator, stir down and add 3%~6% dimethyl formamide respectively by following order, 8%~18%2-phosphonate group-1,2, the 4-butane tricarboxylate, 5%~15% vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multipolymer, 2%~12% Sunmorl N 60S, 1%~5% molybdenum or tungstate, 1%~2% thiazole, 3%~6% Zinc Chloride Anhydrous, 3%~6% tracer agent, after adding, supplies raw material deionized water to quantitative, stir after-filtration, cross the cleaner liquid packing and promptly get the efficient low-phosphorus corrosion dirt dispersion agent.
7. the application of efficient low-phosphorus corrosion dirt dispersion agent as claimed in claim 1, it is characterized in that dispersion agent is used for hardness and adds basicity less than 1100mg/L, chlorion is less than 1000mg/L, pH6.8~9.5, in the circulating water quality of turbidity less than 20NTYU, in recirculated water, add concentration and count 50~80mg/L, add concentration 3~4mg/L in fluorescence intensity by amount of makeup water.
8. the application of efficient low-phosphorus corrosion dirt dispersion agent as claimed in claim 7 is characterized in that being used for recirculated water high concentration multiple operation more than 5 times of middle and lower reach of Yangtze River source quality.
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