CN101560023A - Efficient low-phosphorus corrosion and scale inhibitor - Google Patents
Efficient low-phosphorus corrosion and scale inhibitor Download PDFInfo
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- CN101560023A CN101560023A CNA2009101420589A CN200910142058A CN101560023A CN 101560023 A CN101560023 A CN 101560023A CN A2009101420589 A CNA2009101420589 A CN A2009101420589A CN 200910142058 A CN200910142058 A CN 200910142058A CN 101560023 A CN101560023 A CN 101560023A
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Abstract
The invention relates to a low-phosphorus compound corrosion and scale inhibitor and applications in the treatment of high-alkalinity and high-hardness circulating cooling water thereof. The efficient low-phosphorus corrosion and scale inhibitor is characterized by adding the following components according to the circulating water: 0.2-1.2mg/L of hydroxyethylidene diphosphonic acid, 0.125-1mg/L of 2-phosphonic acid-1,2,4-tricarboxylic acid, 0.14-1.2mg/L of sulphonate copolymer, 0.625-5mg/L of maleic acid-acrylic acid copolymer, 0-1.6mg/L of polyacrylic acid and 0-0.4mg/L of copper relief agent. The low-phosphorus compound corrosion and scale inhibitor can be used for the treatment of circulating cooling water, has the total phosphorus content less than or equal to 0.5mg/L in the circulating water, has the advantages of good comprehensive performance, excellent CaCO3 scale resistance function, corrosion inhibition performance and small dosage of less than or equal to 20mg/L under normal condition, is applicable to the treatment of circulating cooling water, and reduces the hazards of phosphorus emission on environment.
Description
Technical field
The present invention relates to a kind of low-phosphorous composite scale-inhibiting corrosion inhibitor and application in high basicity, high rigidity recirculated cooling water are handled thereof.
Background technology
At present, in recirculating cooling water system, mainly exist fouling, corrosion and microorganism to endanger three aspect problems.Anti-locking system fouling and corrosion most convenient and effective means are to add corrosion inhibiting and descaling agent in recirculated cooling water.The prescription of the at present domestic cooling process that is usually used in circulating mostly is phosphine system prescription, and its host is for containing phosphonate group (PO
3H
2) the direct corrosion inhibiting and descaling agent that links to each other with carbon atom, often be referred to as organic phospho acid.Organic phospho acid has made water technology and technology that considerable progress arranged since the later stage in the sixties is developed and is applied to the recirculated cooling water processing.Compare with the inorganic polyphosphate in the early stage phosphorus line formulation, organic phospho acid have good chemical stability, not facile hydrolysis, can anti-comparatively high temps, dosing is little, and has inhibition concurrently and scale inhibition is difunctional.Organic phospho acid is a class cathode type inhibiter, is again class equivalent Scale inhibitors non-chemically simultaneously, has tangible molten limit effect.Their many metallic ions Ca in ground
2 +, Mg
2 +, Cu
2 +, Zn
2 +Deng all having good sequestering power even the inorganic salts of some metals such as CaCO
3, CaSO
4, MgSiO
3Deng deactivation is preferably also arranged.But P contained compound makes people recognize the importance of control P contained compound discharging gradually to the pollution of water body and the eutrophication problem that causes, the environmental administration of many countries has put into effect the discharging that corresponding regulations limits P contained compound, China GB8979-1996 " integrated wastewater discharge standard " first grade discharging requires all blowdown enterprise phosphorus (in P)≤0.5mg/L, and the application of organic phosphine therefore commonly used is restricted.
Summary of the invention
The objective of the invention is to avoid the deficiencies in the prior art that a kind of efficient low-phosphorus corrosion and scale inhibitor is provided.Big to solve in the Yellow River water system change of water quality, still have good scale inhibition effect at basicity, calcium under firmly up to the situation of 10mmol/L, and reach the requirement of GB8979-1996 " integrated wastewater discharge standard " first grade discharging.
For achieving the above object, the technical scheme that the present invention takes is: a kind of efficient low-phosphorus corrosion and scale inhibitor, its principal feature are by the recirculated water add-on: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 0.2～1.2mg/L; 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) 0.125～1mg/L; Sulfonic acid copolymer 0.14～1.2mg/L; Maleic acid-acrylic acid copolymer (MA/AA) 0.625～5mg/L; Polyacrylic acid (PAA) 0～1.6mg/L; Copper delays agent 0～0.4mg/L.
Described efficient low-phosphorus corrosion and scale inhibitor, described sulfonic acid copolymer be vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multiple copolymer (AA/AMPS) or/and vinylformic acid-acrylate-sulfonate terpolymer or/and carboxylate salt-sulfonate-nonionic terpolymer.
Described efficient low-phosphorus corrosion and scale inhibitor, described copper inhibitor are benzotriazole (BTA) or toluene a pair of horses going side by side triazole (TTA).
Described efficient low-phosphorus corrosion and scale inhibitor preparation method, its principal feature is that step is: earlier copper inhibitor is dissolved in maleic acid-acrylic acid copolymer or the polyacrylic acid, can suitably heat, promote its dissolving, other component adds in the reactor, after the stirring in proportion, the maleic acid-acrylic acid copolymer or the polyacrylic acid that will be dissolved with copper inhibitor are more slowly poured in the reactor, add entry, stirred 20～40 minutes, to mixing.This process is carried out at normal temperatures and pressures.
2-phosphonic acid butane-1,2, the 4-tricarboxylic acid has scale inhibition efficient height, advantage that phosphorus content is low, with the compound use of 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid obvious synergistic effect is arranged, also reduced the medicament usage quantity when strengthening scale inhibition effect, and sulfonic acid copolymer has excellent scale inhibition dissemination and not phosphorous, suitable high temperature, high pH value, height use firmly with under the high-alkali condition, be used with horse-propylene copolymer, still have good effect in turbidity the Yellow River water system higher, that change of water quality is bigger.
The invention has the beneficial effects as follows: low-phosphorous composite scale-inhibiting corrosion inhibitor of the present invention can be used for the processing of recirculated cooling water, and total phosphorous is smaller or equal to 0.5mg/L in recirculated water for it, and good combination property has good resistance CaCO
3Dirt function, corrosion inhibition, consumption is little, adds dose generally speaking smaller or equal to 20mg/L, is applicable to the recirculated cooling water processing, has reduced the harm of phosphorus discharging to environment.The present invention is particularly suitable for the bigger characteristics of the Yellow River water system change of water quality.Still have good scale inhibition effect at basicity, calcium under firmly up to the situation of 10mmol/L, guarantee the circulating water system safe operation.
Embodiment
Below in conjunction with embodiment principle of the present invention and feature are described, institute gives an actual example and only is used to explain the present invention, is not to be used to limit scope of the present invention.
Embodiment 1: a kind of efficient low-phosphorus corrosion and scale inhibitor includes 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 5.76%; 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) 2.5%; Vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multiple copolymer (AA/AMPS) 3%; Maleic acid-acrylic acid copolymer (MA/AA) 21.6%; Benzotriazole (BTA) 1.2%; Surplus is a water.
Preparation method: in 1 ton reactor, prepare
1 earlier 12kgBTA is dissolved in commercially available, solid content be 48% maleic acid-acrylic acid copolymer in 450kg;
Add HEDP (commercially available, solid content is 60%) 96kg in 2 reactors successively, PBTCA (commercially available, solid content is 50%) 50kg, AA/AMPS (commercially available, solid content is 30%) 100kg opens and stirs;
3 are having under the condition of stirring, and the toxilic acid-vinylformic acid mixed solution that slowly will be dissolved with BTA adds in the reactor;
4 add 292kg water, fully stir.
This product solid content is 32%, satisfies power industry, and the requirement of recirculated water corrosion inhibiting and descaling agent solid content 〉=32% is pressed 7mg/L or 14mg/L and added in the recirculated water, and the result is as follows:
When adding dose and being 7mg/L, HEDP 0.40mg/L in the recirculated water, PBTCA 0.175mg/L, sulfonic acid copolymer 0.21mg/L, horse-propylene copolymer 1.51mg/L, BTA 0.084mg/L.
When adding dose and being 14mg/L, HEDP 0.80mg/L in the recirculated water, PBTCA 0.35mg/L, sulfonic acid copolymer 0.42mg/L, horse-propylene copolymer 3.02mg/L, BTA 0.17mg/L.
Phosphorus content meets the requirement of GB8979-1996 " integrated wastewater discharge standard " first grade discharging in the recirculated cooling water.Anticorrosion-antiscaling effect meets every technical requirement of " industrial circulating cooling water processing standard " GB50050-94.
Embodiment 2: a kind of efficient low-phosphorus corrosion and scale inhibitor includes 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 4.8%; 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) 5%; Vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multiple copolymer (AA/AMPS) 6%; Maleic acid-acrylic acid copolymer (MA/AA) 14.4%; Benzotriazole (BTA) 2%; Surplus is a water.
Preparation method: in 1 ton reactor, prepare
1 earlier 20kgBTA is dissolved in commercially available, solid content be 48% maleic acid-acrylic acid copolymer in 300kg;
Add HEDP (commercially available, solid content is 60%) 80kg in 2 reactors successively, PBTCA (commercially available, solid content is 50%) 100kg, AA/AMPS (commercially available, solid content is 30%) 200kg opens and stirs;
3 are having under the condition of stirring, and the toxilic acid-vinylformic acid mixed solution that slowly will be dissolved with BTA adds in the reactor;
4 add 300kg water, fully stir.
This product solid content is 33.3%,, press 17mg/L or 20mg/L and add in the recirculated water, the result is as follows:
When adding dose and being 17mg/L, HEDP 0.82mg/L in the recirculated water, PBTCA 0.85mg/L, sulfonic acid copolymer 1.02mg/L, horse-propylene copolymer 2.45mg/L, BTA 0.34mg/L.
When adding dose and being 20mg/L, HEDP 0.96mg/L in the recirculated water, PBTCA 1.00mg/L, sulfonic acid copolymer 1.2mg/L, horse-propylene copolymer 2.90mg/L, BTA 0.4mg/L.
Embodiment 3: a kind of efficient low-phosphorus corrosion and scale inhibitor includes 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 4.32%; 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) 4.5%; Vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multiple copolymer (AA/AMPS) 5.4%; Maleic acid-acrylic acid copolymer (MA/AA) 12.96%; Polyacrylic acid (PAA) 6.5%; Benzotriazole (BTA) 1%; Surplus is a water.
Preparation method: in 1 ton reactor, prepare
1 earlier 10kgBTA is dissolved in commercially available, solid content be 48% maleic acid-acrylic acid copolymer in 300kg;
Add HEDP (commercially available, solid content is 60%) 72kg in 2 reactors successively, PBTCA (commercially available, solid content is 50%) 90kg, AA/AMPS (commercially available, solid content is 30%) 180kg, PAA (commercially available, solid content 50%) opens stirring;
3 are having under the condition of stirring, and the toxilic acid-vinylformic acid mixed solution that slowly will be dissolved with BTA adds in the reactor;
4 add 248kg water, fully stir.
This product solid content is 33.3%,, press 17mg/L or 20mg/L and add in the recirculated water.
This embodiment is applied to certain power plant's second phase recirculated water dynamic experiment, and former water is Huanghe water, and the result is as follows:
When adding dose and being 17mg/L, HEDP 0.74mg/L in the recirculated water, PBTCA 0.765mg/L, sulfonic acid copolymer 0.92mg/L, horse-propylene copolymer 2.20mg/L, PAA 1.11mg/L, BTA 0.17mg/L.
When adding dose and being 20mg/L, HEDP 0.86mg/L in the recirculated water, PBTCA 0.90mg/L, sulfonic acid copolymer 1.08mg/L, horse-propylene copolymer 2.59mg/L, BTA 0.34mg/L.
Embodiment 4: a kind of efficient low-phosphorus corrosion and scale inhibitor includes 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 6%; 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) 5%; Vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multiple copolymer (AA/AMPS) 6%; Maleic acid-acrylic acid copolymer (MA/AA) 15.36%; Benzotriazole (BTA) 1%; Surplus is a water.
Preparation method: in 1 ton reactor, prepare
1 earlier 10kgBTA is dissolved in commercially available, solid content be 48% maleic acid-acrylic acid copolymer in 320kg;
Add HEDP (commercially available, solid content is 60%) 100kg in 2 reactors successively, PBTCA (commercially available, solid content is 50%) 100kg, AA/AMPS (commercially available, solid content is 30%) 200kg opens and stirs;
3 are having under the condition of stirring, and the toxilic acid-vinylformic acid mixed solution that slowly will be dissolved with BTA adds in the reactor;
4 add 270kg water, fully stir.
This product solid content is 33.3%,, press 12mg/L or 17mg/L and add in the recirculated water.
This embodiment is applied to certain Controlling Auxiliaries in Power Plants water coolant dynamic experiment, and former water is Huanghe water, and the result is as follows:
When adding dose and being 12mg/L, HEDP 0.72mg/L in the recirculated water, PBTCA 0.60mg/L, sulfonic acid copolymer 0.72mg/L, horse-propylene copolymer 1.84mg/L, BTA 0.12mg/L.
When adding dose and being 17mg/L, HEDP 1.02mg/L in the recirculated water, PBTCA 0.85mg/L, sulfonic acid copolymer 1.02mg/L, horse-propylene copolymer 2.61mg/L, BTA 0.17mg/L.
Embodiment 5:-kind efficient low-phosphorus corrosion and scale inhibitor includes 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 4.2%; 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) 2.5%; Vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multiple copolymer (AA/AMPS) 2.8% and vinylformic acid-acrylate-sulfonate terpolymer 2.8%; Maleic acid-acrylic acid copolymer (MA/AA) 12.5%; Polyacrylic acid (PAA) 8%; Surplus is a water.
Embodiment 6: a kind of efficient low-phosphorus corrosion and scale inhibitor includes 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 5.76%; 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) 2.5%; Vinylformic acid-acrylate-sulfonate terpolymer 2.8%; Maleic acid-acrylic acid copolymer (MA/AA) 25%; Polyacrylic acid (PAA) 2%; Toluene a pair of horses going side by side triazole (TTA) 1.2%; Surplus is a water.
Embodiment 7: a kind of efficient low-phosphorus corrosion and scale inhibitor includes 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 5.76%; 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) 2.5%; Vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multiple copolymer (AA/AMPS) 2.8% and carboxylate salt-sulfonate-nonionic terpolymer 2.8%; Maleic acid-acrylic acid copolymer (MA/AA) 22.5%; Polyacrylic acid (PAA) 4%; Toluene a pair of horses going side by side triazole (TTA) 2%; Surplus is a water.
Embodiment 8: a kind of efficient low-phosphorus corrosion and scale inhibitor includes 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) 5.76%; 2-phosphonic acid butane-1,2,4-tricarboxylic acid (PBTCA) 2.5%; Carboxylate salt-sulfonate-nonionic terpolymer 5%; Maleic acid-acrylic acid copolymer (MA/AA) 22.5%; Toluene a pair of horses going side by side triazole (TTA) 1%; Surplus is a water.
Compound method is mixed with the product of certain solid content as example 1～4, carries out dynamic simulation experiment, according to experimental result, adds in the recirculated water by 5～20mg/L.
The above only is preferred embodiment of the present invention, and is in order to restriction the present invention, within the spirit and principles in the present invention not all, any modification of being done, is equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (4)
1. an efficient low-phosphorus corrosion and scale inhibitor is characterized in that by the recirculated water add-on: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 0.2～1.2mg/L; 2-phosphonic acid butane-1,2,4-tricarboxylic acid 0.125～1mg/L; Sulfonic acid copolymer 0.14～1.2mg/L; Maleic acid-acrylic acid copolymer 0.625～5mg/L; Polyacrylic acid 0～1.6mg/L; Copper delays agent 0～0.4mg/L.
2. efficient low-phosphorus corrosion and scale inhibitor as claimed in claim 1, it is characterized in that described sulfonic acid copolymer be vinylformic acid-2-acrylamide-2-methyl propane sulfonic acid multiple copolymer or/and vinylformic acid-acrylate-sulfonate terpolymer or/and carboxylate salt-sulfonate-nonionic terpolymer.
3. efficient low-phosphorus corrosion and scale inhibitor as claimed in claim 1 is characterized in that described copper inhibitor is benzotriazole or toluene a pair of horses going side by side triazole.
4. as the described efficient low-phosphorus corrosion and scale inhibitor preparation method of claim 1 to 3, it is characterized in that step is: earlier copper inhibitor is dissolved in maleic acid-acrylic acid copolymer or the polyacrylic acid, other component adds in the reactor in proportion, after the stirring, the maleic acid-acrylic acid copolymer or the polyacrylic acid that will be dissolved with copper inhibitor are more slowly poured in the reactor, add entry, stirred 20～40 minutes, to mixing.
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