CN1654368A - Environmental-protection high-efficiency low-phosphonic scale inhibitor composition and its preparation method and use - Google Patents
Environmental-protection high-efficiency low-phosphonic scale inhibitor composition and its preparation method and use Download PDFInfo
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- CN1654368A CN1654368A CNA2004100394264A CN200410039426A CN1654368A CN 1654368 A CN1654368 A CN 1654368A CN A2004100394264 A CNA2004100394264 A CN A2004100394264A CN 200410039426 A CN200410039426 A CN 200410039426A CN 1654368 A CN1654368 A CN 1654368A
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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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- 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
Abstract
The present invention discloses one kind of environment protecting high effect low phosphine antiscaling and corrosion inhibiting composition and its preparation process. The antiscaling and corrosion inhibiting composition includes low phosphine polymer, polynary phosphonic acid-carboxylic acid copolymer, copper corrosion inhibitor and water. The preparation process includes pumping ternary copolymer of 2-phospho-1, 2, 4-tricarboxy butane, acrylic acid and sulfonate into reactor and stirring; dissolving benzotriazole in the reactor via stirring; and adding water via stirring. The present invention also provides the application of the composition in the antiscaling and corrosion inhibiting treatment of circular water in thermal apparatus. The present invention has obvious antiscaling and corrosion inhibiting effects.
Description
Technical field
The present invention relates to a kind of environment-friendly highly efficient low-phosphorus antiincrustation corrosion-inhibiting composition, its preparation method and application, relate in particular to scale inhibitor composition and method of making the same and the application in heat power equipment fouling and corrosive circulating water treatment, used.
Background technology
The development of phosphorous anti-incrustation corrosion inhibitor starts from the beginning of the fifties the earliest, in order to reduce chromate content in the water coolant, the U.S. promptly gets down to the principle of utilizing synergistic effect, in the chromic salt prescription, add inorganic phosphate and zinc salt, chromic salt is reduced to below the 20mg/l by original 200mg/l in prescription, alleviated the degree of environmental pollution.
The initial stage sixties, the harm of bringing for human body and environment for fear of chromic salt, the U.S. at first develops and has synthesized organo phosphorous compounds, and complete organic, nonmetal water coolant scheme---organophosphate and polymkeric substance compound prescription have been developed in 1967, this scheme provides the method that suppresses corrosion and scaling under alkaline water coolant condition first, this technical breakthrough has promoted that phosphorus is the development of water conditioner.
To after the eighties, because environmental regulation more becomes strict: explicitly call for the discharging of phosphorus restriction.Conservation of resources and absorption method also require water saving, increase the recycle of water.All these are objectively also providing good opportunity for the development of new and effective anti-incrustation corrosion inhibitor.Be continuous variation and the harsh more condition of water quality that adapts to environmental requirement, one of focus of the development of external water conditioner is exactly organophosphorus carboxylic acid corrosion inhibiting and descaling agent and application and development thereof, wherein the most representative is exactly 2-phosphoric acid butane-1,2,4-tricarboxylic acid (being PBTCA).This product is that German Hass Geffers Cologue was in development synthetic patented product in 1970.Because of it is widely used industrial at the anticorrosion-antiscaling property that shows excellence aspect the water treatment.Invent the phosphorous polymer anti-incrustation corrosion inhibitor in recent years abroad again, and obtained certain application.
Phosphorous anti-incrustation corrosion inhibitor generally can be divided into two big classes, inorganic Phosphorus and organic phosphates.See the following form:
Phosphorous anti-incrustation corrosion inhibitor
| Classification | For example | |
| Inorganic Phosphorus organic phosphine class | Poly-phosphate Organophosphonate organic phosphonate organic phosphine carboxylic acid phosphorous polymer | Hexametaphosphate polyvalent alcohol phosphonic acid ester (POE) 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP) PBTCA Amino Trimethylene Phosphonic Acid (BeLeLene500) |
In China, since the sixties, the development of phosphorous anti-incrustation corrosion inhibitor has been experienced from the inorganic phosphate salt to the organic phosphine class, as the history of organic phospho acid ester, organic phosphonate.After the eighties, because China environmental protection requires the discharging of phosphorus restriction, the lower phosphine carboxylic-acid corrosion inhibiting and descaling agent of phosphorus content has appearred again.Contain phosphino-(PO simultaneously in the phosphine carboxylic-acid corrosion-mitigation scale-inhibition agent molecule
3H) and carboxyl (COOH), representative 2-phosphono-containing butane-1,2,4 tricarboxylic acid (PBTCA) and 2-hydroxyl phosphino-acetate (HPAA) arranged.Phosphine carboxylic-acid anti-incrustation corrosion inhibitor phosphorus content is low, and Heat stability is good has unique anticorrosion-antiscaling effect in the scope of broad, paid close attention to widely in the water treatment agent industry.
In numerous phosphorous anti-incrustation corrosion inhibitors, poly-phosphate, Organophosphonate, organic phosphonate, organic phosphine carboxylic acid were once arranged, contained phosphine polymkeric substance etc., these anti-incrustation corrosion inhibitors have all been brought into play very important effect in the period of its application, but exist shortcoming.
For poly-phosphate, it is a kind of cathode type and precipitation membrane inhibiter, in use existing needs the control pH value, be difficult to control corrosion speed, therefore early overstand in recirculated water increases shortcomings such as percent hydrolysis easily, in the past 10 years, the poly-phosphate anti-incrustation corrosion inhibitor China gradually by the scale inhibitor of other kinds and replace, add acid and transfer the inorganic phosphorus zincification water treatment scheme of pH value also to be eliminated gradually.
Organophosphonate belongs to anode type corrosion inhibitor, and its inhibitor mechanism mainly is to make the lattice distortion of calcium dirt, hinders the normal growth of calcium dirt.Its outstanding advantage is that it can also can carry out under higher cycles of concentration containing maintenance scale inhibitor effect under the smeary condition of water quality, and the total molten solid amount of water coolant can allow to bring up to 3000mg/l.Under the situation that but Organophosphonate is higher in temperature, alkalescence is stronger, also hydrolysis easily, produce ortho-phosphoric acid and corresponding alcohol, the effect of forfeiture scale inhibitor, because the consumption of Organophosphonate is very low, generally have only about 10mg/l, so the calcium phosphate scale that generates after the hydrolysis is unlikely the generation adverse consequences.
Organic phosphonate is to develop successively in the later stage in the sixties, the water treatment agent of determining before and after the seventies, and its appearance makes water technology step major step forward.Organic phosphonate belongs to the cathode type inhibiter, it has compared better chemical stability with inorganic phosphate, but also can resolve into orthophosphoric acid salt under given conditions, hydrolysis may appear, in addition, the corrosion mitigating effect of organic phosphonate is subjected to the content influence of water intermediate ion bigger, and calcium ion concn is too big, and corrosion mitigating effect is just poor.Organic phosphine carboxylic acid, existing phosphatic phosphorus group (PO in its molecular structure
3H
2) have the poly carboxylic acid group (COOH), to have two kinds of performances simultaneously concurrently: inhibition, scale inhibition again.
Containing the phosphine polymkeric substance is relatively specific polymers of a class, is actually by a kind of inorganic monomer Hypophosporous Acid, 50, and it also plays action of evocating when polymerization, form with other organic monomer copolymerization.Be characterized in carboxyl and phosphonate group are combined on the same molecule, therefore be referred to as polyphosphonic acid carboxylic acid (the English PCA of abbreviation).At present that developed more with PCA kind that developing, look the polymer monomers difference and be divided into phosphino-polyacrylic acid extremely multipolymer and phosphino-polymaleic acid and multipolymer thereof.
The more new development of cooling water treatment agent can be described as the result that environmental requirement improves constantly to a great extent.In decades, the development trend of phosphorous anti-incrustation corrosion inhibitor is that the content of phosphorus constantly obtains descending from inorganic Phosphorus to the organic phosphine class, from the organic phospho acid to the organic phosphine carboxylic acid and contain the phosphine polymkeric substance.Following table is the phosphorous scale of phosphorous water conditioner commonly used, and we can see that phosphorous polymer will be the developing direction of phosphorous anti-incrustation corrosion inhibitor in the more than ten years in future from following table.
The phosphorous scale of phosphorous water conditioner commonly used
| Kind | Phosphorous water conditioner | P content (W%) in the molecule |
| Poly-phosphate Organophosphonate organic phosphonate organic phosphine carboxylic acid contains the phosphine polymkeric substance | Sodium phosphate trimer calgon polyalcohol phosphonate ester HEDP ATMP ethylene diamine tetra methylene phosphonic acid sodium PBTCA 2-hydroxyl phosphino-acetic acid ATMP | ???????25.3 ???????30.4 ???????27.8 ???????30.1 ???????31.1 ???????28.4 ???????11.5 ???????19.9 ???????＜3.0 |
Along with the rapid development and the development of economy, social water consumption sharply increases, water saving, and the utilization ratio that improves water resources has been the task of top priority.Each heavy industry large-lot producer, thermal power generation corporations all are the rich anies influential family of water, strengthen the management of water, improve recirculated water management level, and water saving is an inevitable development trend.Yet the recycle of water, the raising of cycles of concentration require to take suitable water technology, to solve the fouling and the etching problem of heat power equipment.The fouling of heat power equipment and corrosion not only can cause the fouling and the corrosion damage of equipment, the more important thing is that it can cause equipment normally to move, and are directly restricting unit safety, economical operation, will bring heavy losses to enterprise when serious.
But still there is the effectively shortcoming of scale inhibition and inhibition in above-mentioned phosphorous anti-incrustation corrosion inhibitor.
Summary of the invention
The purpose of this invention is to provide a kind of environment-friendly highly efficient low phosphine scale inhibitor composition, its preparation method and application, a kind of scale inhibitor composition and method of making the same and application of using in heat power equipment fouling and corrosive circulating water treatment especially be provided, overcome the effectively shortcoming of scale inhibition and inhibition of existing phosphorous anti-incrustation corrosion inhibitor.
A kind of low phosphine environment-friendly type anti-incrustation corrosion inhibitor provided by the invention, be to be the composite water treatment compositions of main component by low phosphine polymkeric substance, phosphine carboxylic acid multicomponent copolymer and extraordinary copper inhibitor, can be widely used in environmental protection and comprehensive utilization of resources field, especially in heat power equipment fouling and corrosive circulating water treatment, use.
The objective of the invention is to be achieved through the following technical solutions:
A kind of environment-friendly highly efficient hangs down phosphine scale inhibitor composition, comprises following component: low phosphine polymkeric substance, phosphine carboxylic acid multicomponent copolymer, copper inhibitor, water.
Described component can be following parts by weight of component: low phosphine polymkeric substance 20-40, phosphine carboxylic acid multicomponent copolymer 40-70, copper inhibitor 2-6, water 55-80;
Be preferably following parts by weight of component: low phosphine polymkeric substance 25-35, phosphine carboxylic acid multicomponent copolymer 50-60, copper inhibitor 3-5, water 60-75;
Be preferably following parts by weight of component: low phosphine polymkeric substance 30, phosphine carboxylic acid multicomponent copolymer 55, copper inhibitor 4, water 68.
The wherein low concrete composition of phosphine polymkeric substance can be 2-phosphono-containing butane-1,2,4 tricarboxylic acid (PBTCA), and molecular formula is C
7H
11O
9P.
Chemical structural formula is:
Its existing phosphonic acids has the structural performance of carboxylic acid again, so can embody good corrosion and scale inhibition performance, with organic phospho acid commonly used, compare as Amino Trimethylene Phosphonic Acid (ATMP), HEDTMP (second diamines four methylenephosphonic acid Na), has remarkable characteristic, simultaneously be far superior to organic phospho acid aspect the high temperature scale-inhibiting properties, can improving the solubleness of zinc, even be also can make zinc be in dissolved state at 9.5 o'clock at pH value.
The concrete composition of phosphine carboxylic acid multicomponent copolymer can be vinylformic acid-sulfonate terpolymer, and molecular formula is [C
3H
4O
2]
n[C
7H
18NO
4S]
m, for can be known integer, and these multipolymers have close effect in the present invention in this copolymer molecule formula for or multiple copolymer more, n and m; Be specially vinylformic acid and 2-acrylamide-2-methyl propane sulfonic acid (AMPS) multiple copolymer, have the performance of inhibition and scale inhibition concurrently, calcium phosphate and zinc dirt there is remarkable scale inhibition ability, ferric oxide there is good dispersing property, being applicable to the water quality of high PH, high basicity, high rigidity, is the ideal dirt dispersion agent of realizing the high concentration multiple operation.Described salt can be known sodium salt, sylvite etc.
The concrete composition of described copper inhibitor can be benzotriazole, and its molecular formula is C
6H
5N
3
Chemical structural formula is:
Benzotriazole is white or Bluish white needle crystal.BTA (benzotriazole) can form covalent linkage and coordinate bond with copper atom, replace into key shape polymer mutually, at copper surface composition multilayer proofing film, make the surface of copper not produce electrochemical reaction, thereby have fabulous corrosion inhibition, metallic substance such as aluminium, cast iron, steel, nickel, zinc are also had same corrosion protection effect.In recirculated cooling water, as with poly-phosphate, molybdate, sulphite and organophosphate etc. and usefulness, can improve the corrosion mitigating effect of this water quality stabilizer.BTA (benzotriazole) also can with multiple dirt dispersion agent, composite as polyacrylic acid, horse propylene copolymer, polymaleic acid, acrylic copolymer etc., corrosion mitigating effect the best in the inclosed recirculated cooling water system especially.BTA (benzotriazole) is because aspects such as rust inhibition, toxicity, thermostability and chemical stability are all good than the domestic benzothiazolyl mercaptan of using morely of past (MBT), so at present external most users replace MBT with BTA, domestic also just having a this development trend.
In the water treatment agent of power industry, for water with high rigidity, high basicity, high pH value " three height " character, common corrosion inhibiting and descaling agent can not satisfy its requirement as electric power plant circulating water system Amino Trimethylene Phosphonic Acid (ATMP) commonly used, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDPA), second diamines four methylenephosphonic acid Na (HEDTMP) etc.Therefore, in this case, should select component thing novel, that have good anti-hardness, alkali resistant degree performance for use.
Among the present invention, 2-phosphate-1,2,4-butane tricarboxylate (PBTCA) has excellent anticorrosion-antiscaling property, its existing phosphonic acids has the structural performance of carboxylic acid again, so can embody good corrosion and scale inhibition performance, with organic phospho acid commonly used, as ATMP (Amino Trimethylene Phosphonic Acid), HEDPA (1-Hydroxy Ethylidene-1,1-Diphosphonic Acid), HEDTMP (second diamines four methylenephosphonic acid Na) compares, have remarkable characteristic, high temperature resistant, resistance to oxidation is being far superior to organic phospho acid aspect the high temperature scale-inhibiting properties simultaneously, calcium dirt to carbon has excellent restraining effect, can improve the solubleness of zinc, even be also can make zinc be in dissolved state at 9.5 o'clock, have good synergy at PH, be a kind of multifunction environment-protection type reagent of low-phosphorus corrosion scale inhibition, be specially adapted to high rigidity, high basicity, high pH value, the water conditioning of high concentration multiple.
The formulation of scale inhibitor composition of the present invention can be liquid.
The present invention also provides described scale inhibitor preparation of compositions method, may further comprise the steps:
Get above-mentioned prescription 2-phosphate-1,2 in proportion, 4-butane tricarboxylate (PBTCA), vinylformic acid-sulfonate terpolymer, benzotriazole (BTA), water, butane;
In PBTCA, vinylformic acid-sulfonate terpolymer suction reactor, stir mixing; Preferred unlatching stirring velocity is 80 rev/mins, mixing 20 minutes;
Under stirring state, benzotriazole (BTA) is added in the reactor, continue to stir, treat the BTA dissolving;
Add the water stirring and evenly mixing; Promptly get the present composition.
The present invention also provides the application of described scale inhibitor composition in heat power equipment fouling and corrosive circulating water treatment, in recirculated cooling waters such as petrochemical system, iron and steel system and chemical industry, said composition is by moisturizing, its dosage is preferably 50～100mg/l, and in the processing of the recirculated cooling water of power industry, said composition is by moisturizing, and its dosage is preferably 8～12mg/l, demonstrates fully the characteristic of its low dosage.
The present invention has the following advantages:
1, environment-friendly highly efficient low-phosphorus antiincrustation corrosion-inhibiting composition of the present invention is the circulating water treatment composition that fouling and etching problem at heat power equipment develop, its scale inhibition performance can reach more than 95%, corrosion rate then is lower than national standard (0.005 μ m/a), and technical superiority is obvious.It also allows industrial circulating water that the final condition of broad is arranged outside satisfying the condition by phosphorus value p＜0.5mg/l in the draining the national requirements for environmental protection, particularly to high incrustation ion water, uses this medicament can make the recirculated water cycles of concentration break through 3 times-4.5 times.Therefore, this anti-incrustation corrosion inhibitor is a kind of environment-friendly type anti-incrustation corrosion inhibitor of efficient low-phosphorus.
2, the present invention has low dosage, energy-efficient technique effect.In the recirculated cooling water of power industry is handled, the pharmaceutical products dosage of standard is 8～12 gram/tons (by moisturizings), the pharmaceutical products dosage of standard is 50～100 gram/tons (by moisturizings) in recirculated cooling waters such as petrochemical system, iron and steel system and chemical industry, as seen its using dosage is very low, but has energy-efficient property.
3, the present invention is by its high comprehensive performance of a large amount of evidences.Its compound prescription is fit to the water conditioning of severe condition more, makes the calcium of recirculated water can reach 2000mg/l firmly, and chlorion or sulfate ion can reach 5000mg/l.And treatment effect further improves, and cycles of concentration can reach 6-8, and Corrosion rate in Carbon Steel adheres to speed less than 15mcm less than 0.075mm/a.Phosphorus content is (with PO in recirculated cooling water
4 3-Meter) under the situation less than 2.5mg/l, the scale-inhibiting properties of TW-38 medicament reaches the requirement of national Design of Circulation Cooling Water Treatment standard.Remarkable by different on-the-spot water quality being carried out dynamic and static evidence effect, concentrated times can reach 8-10 doubly, and the equipment non-scaling does not corrode.
4, the present composition has carried out the trial run in 1 year by a definite date, open condenser after, copper pipe surface has one deck chocolate protective membrane, no fouling, corrosion take place.The proof present composition has been filled up recirculated water need not increase facility investment, only adds the blank that medicament can reach zero release.
5, the present composition has reliable in quality, tolerance is big, widely applicable, and in its industrial application, every operating index and detection index all reach and be better than the requirement of GBJ50-83, production department of main office of China Petrochemical Industry relevant regulations.No matter after using the present composition, carry out equipment inspection, be simple steel heat exchanger, or copper and copper alloy interchanger, water tank tube bank inwall and end socket all do not have obvious corrosion, dirt takes place, no spot corrosion and rust gold-plating, and the equipment inspection state obviously is better than the domestic same device level same period.Compare and other like products, environment-friendly highly efficient low-phosphorus antiincrustation corrosion inhibitor advanced technology, than still having anticorrosion-antiscaling property preferably under the mal-condition, described high concentration multiple is meant the water quality that saliferous is high at high rigidity, high basicity, high pH value, high concentration multiple etc.It will be further appreciated that, use the formed dirt of water after the environment-friendly highly efficient low-phosphorus antiincrustation corrosion inhibitor is handled to be netted fish scale shape, and loose, so neither influence is conducted heat, and is convenient to clean.Simultaneously, the prescription of environment-friendly highly efficient low-phosphorus antiincrustation corrosion inhibitor has low-phosphorous characteristics, and good environmental protection does not constitute a threat to environmental emission.
6; in all heat-exchanging process processes of industrial production; because the requirement of water saving; need by improving the utilization coefficient again of recirculated cooling water; it is the purpose that cycles of concentration reaches water saving; concentrating of water will cause various dissolved salts content increases in the water; suitable temperature and illumination can impel the bacterium algae to grow again; cause water quality deterioration; at heat-exchange equipment; promptly can cause fouling; corrosion; foundry loam and bacterium algae adhere to, and have reduced the rate of heat exchange of heat-exchange equipment, and serious will cause interchanger; the pipe plug plug; perforation; cause the equipment non-programmed halt, have a strong impact on normal industrial production activity.
Environment-friendly highly efficient low-phosphorus antiincrustation corrosion inhibitor of the present invention is at industrial circulating cooling water water quality and industrial manufacture process characteristics and efficient scale, inhibition, dispersion, the fungicidal composition developed, can prevent effectively that the problems referred to above from taking place, when cycles of concentration reaches 2 times, can economize on water more than 95%, the work-ing life of prolongation equipment, improve heat exchange efficiency, reduce consuming, increase output, the equipment that guaranteed stably moves; Simultaneously, for Steel Plant and enterprise, this class causes the enterprise of environmental pollution easily, the high scale inhibition performance and the rust inhibition of environment-friendly highly efficient low-phosphorus antiincrustation corrosion inhibitor, and unique low-phosphorous, feature of environmental protection will reduce the equipment amortization rate effectively and alleviate produces the pollution problem that is brought.
For proving above-mentioned advantage and effect, the present invention has carried out following performance comparison test:
The performance comparison test of the present invention and domestic and international similar reagent:
The pharmaceutical products dosage of standard is 50～100mg/l (by moisturizing) in recirculated cooling waters such as petrochemical system, iron and steel system and chemical industry, and in the processing of the recirculated cooling water of power industry, the pharmaceutical products dosage of standard is 8～12mg/l (by moisturizing)], and under the field control, its scale inhibition performance can reach more than 95%, corrosion rate then is lower than national standard (0.005 μ m/a), and technical superiority is obvious.It is except satisfying the national requirements for environmental protection in the draining phosphorus value＜1.5mg/l (with PO
4 3-Meter) outside the condition, also allows industrial circulating water that the final condition of broad is arranged,, use this medicament can make the recirculated water cycles of concentration break through 3-4.5 doubly particularly to high incrustation ion water.Therefore, this anti-incrustation corrosion inhibitor is a kind of environment-friendly type anti-incrustation corrosion inhibitor of efficient low-phosphorus.
The said composition technical performance index:
Outward appearance: faint yellow or deep yellow transparent liquid
Solids content (%):＞33
Copper inhibitor (%):＞3.0
Total phosphorus (%): 6.8-8
PH value (1% aqueous solution): 1.5-2.5
Density g/cm
3(20 ℃): 1.1-1.3
What domestic water treatment agent was mainly taked is phosphorus line formulation, is to adopt inorganic poly-phosphate or organophosphate to make inhibiter.Generally all has the shortcoming of high phosphorus, and effect is not remarkable.
Following table is that this project is at Ca
3(PO
4)
2The antisludging test result
| N (cycles of concentration) | The present composition | Inhibiter A (Amino Trimethylene Phosphonic Acid) | Inhibiter B (Amino Trimethylene Phosphonic Acid) |
| ????????????Ca 3(PO 4) 2Scale inhibition performance (%) | |||
| ?????1.5 | ????85.80 | ????79.50 | ????77.90 |
| ?????2.0 | ????80.36 | ????50.69 | ????58.32 |
| ?????3.0 | ????82.19 | ????36.21 | ????41.57 |
| ?????4.0 | ????75.96 | ????37.94 | ????40.92 |
Through contrast as seen, anti-incrustation corrosion inhibitor of the present invention has the characteristics of efficient low-phosphorus, and effect is remarkable.
2, performance analysis
The quality of industrial circulating cooling water water quality is related to the fouling corrosion problem and the working order of machine.Because the limitation of recirculated cooling water treatment technology, prescription and level of management, low multiple circulating phenomenon accounts for the overwhelming majority.Therefore, in water treatment market, the demand and the consumption of the environment-friendly type scale inhibitor type water conditioner of water treatment high concentration multiple also constantly increased.According to domestic, world market current situation and prospect statistics, market estimates that 2004 demand will reach 2,000,000 tons, and this type of product demand increases progressively and will remain on about 25% in 5 years from now on.Because becoming increasingly conspicuous of shortage of water resources contradiction, the service water price also increased to 1.1 yuan/ton by 0.3 yuan/ton of past, and had reached 2.0 yuan/ton in high water-deficient area, and the cyclic utilization rate and the water-saving rate that improve water coolant also more and more receive publicity.If use this kind environment-friendly highly efficient low-phosphorus antiincrustation corrosion inhibitor in 40% scope in the middle of numerous Steel Plant and other waters rich and influential family, its consumption will reach about 1000 tons.In addition, in industrial application, use the present composition industrial water fee and effluent charge can be reduced to 10%, and can reduce the ratio of depreciation of equipment, reduce maintenance of equipment, direct economic benefit and indirect economic effect are all very remarkable.
Description of drawings
Fig. 1 is three river electric power plant circulating water test synthesizing maps
To represent basicity, YD to represent hardness, Kcl-be that the concentration rate of Cl-, concentration rate, Δ A that KCa2+ is Ca2+ are that Kcl--KCa2+, KMa are that concentration rate, the KYD of basicity is the concentration rate of hardness to JD among the figure.
Fig. 2 is corrosive nature test erosion rate contrast figure
A is that blank B is the water after concentrating 4 times
Embodiment
Embodiment 1
A kind of environment-friendly highly efficient low-phosphorus antiincrustation corrosion-inhibiting composition contains following component (kilogram): 2-phosphino--1,2,4 butane tricarboxylates (PBTCA) 30, vinylformic acid-sodium sulfonate terpolymer 55, benzotriazole (BTA) 4, water 68.
The preparation method of said composition is:
1, gets the raw materials ready:, successively PBTCA, vinylformic acid-sodium sulfonate terpolymer, water, butane are weighed with volume pump according to above-mentioned formulation ratio.
2, produce: open vacuum pump, in PBTCA, vinylformic acid-sodium sulfonate terpolymer suction reactor, open and stir, 80 rev/mins of stirring velocitys, about 20 minutes, mixing; Under stirring state, BTA is added in the reactor, continue to stir, treat that BTA all dissolved about 40 minutes; Add the water stirring and evenly mixing, packing promptly gets the present composition.
Embodiment 2
A kind of environment-friendly highly efficient low-phosphorus antiincrustation corrosion-inhibiting composition contains following component (kilogram): 2-phosphino--1,2,4 butane tricarboxylates 25, vinylformic acid and 2-acrylamide-2-methyl propane sulfonic acid (AMPS) multiple copolymer 50, benzotriazole 3, water 60.
The preparation method of said composition is: with embodiment 1.
Embodiment 3
A kind of environment-friendly highly efficient low-phosphorus antiincrustation corrosion-inhibiting composition contains following component (kilogram): 2-phosphino--1,2,4 butane tricarboxylates 35, vinylformic acid-potassium sulfonate terpolymer 60, benzotriazole 5, water 75.
The preparation method of said composition is: with embodiment 1.
Embodiment 4
A kind of environment-friendly highly efficient low-phosphorus antiincrustation corrosion-inhibiting composition contains following component (kilogram): 2-phosphino--1,2,4 butane tricarboxylates 20, vinylformic acid-sodium sulfonate terpolymer 40, benzotriazole 2, water 55.
The preparation method of said composition is: with embodiment 1.
Embodiment 5
A kind of environment-friendly highly efficient low-phosphorus antiincrustation corrosion-inhibiting composition contains following component (kilogram): 2-phosphino--1,2,4 butane tricarboxylates 40, vinylformic acid-sodium sulfonate terpolymer 70, benzotriazole 6, water 80.
The preparation method of said composition is: with embodiment 1.
Embodiment 6
The application of a kind of scale inhibitor composition in heat power equipment fouling and corrosive circulating water treatment, this scale inhibitor composition is the composition of embodiment 1, in petrochemical system, iron and steel system and chemical industry recirculated cooling water, said composition is by moisturizing, and its dosage is 50～100mg/l, and in the processing of the recirculated cooling water of power industry, said composition is by moisturizing, its dosage is 8～12mg/l, demonstrates fully the characteristic of its low dosage, and the present invention has significant scale inhibitor effect.
Described composition scale inhibition and corrosion experiment are as follows:
One, present embodiment 1 composition scale-inhibiting properties experiment
1.1 experiment purpose
Add water stablizer combination treatment three river generating plant circulation-waters by sulfuric acid, check out according to the polarity carbonate hardness to reach the highest concentration rate.
1.2 experiment condition
(1) controlling this composition TW38 water stablizer add-on is 3.5mg/L (active ingredient).
(2) adding the sour pH value of regulating recirculated water is controlled in 8.0～8.5 scopes.
(3) experimental water is provided by power station, three rivers.
1.3 experimental procedure
Get 5 liters of beakers and accurately pour the 5L experimental water into, add the water stablizer stock solution of volume calculated, the 0# cup does not add as blank.Beaker inserted carry out evaporation concentration in the water bath with thermostatic control that is warming up to 50 ± 1 ℃, the control agitator speed is 150r/min, uses the electric fan air blast simultaneously, regulate tongs replenish in the beaker continuously experimental water to the 5000ml scale marks with additional vaporization losses; Regularly in beaker, replenish experimental water exactly in addition, taken a sample at every turn and replenished the water distribution of respective volume immediately, and record.PH value of test in per four hours is regulated circulating water PH value to specialized range with the sulfuric acid of 3mol/l.
1.4 test event
1) before the experiment, the hardness in the test experiments water sample, basicity, calcium ion, chlorine root, pH value.
Hardness, basicity, calcium ion, chlorine root, pH value in per four hours test experiments solution in the experimentation, and calculate Kcl, Kca, KMA, KYD and Δ A value.After finishing, experiment increases total phosphorus and the positive phosphorus surveyed in the water sample.
1.5 three river generating plant circulation-water make up water water-quality guideline are analyzed (see Table 1, Fig. 1)
Hardness in table 1 water sample, basicity, calcium ion, chlorine root, PH initial value index analysis
| ????JD ????mmol/L | ??YD ??mmol/L | ??Ca 2+??mmol/L | ????Cl -????mg/L | ????PH |
| ????4.10 | ??3.91 | ??2.26 | ????6.06 | ????7.78 |
Annotate: on behalf of basicity, YD, the JD in Fig. 1 and the table 1 represent hardness, K
Cl -Be Cl
-Concentration rate, K
Ca 2+Be Ca
2+Concentration rate, Δ A be K
Cl --K
Ca 2+, K
MaConcentration rate, K for basicity
YDBe the concentration rate of hardness,
Conclusion:
This experiment is from 11 to 24 April in 2002, from table 1 and Fig. 1 as can be known, and along with the continuous evaporation concentration of water sample, the Cl in the recirculated water
-, YD, Ca
2+, content constantly increases, and is the growth of linear property, Cl
-Increase to 35.80mmol/L from 6.06mmol/L; YD increases to 22.74mmol/L from 3.91mmol/L; Ca
2+Increase to 13.15mmol/L from 2.26mmol/L, and PH and JD fluctuate within the specific limits owing to adding acid, PH roughly exists; 8.0 between～8.5, JD is about 3.00mmol/L.
Along with the continuous evaporation concentration of water sample, Cl
-, YD, Ca
2+Concentration rate be the growth of linear property, to 7:30 Cl on April 24
-Concentration rate increases to 5.908 times, and the YD concentration rate increases to 5.816 times, Ca
2+Concentration rate increase to 5.819 times, judge that experiment finishes.Total phosphorus is 4.8 in the mensuration recirculated water of experiment end back, and positive phosphorus is 0.5.YD, Ca as calculated
2+Δ A all less than 0.2, show in the whole experiment that recirculated water fouling does not take place to analyse phenomenon.
Above-mentioned description of test, the present composition have significant scale inhibition ability.
Two, the present composition (being designated hereinafter simply as TW38) corrosive nature test
1.1 experiment purpose
Adopt known rotary hanging plate corrosion measurement method, investigate three river generating plant circulation-waters and reach after 4 times corrosive property, will pass judgment on by the index comprehensives such as erosion rate that appearance color changes, weight-loss method records of testing the back copper pipe to the condensing copper pipe at cycles of concentration.
1.2 experiment condition
Experiment water quality: experiment water is concentrated into 4 times, and experimental water is provided by power station, three rivers.Water stablizer add-on is 3.5mg/L (active ingredient); Experiment water temperature: 45 ± 1 ℃.Rotating speed: 150r/min; Time: 7 days; Hang the copper tube sheets number: in every glass three.
1.3 experimental procedure
The test piece of condensing copper pipe is cut into the long pipeline section of 15mm, and 180 degree are cut open then, and test piece is used dehydrated alcohol and acetone wiped clean at last earlier after 200～No. 1000 sand paper are polished successively, and dry back is with the accurate weighing of balance.The basicity of routine test water sample, hardness, chlorine root and pH value in the experimentation, the appearance change of record copper pipe test piece after experiment finishes, is weighed to the copper pipe lacing film that takes out, and calculates erosion rate.
1.4 the analysis of water sample in the corrosion experiment
| ???JD ???mmol/L | ??YD ??mmol/L | ??Ca 2+??mmol/L | ??Cl -??mg/L | ??PH | ??SO42 -??mg/L | Total phosphorus mg/L | Positive phosphorus mg/L |
| ???2.80 | ??15.70 | ??9.08 | ??24.30 | ??8.02 | ??150 | ?3.2 | ?0.4 |
1.5 corrosive nature experimental analysis and conclusion
1) experiment back copper pipe test piece appearance change
| The water sample title | Copper pipe test piece appearance color |
| Blank | Chocolate, the surface is sent out dirty, with corrosion product |
| Concentrate 4 times of water | Golden yellow, cleaning surfaces light, corrosion phenomenon are not obvious |
2) experiment copper pipe lacing film rate analysis figure sees Fig. 2; from figure as can be known; blank sample erosion rate is to add 5.5 times of water sample after the present composition concentrates; the erosion rate that adds the concentrated back of present composition water sample is 0.0018mm/a; reach national requirements (＜0.005mm/a); in the present invention's test; sulfate radical in the recirculated water is about 130～150mg/L; improve more than cycles of concentration to 3.5～4 times along with adding acid; the recirculated water saltiness sharply increases; severe corrosive ion content wherein obviously strengthens, and this has just strengthened the corrosion tendency of condenser copper tube, but experiment as seen; the present composition has played good provide protection to copper pipe; the copper pipe test piece does not have the obvious corrosion feature, and its surface formed relatively successive protective membrane of one deck, and the erosion rate of its lacing film only is equivalent to 1/3 of national standard in addition.
Conclusion: from accompanying drawing 2 as can be known, blank sample erosion rate is 5.5 times that the adding present composition concentrates the back water sample, answer this, and provable this recirculated water combination treatment scheme can play significant inhibitory effect to the corrosion tendency of condensing copper pipe.
Claims (8)
1, the low phosphine scale inhibitor composition of a kind of environment-friendly highly efficient comprises following component: low phosphine polymkeric substance, phosphine carboxylic acid multicomponent copolymer, copper inhibitor, water.
2, according to the efficient low phosphine scale inhibitor composition of claim 1, described component can be following parts by weight of component: low phosphine polymkeric substance 20-40, phosphine carboxylic acid multicomponent copolymer 40-70, copper inhibitor 2-6, water 55-80.
3, according to the efficient low phosphine scale inhibitor composition of claim 1 or 2, described component can be following parts by weight of component: low phosphine polymkeric substance 25-35, phosphine carboxylic acid multicomponent copolymer 50-60, copper inhibitor 3-5, water 60-75.
4, according to the efficient low phosphine scale inhibitor composition of claim 1 or 2, described component can be following parts by weight of component: low phosphine polymkeric substance 30, phosphine carboxylic acid multicomponent copolymer 55, copper inhibitor 4, water 68.
5, according to the efficient low phosphine scale inhibitor composition of one of claim 1-4, wherein low phosphine polymkeric substance is a 2-phosphino--1,2,4 butane tricarboxylates; The phosphine carboxylic acid multicomponent copolymer is vinylformic acid-sulfonate terpolymer; Described copper inhibitor is a benzotriazole.
6, the low phosphine scale inhibitor preparation of compositions method of the environment-friendly highly efficient of one of a kind of claim 1-5 may further comprise the steps:
Get component 2-phosphate-1,2 in proportion, 4-butane tricarboxylate, vinylformic acid-sulfonate terpolymer, benzotriazole, water, butane;
With 2-phosphate-1,2, in 4-butane tricarboxylate, the vinylformic acid-sulfonate terpolymer suction reactor, stir mixing;
Under stirring state, benzotriazole is added in the reactor, continue to stir, treat the benzotriazole dissolving;
Add the water stirring and evenly mixing, promptly get the present composition.
7, the low application of phosphine scale inhibitor composition in heat power equipment fouling and corrosive circulating water treatment of the environment-friendly highly efficient of one of claim 1-5.
8, the environment-friendly highly efficient according to claim 7 hangs down the application of phosphine scale inhibitor composition in heat power equipment fouling and corrosive circulating water treatment, said composition is in petrochemical system, iron and steel system and chemical industry recirculated cooling water, said composition is by moisturizing, and its dosage is 50～100mg/l; Or in the processing of the recirculated cooling water of power industry, said composition is by moisturizing, and its dosage is 8～12mg/l.
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