CN1919752A - Environment-friendly type composite corrosion and scale inhibitor - Google Patents
Environment-friendly type composite corrosion and scale inhibitor Download PDFInfo
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- CN1919752A CN1919752A CN 200610127172 CN200610127172A CN1919752A CN 1919752 A CN1919752 A CN 1919752A CN 200610127172 CN200610127172 CN 200610127172 CN 200610127172 A CN200610127172 A CN 200610127172A CN 1919752 A CN1919752 A CN 1919752A
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Abstract
The invention discloses an environmental-protective composite inhibiting antisludging agent, which comprises the following parts: inhibiting component, antisludging component and deionized water, wherein the inhibiting component is composed of one or more materials in the molybdate, tungstate, borate, organic substituted carboxylic acid or organic heterocyclic compound; the inhibiting component contains one or more materials in the natural macromolecular compound, epoxy succinic acid or acroleic acid ternary copolymer.
Description
Technical field
The present invention relates to a kind of circulating water treatment water quality stabilizer, relate in particular to a kind of environment-friendly composite corrosion and scale inhibitor that is used for the cycle of treatment water coolant.
Background technology
21 century, the problem of maximum was global shortage of water resources problem, and this problem has caused mondial great attention.Simultaneously, along with China's constant development of economy, environmental pressure also constantly increases the weight of.Problem of environmental pollution also becomes the urgently problem of generation solution of China.In industry; industrial circulating cooling water is the water rich and influential family; be that chemical industry, metallurgy, thermal power generation or large-scale central air-conditioning all adopt recirculated water to carry out heat exchange; so; improve the service efficiency of industry or civilian recirculated water; adopt environmentally friendly chemical agent, for the conserve water resource, reduce production costs and strengthen environmental protection significant.
China's circulating water treatment is through after the early stage direct discharging, and along with the introduction of large-scale chemical fertilizer plant, industrial circulating water has entered the seventies and added the stage that water conditioner carries out circular treatment.Realized the advanced pattern of Automatic Dosing Online Monitoring Control till now, water treatment agent is also developed many pharmaceutical preparations that are applied to different cooling water systems.Said employing chromic salt or chromic salt/zinc salt water conditioner are handled in Xu Shouchang chief editor's " industrial colling treatment process " (publishing in the 1984) book, corrosion mitigating effect is remarkable, but because the toxicity of chromic salt is bigger, institute's effluent environmental pollution is bigger, and therefore eliminating need not.After this, China has introduced the water conditioner prescription S-6450 of Castanea crenata field company, this prescription adopts organic phosphonate, inorganic phosphate, zinc salt to constitute composite scale-inhibiting corrosion inhibitor, and its zinc salt content is up to 8.3%, and this prescription is applied on the many circulating water devices of China, and effect is better, yet, because zinc content is very high, so form the zinc dirt easily, contain various inorganic phosphorus and/or organophosphorus in the medicament simultaneously, the sewage of discharging has also brought certain pollution to environment.On January 29th, 2003, disclosed Chinese patent application CN1124990 introduced a kind of inhibiter based on polyetheramides and molybdate, on November 2nd, 2004 laid-open U.S. Patents USP6,811,747 to have introduced a kind of be the water conditioner of inhibition composition with cyanuric acid and molybdate or silicate.But this medicament causes processing cost very high owing to used expensive molybdate in a large number, is difficult to application.
Summary of the invention
The invention provides a kind of environment-friendly composite corrosion and scale inhibitor that is used for the cycle of treatment water coolant and has environmental protection, efficient scale characteristics, it has overcome the pollution problem to environment of nitrite in the existing composite slow-corrosion scale resistor, phosphorus.
The technical solution used in the present invention is as follows:
A kind of environment-friendly composite corrosion and scale inhibitor, be used for the cycle of treatment water coolant, it is characterized in that, this environment-friendly composite corrosion and scale inhibitor is formulated by inhibition component, inhibiting component and deionized water, and the inhibition component is made up of one or more the material in molybdate, tungstate, borate, organic substituted carboxylic acid or the organic heterocyclic compounds; Inhibiting component is made up of one or more the material in natural high moleculer eompound, Epoxysuccinic acid or the acrylic terpolymer.
The mass percent concentration of inhibition component is 25%～55% in the described slowly-releasing Scale inhibitors, and the mass percent concentration of inhibiting component is 10%～45%, and the total content maximum value of inhibition component and inhibiting component is 80% in the slowly-releasing Scale inhibitors.
Molybdate in the described inhibition component is selected from Sodium orthomolybdate, zinc molybdate or ammonium molybdate, and tungstate is selected from Sodium orthomolybdate, zinc molybdate or ammonium molybdate, borate is selected from sodium tetraborate or zinc borate.
Organic substituted carboxylic acid in the described inhibition component is selected from lauroyl propylene diamine nitrilotriacetic, α-dredge one or more the mixture in basic lauric acid, lauryl mercaptan acetate, Whitfield's ointment or the phenylformic acid.
The mixture of one or more in the organic heterocyclic compounds selected from mercapto benzothiazole (MBT) in the described inhibition component, benzotriazole (BTA) or the methyl benzotriazazole (TTA).
The macromolecular compound of described inhibiting component is selected from one or more the mixture in starch, Sunmorl N 60S, Weibull or the xylogen.
The acrylic terpolymer of described inhibiting component is selected from one or more in the rare amide copolymer of vinylformic acid/methyl acrylate/third, vinylformic acid/vinyl sulfonic acid/vinyl acetate copolymer or vinylformic acid/ethyl propenoate/2-third rare acid amides-2-methyl propane sulfonic acid multipolymer.
The epoxy succinic acids material of described inhibiting component is selected from one or more in Epoxysuccinic acid, poly-epoxy succinic acid or the polyepoxy sodium succinate.
The raw materials used commercial industrial product that is of the present invention, by the composite compound corrosion inhibiting and descaling agent that gets of raw material, its preparation method can adopt conventional blending means.The effect of the corrosion inhibiting and descaling agent of reinforced ordered pair preparation of each component there is no negative impact.Best controlled temperature is 50-60 ℃ when composite, in proportion the each component raw material is added in the reactor, fully stirs, until dissolving fully, the desired product that gets final product.This product appearance is a yellow transparent liquid.
Environment-friendly type inhibition anti-sludging agent of the present invention is applicable to Enclosed Type Circulating Cooling Water System, and suitable water quality is de-salted water, softening water, deionized water.Get final product in the pipe network of environment-friendly type inhibition anti-sludging agent that only needs during use to prepare by desired concn adding recirculating cooling water system.
Composite scale-inhibiting corrosion inhibitor of the present invention is compared with existing anti-incrustation corrosion inhibitor and is had the following advantages:
1) proportioning of various components has singularity in the technical formula of this environment-friendly type inhibition anti-sludging agent.
2) the various material components that the present invention relates to do not contain chromic salt, nitrite and phosphoric acid salt etc. to human body and the deleterious material of environment.Raw materials usedly be nontoxic product, can to environment for use and discharging cause environmental pollution, be the new and effective corrosion inhibiting and descaling agent of a kind of environmental protection.
3) environment-friendly type inhibition anti-sludging agent of the present invention has the advantage that the scale inhibition ability is strong, corrosion mitigating effect is good, and effective drug duration is long, can not degrade for a long time.Materials such as carbon steel, stainless steel and copper alloy are played good provide protection.So just prolong the work-ing life of heat-exchange equipment and pipeline greatly, helped guaranteeing the safe and stable operation of recirculating cooling water system again.
4) environment-friendly type inhibition anti-sludging agent of the present invention also has the function of bactericidal.So just solved the water quality deterioration problem that occurs in the recirculated cooling water long-term operation, made recirculating cooling water system be in the good plateau of water quality all the time.Good promoter action is played in the steady running of environment protection and recirculating cooling water system.
5) preparation method of environment-friendly type inhibition anti-sludging agent of the present invention is simple, and raw materials for production are more easily bought, and cost is lower, and effect is remarkable, and producer and user are all had good economic benefits, helps wide popularization and application in China.
6) environment-friendly type of the present invention is looked around Scale inhibitors and is had characteristics easy to use.Because this water treatment agent is a liquid state, need not dissolution process, gets final product so in use directly add recirculating cooling water system; Or adopt automatic medicine adding apparatus adding recirculating cooling water system also can behind the dilute with water.
7) environment-friendly type inhibition anti-sludging agent of the present invention is compared with like product, has the low advantage of adding consistency.At present, general inhibiter of the same type add dose about 1000-1500ppm, this medicament add concentration about 300-500ppm at different quality, this just provides assurance for the recirculating cooling water system low cost movement, has saved a large amount of funds for the user on running cost.Created strong condition for non-pollution discharge simultaneously.
At present, all environment protection is had higher requirement both at home and abroad, this also proposes new standard to water treatment field.In numerous recirculated water medicaments, there are many medicaments to contain poisonous composition, or seriously polluted.For example: chromic salt not only has severe toxicity, and when discharging environmental pollution very serious; Nitrite then is well-known carcinogenic substance, bans use of so far; Phosphorus line formulation is at present in national widespread use.The advantage of phosphorus line formulation is that treatment effect is good, cheap, is widely used.But phosphorus is the nutrition source of bacterium and algae, very easily causes a large amount of breedings of system bacterium algae and worsens water quality.Then discharge the phosphorated eutrophic water during blowdown, cause eutrophication for the rivers and lakes of China, make the waterplant overgrowing, water hypoxia, water quality fouls.Also have some water treatment agents to belong to nontoxic or low toxicity, can not pollute, but, limited its application and popularization owing to cost an arm and a leg to environment, for example molybdate, tungstate, Epoxysuccinic acid, some then is in application test stage such as aspartic acid etc.Present water treatment field good, cheap, the free from environmental pollution water treatment agent of demanding a kind of treatment effect urgently, the contriver is according to the market requirement, and through test for many years, it is low that specific aim is developed a kind of price, effective environment-friendly type inhibition anti-sludging agent.Environment-friendly type inhibition anti-sludging agent of the present invention is a kind of composite water disposal agent of low molybdenum/tungsten, molybdenum/tungsten is only kept 5-10mg/L in recirculated cooling water, mainly be by the synergistic function between chromium kind medicament,, satisfy the low requirement of price simultaneously to reach good water treatment effect.In a single day environment-friendly type inhibition anti-sludging agent of the present invention is promoted widely, and the water treatment field of China is benefited, and also can make due contribution for the environmental protection cause of China.
Embodiment:
The invention will be further described below in conjunction with embodiment, but these embodiment do not limit protection scope of the present invention.
The following example all carries out static-state scale inhibition test and rotary hanging plate corrosion test according to national standard " the mensuration tosca method of water conditioner scale-inhibiting properties " GB/T 16632-1996 and " the mensuration rotary hanging plate method of water conditioner corrosion inhibition " GB/T 18175-2000, to check its inhibition and scale inhibition effect.
Embodiment 1
The preparation of this environment-friendly type inhibition anti-sludging agent:
Epoxysuccinic acid with 15.0%, 5.0% sodium wolframate, 12.5% sodium salicylate, 20.0% sodium tetraborate, 1.2% mercaptobenzothiazole and deionized water add in the container, heated and stirred to 50 ℃, continue to be stirred to dissolving fully, promptly get environment-friendly composite corrosion and scale inhibitor of the present invention.
Under following water quality situation, experimentize: Ca
2+6.61mg/L, Mg
2+1.12mg/L, Cl
-11.74mg/L, SO
4 2-2.82mg/L, total alkalinity 36.19mg/L, specific conductivity 160 μ s/cm, pH7.9, total molten solid 91.6mg/L.
Above-mentioned environment-friendly composite corrosion and scale inhibitor 400ppm is dropped in the above-mentioned water quality, carried out not concentration test of static state 168 hours, scale inhibition performance reaches 100%; Rotary hanging plate experiment A3 steel corrosion speed 0.023mm/a, H68 steel corrosion speed 0.0018mm/a, OCr
18Ni
9Stainless steel 0.0001mm/a.
Embodiment 2
The preparation of this environment-friendly type inhibition anti-sludging agent: the basic lauric acid of the acrylic acid and acrylic ester copolymers with 18.0%, 4.0% Sodium orthomolybdate, 15.0% α-dredge, 25.0% sodium tetraborate, 0.8% methyl benzotriazazole tyrosine and 45.2% deionized water add in the container, be heated with stirring to 50 ℃, continue to be stirred to dissolving fully, promptly get environment-friendly composite corrosion and scale inhibitor of the present invention.
Under following water quality situation, experimentize: Ca
2+11.08mg/L, Mg
2+2.42mg/L, Cl
-17.13mg/L, SO
4 2-15.70mg/L, total alkalinity 86.88mg/L, specific conductivity 310 μ s/cm, pH8.55, total molten solid 236mg/L.
Above-mentioned composite scale-inhibiting corrosion inhibitor 500ppm is dropped into above-mentioned water quality, and static state does not concentrate 168 hours, scale inhibition performance 99.99%.Rotary hanging plate test: A
3Steel corrosion speed 0.057mm/a, H68 copper corrosion speed 0.0026mm/a, OCr
18Ni
9Corrosion of Stainless Steel rate 0.00013mm/a.
Embodiment 3
The preparation of this environment-friendly type inhibition anti-sludging agent:
Sulfonated lignin with 10.0%, 3.5% zinc tungstate, 12.0% lauroyl propylene diamine nitrilotriacetic, 20.0% zinc borate, 1.2% benzotriazole, 2.5% Weibull, 50.8% deionized water add in the container; be heated with stirring to 50 ℃; continue to be stirred to dissolving fully, promptly get environment-friendly composite corrosion and scale inhibitor of the present invention.
Under following water quality situation, experimentize: Ca
2+3.25mg/L, Mg
2+0.28mg/L, Cl
-22.51mg/L, SO
4 2-20.01mg/L, total alkalinity 105.66mg/L, specific conductivity 276 μ s/cm, total molten solid 184.49mg/L.
Above-mentioned composite scale-inhibiting corrosion inhibitor 500ppm is dropped into above-mentioned water quality, and static state does not concentrate 168 hours, scale inhibition performance 100%.Rotary hanging plate test: A
3Steel corrosion speed 0.077mm/a, H68 copper corrosion speed 0.0019mm/a, OCr
18Ni
9Corrosion of Stainless Steel rate 0.00016mm/a.
Embodiment 4
The preparation of this environment-friendly type inhibition anti-sludging agent:
Epoxysuccinic acid with 10.0%, 3.0% Sodium orthomolybdate, 25.0% phenylformic acid, 1.2% sodium tetraborate, 0.5% methyl benzotriazazole and 52.5% deionized water add in the container, be heated with stirring to 50 ℃, continue to be stirred to dissolving fully, promptly get environment-friendly composite corrosion and scale inhibitor of the present invention.
Under following water quality situation, experimentize: Ca
2+4.28mg/L, Mg
2+0.11mg/L, Cl
-8.78mg/L, SO
4 2-16.89mg/L, total alkalinity 23.15mg/L, total molten solid 72.37mg/L.
Above-mentioned composite scale-inhibiting corrosion inhibitor 400ppm is dropped into above-mentioned water quality, and static state does not concentrate 168 hours, scale inhibition performance 100%.Rotary hanging plate test: A
3Steel corrosion speed 0.075mm/a, H68 copper corrosion speed 0.0029mm/a, OCr
18Ni
9Corrosion of Stainless Steel rate 0.00046mm/a.
Embodiment 5
The preparation of this environment-friendly type inhibition anti-sludging agent:
The basic lauric acid of Sunmorl N 60S with 15.5%, 2.0% ammonium tungstate, 8.2% α-dredge, 17.5% sodium tetraborate, 1.0% benzotriazole and 45.8% deionized water add in the container, be heated with stirring to 50 ℃, continue to be stirred to dissolving fully, promptly get environment-friendly composite corrosion and scale inhibitor of the present invention.
Under following water quality situation, experimentize: Ca
2+0.58mg/L, Mg
2+0.27mg/L, Cl
-3.25mg/L, SO
4 2-2.38mg/L, total alkalinity 3.07mg/L, total molten solid 22.46mg/L, pH9.2.
Above-mentioned composite scale-inhibiting corrosion inhibitor 500ppm is dropped into above-mentioned water quality, and static state does not concentrate 168 hours, scale inhibition performance 100%.Rotary hanging plate test: A
3Steel corrosion speed 0.035mm/a, H68 copper corrosion speed 0.0014mm/a, OCr
18Ni
9Corrosion of Stainless Steel rate 0.00024mm/a.
Embodiment 6
The preparation of this environment-friendly type inhibition anti-sludging agent:
Sulfonated lignin with 18.0%, 1.5% Sodium orthomolybdate, 12.0% Sunmorl N 60S, 2.0% Weibull, 21.5% sodium tetraborate, 1.0% mercaptobenzothiazole and 44.0% deionized water add in the container, be heated with stirring to 50 ℃, continue to be stirred to dissolving fully, promptly get environment-friendly composite corrosion and scale inhibitor of the present invention.
Under following water quality situation, experimentize: Ca
2+0.66mg/L, Mg
2+0.12mg/L, Cl
-1.175mg/L, SO
4 2-0.84mg/L, total alkalinity 1.29mg/L, total molten solid 10.88mg/L, pH8.6.
Above-mentioned composite scale-inhibiting corrosion inhibitor 500ppm is dropped into above-mentioned water quality, and static state does not concentrate 168 hours, scale inhibition performance 100%.Rotary hanging plate test: A
3Steel corrosion speed 0.016mm/a, H68 copper corrosion speed 0.0012mm/a, OCr
18Ni
9Corrosion of Stainless Steel rate 0.0001mm/a.
Embodiment 7
The preparation of this environment-friendly type inhibition anti-sludging agent:
Sulfonated lignin with 18.0%, 0.5% starch, 1.5% ammonium molybdate, 12.0% Sunmorl N 60S, 2.0% Weibull, 21.5% sodium tetraborate, vinylformic acid/vinyl sulfonic acid/vinyl acetate copolymer of 2.0%, 1.0% mercaptobenzothiazole and deionized water add in the container, be heated with stirring to 50 ℃, continue to be stirred to dissolving fully, promptly get environment-friendly composite corrosion and scale inhibitor of the present invention.
Under following water quality situation, experimentize: Ca
2+0.66mg/L, Mg
2+0.12mg/L, Cl
-1.175mg/L, SO
4 2-0.84mg/L, total alkalinity 1.29mg/L, total molten solid 10.88mg/L, pH8.6.
Above-mentioned composite scale-inhibiting corrosion inhibitor 500ppm is dropped into above-mentioned water quality, and static state does not concentrate 168 hours, scale inhibition performance 100%.Rotary hanging plate test: A
3Steel corrosion speed 0.018mm/a, H68 copper corrosion speed 0.0013mm/a, OCr
18Ni
9Corrosion of Stainless Steel rate 0.00006mm/a.
Embodiment 8
The preparation of this environment-friendly type inhibition anti-sludging agent:
Sunmorl N 60S with 15.5%, 1.5% starch, 2.0% ammonium tungstate, α-thin basic lauric acid of 8.2%, 17.5% sodium tetraborate, 1.0% benzotriazole, 0.5% vinylformic acid/ethyl propenoate/2-third rare acid amides-2-methyl propane sulfonic acid multipolymer, the rare amide copolymer of 2.4% vinylformic acid/methyl acrylate/third and deionized water add in the container, be heated with stirring to 50 ℃, continue to be stirred to dissolving fully, promptly get environment-friendly composite corrosion and scale inhibitor of the present invention.
Under following water quality situation, experimentize: Ca
2+0.58mg/L, Mg
2+0.27mg/L, Cl
-3.25mg/L, SO
4 2-2.38mg/L, total alkalinity 3.07mg/L, total molten solid 22.46mg/L, pH9.2.
Above-mentioned composite scale-inhibiting corrosion inhibitor 500ppm is dropped into above-mentioned water quality, and static state does not concentrate 168 hours, scale inhibition performance 100%.Rotary hanging plate test: A
3Steel corrosion speed 0.030mm/a, H68 copper corrosion speed 0.0009mm/a, OCr
18Ni
9Corrosion of Stainless Steel rate 0.00012mm/a.
This shows that environment-friendly type inhibition anti-sludging agent provided by the invention has the characteristics of efficient scale and inhibition, every technical indicator can meet and be better than national standard fully.
Claims (8)
1, a kind of environment-friendly composite corrosion and scale inhibitor, be used for the cycle of treatment water coolant, it is characterized in that, this environment-friendly composite corrosion and scale inhibitor is formulated by inhibition component, inhibiting component and deionized water, and the inhibition component is made up of one or more the material in molybdate, tungstate, borate, organic substituted carboxylic acid or the organic heterocyclic compounds; Inhibiting component is made up of one or more the material in natural high moleculer eompound, epoxy succinic acids material or the acrylic terpolymer.
2, environment-friendly composite corrosion and scale inhibitor according to claim 1, the mass percent concentration that it is characterized in that inhibition component in the described corrosion inhibiting and descaling agent is 25%～55%, the mass percent concentration of inhibiting component is 10%～45%, and the total content maximum value of inhibition component and inhibiting component is 80% in the corrosion inhibiting and descaling agent.
3, environment-friendly composite corrosion and scale inhibitor according to claim 1, it is characterized in that the molybdate in the described inhibition component is selected from Sodium orthomolybdate, zinc molybdate or ammonium molybdate, tungstate is selected from Sodium orthomolybdate, zinc molybdate or ammonium molybdate, borate is selected from sodium tetraborate or zinc borate.
4, environment-friendly composite corrosion and scale inhibitor according to claim 1 is characterized in that organic substituted carboxylic acid in the described inhibition component is selected from lauroyl propylene diamine nitrilotriacetic, α-dredge one or more the mixture in basic lauric acid, lauryl mercaptan acetate, Whitfield's ointment or the phenylformic acid.
5, environment-friendly composite corrosion and scale inhibitor according to claim 1 is characterized in that one or more the mixture in organic heterocyclic compounds selected from mercapto benzothiazole (MBT), benzotriazole (BTA) or the methyl benzotriazazole (TTA) in the described inhibition component.
6, environment-friendly composite corrosion and scale inhibitor according to claim 1, the macromolecular compound that it is characterized in that described inhibiting component are selected from one or more the mixture in starch, Sunmorl N 60S, Weibull or the xylogen.
7. environment-friendly composite corrosion and scale inhibitor according to claim 1, the acrylic terpolymer that it is characterized in that described inhibiting component is selected from one or more in the rare amide copolymer of vinylformic acid/methyl acrylate/third, vinylformic acid/vinyl sulfonic acid/vinyl acetate copolymer or vinylformic acid/ethyl propenoate/2-third rare acid amides-2-methyl propane sulfonic acid multipolymer.
8. environment-friendly composite corrosion and scale inhibitor according to claim 1, the epoxy succinic acids material that it is characterized in that described inhibiting component is selected from one or more in poly-epoxy succinic acid or the polyepoxy sodium succinate.
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| CN101941764A (en) * | 2010-08-31 | 2011-01-12 | 仙桃市中楚化工有限责任公司 | Circulating cooling water scale inhibition corrosion inhibitor and preparation method thereof |
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| CN102408162B (en) * | 2010-09-21 | 2013-06-19 | 中国石油化工股份有限公司 | Phosphorus-free corrosion and scale inhibitor used for industrial circulation cooling water |
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| CN105776592A (en) * | 2016-03-08 | 2016-07-20 | 佛山市聚成生化技术研发有限公司 | Biodegradable scale inhibition and dispersion agent |
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| CN114772754A (en) * | 2022-05-26 | 2022-07-22 | 山东天庆科技发展有限公司 | Circulating cooling water scale and corrosion inhibitor and preparation method thereof |
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