CN102351327A - Method for preparing phosphor-free anti-scaling corrosion inhibitor - Google Patents
Method for preparing phosphor-free anti-scaling corrosion inhibitor Download PDFInfo
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- CN102351327A CN102351327A CN2011102502174A CN201110250217A CN102351327A CN 102351327 A CN102351327 A CN 102351327A CN 2011102502174 A CN2011102502174 A CN 2011102502174A CN 201110250217 A CN201110250217 A CN 201110250217A CN 102351327 A CN102351327 A CN 102351327A
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Abstract
The invention provides a method for preparing a phosphor-free anti-scaling corrosion inhibitor. The method is characterized in that: the phosphor-free anti-scaling corrosion inhibitor is a composition consisting of the following raw materials in parts by weight: 5 to 50 parts of deionized water, 1 to 5 parts of sodium molybdate, 30 to 50 parts of polyaspartic acid, 20 to 30 parts of polycarboxylic acid, 1 to 4 parts of methylbenzotriazole, and 1 to 3 parts of zinc salt. The method comprises the following step of mixing the raw materials in a reaction kettle according to a preset proportion to prepare the required phosphor-free anti-scaling corrosion inhibitor, wherein the mixing environmental temperature is between 20 DEG C and 30 DEG C. According to the method, monomers have excellent synergic action and long stable phase, emission of 'the three wastes' is prevented, the environmental pollution problem caused by phosphor is completely eliminated, the concentration rate of industrial recycling cooling water reaches over 5 times, and massive water resources are saved. Test results prove that scale inhibition rate is over 95 percent, the environmentally friendly requirement for the industrial recycling cooling water treatment discharge is fulfilled.
Description
Technical field
The invention belongs to the industrial cycle water-treatment technology field, relate to a kind of anti-incrustation corrosion inhibitor.
Background technology
It mainly is the problem that solves fouling in the industrial circulating cooling water system, corrosion and three aspects of microorganism harm that industrial circulating cooling water is handled.In recirculating cooling water system, adding anti-incrustation corrosion inhibitor is topmost processing mode; The anti-incrustation corrosion inhibitor total phosphorous that the production unit of present most of anti-incrustation corrosion inhibitors and application units produce and use is than higher; General total phosphorous is more than 6.8%; Cause that total phosphorus is generally 7～15mg/L in the industrial circulating cooling water; Though the higher anti-incrustation corrosion inhibitor of total phosphorous itself belongs to the water conditioner of nontoxic or low toxicity, they can cause the environmental problem such as eutrophication, water quality severe exacerbation of water body.The primary standard of the highest permission emission concentration of " integrated wastewater discharge standard " GB8978-1996 pair total phosphorus (in P) is 0.5mg/L.
Though handle the prior art of industrial circulating cooling water at present the low-phosphorus antiincrustation corrosion inhibitor technology is arranged; But the low-phosphorus antiincrustation corrosion inhibitor kind is not only fewer; And its amount ratio is bigger; As being in the case study on implementation 1 of CN1743281A at notification number; Though the total phosphorous of the anti-incrustation corrosion inhibitor that is provided is smaller; But amount ratio is bigger, and adding concentration is 100mg/L, and total phosphorus is (with PO
4 3-Meter) though only be 0.7mg/L, when this water quality was concentrated into notification number and is 4 times that dynamic analog test is mentioned among the CN1743281A embodiment 8, total phosphorus reached 2.8mg/L (with PO
4 3-Meter), then be 0.91mg/L in P, far surpassed among " integrated wastewater discharge standard " GB8978-1996 first discharge standard 0.5mg/L to the highest permission emission concentration of total phosphorus (in P).Therefore the water that is discharged also causes environmental problems such as the eutrophication, water quality severe exacerbation of water body easily.
Summary of the invention
The purpose of this invention is to provide a kind of non-phosphorus scale and corrosion inhibitor compound method, handle to solve prior art that the total phosphorous of the fouling of industrial circulating cooling water, the used anti-incrustation corrosion inhibitor of burn into microorganism problem is higher, during the industrial circulating cooling water discharging in the problems such as safe and stable operation needs that content is higher, environmental protection policy that do not meet country required, can not satisfy industrial circulating cooling water of total phosphorus.
The technical solution adopted for the present invention to solve the technical problems is the mixture that this non-phosphorus scale and corrosion inhibitor is made up of multiple without phosphorus monomer, and raw material has: deionized water, Sodium orthomolybdate, poly aspartic acid, poly carboxylic acid, tolyltriazole, zinc salt.Its raw material weight ratio is: 5～50 parts of deionized waters, 1～5 part of Sodium orthomolybdate, 30～50 parts of poly aspartic acids, 20～30 parts of poly carboxylic acid, 1～4 part of tolyltriazole, 1～3 part of zinc salt.
Above-mentioned raw materials is mixed in reaction kettle by predetermined proportion, and the mixed environment temperature is 20～30 ℃, can make required non-phosphorus scale and corrosion inhibitor.
Poly carboxylic acid of the present invention is copolymer or terpolymer, is preferably at least a vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/sodium allylsulfonate multipolymer, vinylformic acid/Propylene glycol monoacrylate/styrene sulfonic acid multipolymer, the vinylformic acid/Propylene glycol monoacrylate/2-methyl-2 of being selected from
/-acrylamido propane sulfonic acid multipolymer.
Zinc salt of the present invention is zinc sulfate or zinc chloride.
The inhibitor mechanism of poly carboxylic acid of the present invention is: the relative molecular mass of poly carboxylic acid is quite big; It is linear polymer; One end is adsorbed on lime carbonate etc. and becomes on the crystal grain of the dirty factor, and rest part is then around around crystal grain, it can't be increased and becomes slick and sly.Grain growth is interfered and distorts, and it is tiny that crystal grain becomes, and the dirt layer of formation is soft, is very easily rinsed out by current.
Tolyltriazole of the present invention plays corrosion inhibition; Can combine with copper atom with covalent linkage and coordinate bond; Each other alternately, form the key shaped polymer, form insoluble protective membrane in the metallic surface; Thereby suppress the corrosion of copper and alloy; The copper dissolution that it not only can suppress on the metallic matrix gets in the water, and can also make the cupric ion passivation that gets in the water, prevents the deposition of copper in steel, aluminium, zinc and galvanized iron and the dezincify of brass; In addition, ferrous metal also there is corrosion inhibition.
Poly aspartic acid of the present invention plays scale inhibition and dissemination, the CaCO in the disperse water
3, CaSO
4, settlings such as calcium phosphate, barium sulfate, ferric oxide, clay, stop the deposition of lime carbonate and suspended substance.Poly aspartic acid is that a kind of being prone to do not existed the ring pollution problem by biological degradation.
Sodium orthomolybdate of the present invention is a kind of non-oxidizable or weak oxide property inhibiter in water coolant, and in the open type recirculated cooling water, ready-made and abundant dissolved oxygen produces layer protecting film as oxygenant and Sodium orthomolybdate acting in conjunction in the metallic surface.
Zinc salt plays carbon steel corrosion inhibitor.
The detection method that non-phosphorus scale and corrosion inhibitor of the present invention is added in the recirculated cooling water adopts " the mensuration thiocyanate-spectrophotometry of molybdate in the industrial circulating cooling water " GB/T 23836-2009, detects the molybdenum acid ion content in the recirculated cooling water.
Adopting positively effect of the present invention is that described anti-incrustation corrosion inhibitor is all selected environment amenable nontoxic, pollution-free raw material for use from raw material; Synergy is very good between each monomer; Stationary phase is long; There is not " three wastes " discharging in the production process; The concentration rate of industrial circulating cooling water is reached more than 5 times, practiced thrift a large amount of fresh process waters.Show through dynamic hanging test and rotary hanging plate test: the scale inhibition performance of this non-phosphorus scale and corrosion inhibitor all satisfies the related request among " industrial circulating cooling water water treatment design specifications " GB50050-2007 more than 95% to stainless steel, copper, corrosion of Carbon Steel rate.
The concentration that adds when a kind of non-phosphorus scale and corrosion inhibitor provided by the present invention is handled industrial circulating cooling water is generally 8～30mg/L; Used always in handling with present industrial circulating cooling water contain total phosphorus content than higher anti-incrustation corrosion inhibitor to add concentration basic identical; Be able to thoroughly eliminate the problem of environmental pollution that causes because of phosphorus, satisfy the environmental protection needs that industrial circulating cooling water is handled discharging.
Embodiment
Be the different proportioning consumptions of starting material of the present invention below, the practical implementation example under the different the next kind situation of Similar types of materials:
Embodiment 1:
Take by weighing 50 ㎏ Sodium orthomolybdates, poly aspartic acid 500 ㎏, copolymer 300 ㎏, tolyltriazole 40 ㎏, zinc sulfate 30 ㎏, deionized water 80 ㎏ are made into 1000 ㎏.
The above-mentioned raw materials proportional mixing is carried out in reaction kettle composite, 20 ℃ of combinational environment temperature.
Certain chemical plant is a plate-type heat exchanger, and the recirculating cooling water system volume is 2000m
3, internal circulating load is 3000m
3, the interchanger material is TP304, pipeline is a carbon steel piping.5.5 times of concentration rates; Add environmental protection and saving type non-phosphorus scale and corrosion inhibitor 30mg/L of the present invention by rate of water make-up; Theoretical Calculation molybdate content is 5.0% * 66.1% * 30 * 5.5=5.4mg/L, is 5.3mg/L through " the mensuration thiocyanate-spectrophotometry of molybdate in the industrial circulating cooling water " GB/T 23836-2009 actual detected molybdate content.
Annotate: 66.1% is molybdenum acid ion (MoO
4 2-) at Sodium orthomolybdate (Na
2MoO
42H
2O) shared part by weight in, as follows.
Through reaching the operation in 1 year; Analyze water-quality guideline; Scale inhibition performance is all the time more than 95%; The corrosion rate of stainless steel TP304 test piece, the carbon steel test piece of hanging all satisfies the related request among " industrial circulating cooling water water treatment design specifications " GB50050-2007; The constant interval of observing temperature of charge is in the normal change scope; Normal operation was opened interchanger and is observed after 1 year, did not have the no corrosion phenomenon of dirt.It is stable to illustrate that this system adds non-phosphorus scale and corrosion inhibitor of the present invention.
Case study on implementation 2:
Take by weighing 10 ㎏ Sodium orthomolybdates, poly aspartic acid 300 ㎏, terpolymer 200 ㎏, tolyltriazole 10 ㎏, zinc chloride 10 ㎏, deionized water 470 ㎏ are made into 1000 ㎏.
The above-mentioned raw materials proportional mixing is carried out in reaction kettle composite, 25 ℃ of combinational environment temperature.
Certain heat power plant is the shell and tube condenser, and the recirculating cooling water system volume is 5000m
3, internal circulating load is 10800m
3, the interchanger material is a H68 brass, pipeline is a carbon steel piping.6 times of concentration rates; Add non-phosphorus scale and corrosion inhibitor 20mg/L of the present invention by rate of water make-up; Theoretical Calculation molybdate content is 1% * 66.1% * 20 * 6=0.79mg/L, is 0.76mg/L through " the mensuration thiocyanate-spectrophotometry of molybdate in the industrial circulating cooling water " GB/T 23836-2009 actual detected molybdate content.
Through reaching the operation in 2 years; Analyze water-quality guideline; Scale inhibition performance is all the time more than 95%; The corrosion rate of stainless steel H68 test piece, the carbon steel test piece of hanging all satisfies the related request among " industrial circulating cooling water water treatment design specifications " GB50050-2007; Vacuum tightness, end difference are all in normal range; Normal operation was opened condenser and is observed after 2 years, did not have the no corrosion phenomenon of dirt.It is stable to illustrate that this system adds non-phosphorus scale and corrosion inhibitor of the present invention.
Case study on implementation 3:
Take by weighing 20 ㎏ Sodium orthomolybdates, poly aspartic acid 450 ㎏, terpolymer 250 ㎏, tolyltriazole 30 ㎏, zinc chloride 20 ㎏, deionized water 230 ㎏ are made into 1000 ㎏.
The above-mentioned raw materials proportional mixing is carried out in reaction kettle composite, 30 ℃ of combinational environment temperature.
Certain power station is a shell and tube heat exchanger, and the recirculating cooling water system volume is 13000m
3, internal circulating load is 22000m
3, the condenser material is the TP316 stainless steel, pipeline is a carbon steel piping.5.5 times of concentration rates; Add non-phosphorus scale and corrosion inhibitor 28mg/L of the present invention by rate of water make-up; Theoretical Calculation molybdate content is 2% * 66.1% * 28 * 5.5=2.04mg/L, is 2.02mg/L through " the mensuration thiocyanate-spectrophotometry of molybdate in the industrial circulating cooling water " GB/T 23836-2009 actual detected molybdate content.
Through reaching the operation in 1 year; Analyze water-quality guideline; Scale inhibition performance is all the time more than 95%; The corrosion rate of stainless steel TP316 test piece, the carbon steel test piece of hanging all satisfies the related request among " industrial circulating cooling water water treatment design specifications " GB50050-2007; Vacuum tightness, end difference are all in normal range; Normal operation was opened condenser and is observed after 1 year, did not have the no corrosion phenomenon of dirt.It is stable to illustrate that this system adds non-phosphorus scale and corrosion inhibitor of the present invention.
Case study on implementation 4:
Take by weighing 30 ㎏ Sodium orthomolybdates, poly aspartic acid 400 ㎏, copolymer 200 ㎏, tolyltriazole 20 ㎏, zinc chloride 10 ㎏, deionized water 340 ㎏ are made into 1000 ㎏.
The above-mentioned raw materials proportional mixing is carried out in reaction kettle composite, 28 ℃ of combinational environment temperature.
Certain chemical industry is a shell and tube heat exchanger, and the recirculating cooling water system volume is 9000m
3, internal circulating load is 13000m
3, the condenser material is a brass, pipeline is a carbon steel piping.5 times of concentration rates; Add non-phosphorus scale and corrosion inhibitor 15mg/L of the present invention by rate of water make-up; Theoretical Calculation molybdate content is 3% * 66.1% * 15 * 5=1.49mg/L, is 1.45mg/L through " the mensuration thiocyanate-spectrophotometry of molybdate in the industrial circulating cooling water " GB/T 23836-2009 actual detected molybdate content.
Through reaching the operation in 1 year; Analyze water-quality guideline; Scale inhibition performance is all the time more than 95%; The corrosion rate of the brass test piece of hanging, carbon steel test piece all satisfies the related request among " industrial circulating cooling water water treatment design specifications " GB50050-2007; Material temperature difference is all in normal range; Normal operation was opened condenser and is observed after 1 year, did not have the no corrosion phenomenon of dirt.It is stable to illustrate that this system adds non-phosphorus scale and corrosion inhibitor of the present invention.
Case study on implementation 5:
Take by weighing 40 ㎏ Sodium orthomolybdates, poly aspartic acid 350 ㎏, copolymer 270 ㎏, tolyltriazole 20 ㎏, zinc sulfate 20 ㎏, deionized water 300 ㎏ are made into 1000 ㎏.
The above-mentioned raw materials proportional mixing is carried out in reaction kettle composite, 22 ℃ of combinational environment temperature.
Certain chemical industry is a shell and tube heat exchanger, and the recirculating cooling water system volume is 5000m
3, internal circulating load is 8000m
3, the condenser material is brass HSn70-1A, pipeline is a carbon steel piping.5 times of concentration rates; Add non-phosphorus scale and corrosion inhibitor 20mg/L of the present invention by rate of water make-up; Theoretical Calculation molybdate content is 4% * 66.1% * 20 * 5=2.64mg/L, is 2.63mg/L through " the mensuration thiocyanate-spectrophotometry of molybdate in the industrial circulating cooling water " GB/T 23836-2009 actual detected molybdate content.
Through reaching the operation in 2 years; Analyze water-quality guideline; Scale inhibition performance is all the time more than 95%; The corrosion rate of the HSn70 that hangs-1A test piece, carbon steel test piece all satisfies the related request among " industrial circulating cooling water water treatment design specifications " GB50050-2007; Material temperature difference is all in normal range; Normal operation was opened condenser and is observed after 2 years, did not have the no corrosion phenomenon of dirt.It is stable to illustrate that this system adds non-phosphorus scale and corrosion inhibitor of the present invention.
Claims (1)
1. non-phosphorus scale and corrosion inhibitor compound method; It is characterized in that this non-phosphorus scale and corrosion inhibitor is by deionized water, Sodium orthomolybdate, poly aspartic acid, poly carboxylic acid; The mixture that tolyltriazole, the without phosphorus monomer of zinc salt are formed, its raw material weight ratio is: 5～50 parts of deionized waters, 1～5 part of Sodium orthomolybdate, 30～50 parts of poly aspartic acids, 20～30 parts of poly carboxylic acid, 1～4 part of tolyltriazole, 1～3 part of zinc salt; Above-mentioned raw materials is mixed in reaction kettle by predetermined proportion, and the mixed environment temperature is 20～30 ℃, can make required non-phosphorus scale and corrosion inhibitor.
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| CN 201110250217 CN102351327B (en) | 2011-08-29 | 2011-08-29 | Method for preparing phosphor-free anti-scaling corrosion inhibitor |
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|---|---|---|---|
| CN 201110250217 CN102351327B (en) | 2011-08-29 | 2011-08-29 | Method for preparing phosphor-free anti-scaling corrosion inhibitor |
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| CN102351327A true CN102351327A (en) | 2012-02-15 |
| CN102351327B CN102351327B (en) | 2012-12-05 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103449616A (en) * | 2013-09-03 | 2013-12-18 | 山东天庆科技发展有限公司 | Biodegradable non-phosphorus scale inhibition dispersion agent and preparation method thereof |
| CN104884395A (en) * | 2012-12-28 | 2015-09-02 | 埃科莱布美国股份有限公司 | Corrosion and fouling mitigation using non-phosphorus based additives |
| CN110980971A (en) * | 2019-12-16 | 2020-04-10 | 武汉中新同和科技有限责任公司 | Non-phosphorus scale and corrosion inhibitor for industrial circulating water and preparation method thereof |
| CN111377549A (en) * | 2020-03-13 | 2020-07-07 | 大唐绥化热电有限公司 | Special corrosion and scale inhibitor for recycling reclaimed water in power plant and preparation method thereof |
| CN114749134A (en) * | 2022-04-25 | 2022-07-15 | 宜兴金兑化工有限公司 | Preparation method of atmospheric and vacuum corrosion inhibitor and special filling device thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104884395A (en) * | 2012-12-28 | 2015-09-02 | 埃科莱布美国股份有限公司 | Corrosion and fouling mitigation using non-phosphorus based additives |
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| CN110980971A (en) * | 2019-12-16 | 2020-04-10 | 武汉中新同和科技有限责任公司 | Non-phosphorus scale and corrosion inhibitor for industrial circulating water and preparation method thereof |
| CN110980971B (en) * | 2019-12-16 | 2022-05-13 | 武汉中新同和科技有限责任公司 | Non-phosphorus scale and corrosion inhibitor for industrial circulating water and preparation method thereof |
| CN111377549A (en) * | 2020-03-13 | 2020-07-07 | 大唐绥化热电有限公司 | Special corrosion and scale inhibitor for recycling reclaimed water in power plant and preparation method thereof |
| CN114749134A (en) * | 2022-04-25 | 2022-07-15 | 宜兴金兑化工有限公司 | Preparation method of atmospheric and vacuum corrosion inhibitor and special filling device thereof |
| CN114749134B (en) * | 2022-04-25 | 2023-10-03 | 宜兴金兑化工有限公司 | Preparation method of atmospheric and vacuum corrosion inhibitor and special filling device thereof |
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| CN102351327B (en) | 2012-12-05 |
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