CN1565994A - Polynary composite water treatment agent - Google Patents
Polynary composite water treatment agent Download PDFInfo
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- CN1565994A CN1565994A CNA031376037A CN03137603A CN1565994A CN 1565994 A CN1565994 A CN 1565994A CN A031376037 A CNA031376037 A CN A031376037A CN 03137603 A CN03137603 A CN 03137603A CN 1565994 A CN1565994 A CN 1565994A
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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
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- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to a polynary composite water treatment agent which mainly comprises terpolymer containing sulfonic acid radicals, organophosphorus acids, zinc salts and metal inhibitors, wherein the effective concentration weight ratio being 20-40 : 1-10 : 0.5-4 : 0-3.
Description
Technical field
The present invention relates to a kind of polynary composite water disposal agent, especially a kind of industrial cycle water conditioner based on terpolymer.
Background technology
The industrial water conditioner that generally adds in water coolant reduces corrosion and fouling.For (hardness or basicity＞200mg/L, hardness or basicity are with CaCO with higher hardness and basicity water
3Meter, down together) be the cooling water system of make up water, though at present more water treatment prescription is arranged, subject matter is: component of 1) selecting for use and set of dispense ratio do not obtain bigger embodiment with the synergetic property of medicament; 2) components selection does not embody the requirement of comprehensive scale inhibitor and stability effectively; 3) should meet the trend of environmental protection, it is without phosphorus or low-phosphorous that draining is accomplished as far as possible, medicament low toxicity or nontoxic; 4) should embody low amount and reach principle efficiently.CN1258649 discloses a kind of Recompounded multielement antisludging corrosion inhibitor, include machine phosphonic acid (4～15mg/l), contain the sulfonic group multipolymer (4～15mg/l), zinc salt (1.5～5mg/l) and look particular case and the copper material corrosion inhibitor (0.5～1.5mg/l) that exists.Suit under cycles of concentration is 2.3 ± 0.2 condition, to use.Because factors such as environment, population and industrialization, the supporting capacity of water resources is faced with severe tests.Process water accounts for about 70% of urban water consumption at present, and water coolant accounts for 60～70% of process water.Cycles of concentration K is an important indicator of recirculated water, and its size has determined the level of water saving, the height of the repeating utilization factor of decision water, and the relation of cycles of concentration and water-saving rate sees Table 1.Therefore, thus improving the cycles of concentration water saving to greatest extent when guaranteeing the anticorrosive and scale inhibition effect of water conditioner has meaning.
Table 1 cycles of concentration and water-saving rate
| Cycles of concentration K | ?1.2 | ?1.4 | ?1.6 | ?1.8 | ?2.0 | ?3.0 | ?4.0 | ?5.0 | |
| Amount of makeup water m 3/hr | ?1020 | ?595 | ?453 | ?382 | ?340 | ?255 | ?227 | ?212 | |
| Water amount of blowdown m 3/hr | ?840 | ?415 | ?273 | ?202 | ?160 | ?75 | ?47 | ?32 | |
| K=1.2 is the water-saving amount of benchmark | Water-saving amount m 3/hr | ?425 | ?567 | ?638 | ?680 | ?765 | ?792 | ?808 | |
| Water-saving rate % | ?42 | ?56 | ?63 | ?66.6 | ?75 | ?78 | ?80 | ||
| K=1.2 is the blowdown reduction amount of benchmark | Blowdown flow rate m 3/hr | ?425 | ?567 | ?638 | ?680 | ?765 | ?792 | ?808 | |
| Blowdown reduced rate % | ?50 | ?67.5 | ?76 | ?81 | ?91 | ?94.4 | ?96 | ||
Annotate: condition is quantity of circulating water 10000m
3/ hr; Recirculated water vaporization losses 1.7%, spatter loss 0.1%; Producing leakage is zero.
Summary of the invention
The object of the present invention is to provide a kind of improved polynary composite water disposal agent, when keeping anticorrosion and scale inhibition effect, improve water-saving rate to greatest extent.The polynary composite water disposal agent of the present invention is mainly formed by containing sulfonic terpolymer, organic phospho acid, zinc salt and metal inhibitor, its weight (effective concentration) is than being 20～40: 1～10: 0.5～4: 0～3, water quality for higher hardness and basicity, the suggestion proportional range is 25～35: 1～10: 0.5～1: 0～2, and zinc salt weight is in zinc.Suitable of the present inventionly contain sulfonic terpolymer and comprise vinylformic acid/2-acrylamide-2-methyl-propyl sulfonic acid/2-acrylamide-2-methyl-propyl phosphonic acids (AA/AMPS/AMPP), vinylformic acid/2-acrylamide-2-methyl-propyl sulfonic acid/acrylamide (AA/AMPS/AM), vinylformic acid/2-acrylamide-2-methyl-propyl sulfonic acid/Propylene glycol monoacrylate (AA/AMPS/HPA), vinylformic acid/2-acrylamide-2-methyl-propyl sulfonic acid/styrene sulfonic acid (AA/AMPS/SS) etc., it is not only to lime carbonate, and dirts such as calcium phosphate, calcium sulfate are had more excellent restraining effect.Suitable organic phospho acid of the present invention comprises hydroxy ethylene diphosphonic acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), 2-phosphinylidyne butane-1; 2; 4 tricarboxylic acid (PBTCA), ethylene diamine tetramethylene phosphonic acid (EDTMP) etc., it has stability and oxidation-resistance preferably.Suitable zinc salt of the present invention comprises zinc sulfate, zinc chloride, can form protective membrane in the metallic surface.Suitable metal inhibitor of the present invention comprises mercaptobenzothiazole (MBT), benzotriazole (BTA), methyl benzotriazazole (MBTA), and non-ferrous metal is had corrosion inhibition preferably, uses when therefore the non-ferrous metal interchanger being arranged in circulating water system.The polynary composite water disposal agent of the present invention suits at pH to be preferably in the water system between 8.0～9.0 greater than 7.2, can guarantee that like this each component all can have an effect, and the suggestion cycles of concentration is more suitable for 3.5 between 3.0～3.7.When water conditioner effective concentration was 30%, all not high in hardness and basicity, cycles of concentration was less than under 3.5 the condition, water conditioner adds concentration and is controlled at 30～40mg/L, the water quality of high rigidity and basicity, or cycles of concentration is greater than 3.5 o'clock, and adding concentration is 40～50mg/L.
The polynary composite water disposal agent of the present invention can be prepared with ordinary method.For example by final water conditioner effective concentration, calculate the each component consumption according to proportioning, pour water and each component into, stir, temperature is risen to 70～75 ℃, keep 10～15 minutes postcooling to normal temperature to get final product, obtaining product is translucent liquid.
The present invention is owing to adjusted component content, and the effective concentration that especially will contain the sulfonic group terpolymer is brought up to 20～40mg/l, thereby cooperates other component to improve the cycles of concentration of water conditioner greatly again when guaranteeing anticorrosion and scale inhibition effect.Adopt " water coolant analysis and experimental technique " middle static-state scale inhibition evaluation experimental technique of China Petrochemical Industry, analyze by experiment and draw scale inhibition performance more than 80%, in the corrosion speed 0.04mm/a.
Embodiment
Change the kind and the consumption that contain sulfonic group terpolymer, organic phosphoric acid, zinc salt, metal inhibitor and carry out embodiment 1-7, proportioning raw materials and test-results see Table 2.
Table 2 proportioning raw materials and test-results
| Sequence number | Corrosion speed mm/a | Scale inhibition performance % | The medicament proportioning |
| Embodiment 1 | ????0.040 | ????80.6 | ????AA/AMPS/HPA∶HEDP∶Zn 2+＝20∶6∶1 |
| Embodiment 2 | ????0.019 | ????87.20 | ????AA/AMPS/HPA∶HEDP∶Zn 2+＝30∶5∶1 |
| Embodiment 3 | ????0.040 | ????81.60 | ????AA/AMPS/HPA∶PBTCA∶Zn 2+＝20∶10∶1 |
| Embodiment 4 | ????0.040 | ????80.36 | ????AA/AMPS/AM∶HEDP∶Zn 2+＝20∶8∶1 |
| Embodiment 5 | ????0.037 | ????80.23 | ????AA/AMPS/AMPP∶HEDP∶Zn 2+＝20∶5∶1 |
| Embodiment 6 | ????0.023 | ????91.80 | ????AA/AMPS/HPA∶HEDP∶BTA∶Zn 2+＝30∶5∶1∶1 |
| Embodiment 7 | ????0.030 | ????92.10 | ????AA/AMPS/HPA∶HEDP∶BTA∶Zn 2+＝35∶5∶1∶2 |
The used water quality of above-mentioned test sees Table 3,
Table 3 experimental water water quality
| Project | PH | Specific conductivity μ S/cm | Total alkali mg/L | Total hard mg/L | Calcium ion mg/L | Chlorion mg/L | Total molten solid mg/L | Turbidity mg/L |
| Analytical value | 8.3 | 480 | 165 | 230 | 136 | 60 | 3 | 2.23 |
The methods involving that corrosion speed, scale inhibition performance are tested in " water coolant analysis and the experimental technique " that all adopts China Petrochemical Industry carries out.The calculation of correlation formula is:
: the corrosion vector (g) of test specimen
A: the area (cm of test specimen
2)
T: corrosion test time (hr)
ρ: the density (kg/m of material for test
3)
Scale inhibition performance is by following formula:
Ca
0 2+The Ca of actual measurement before the test of-test solution
2 2+Concentration multiply by cycles of concentration again and theoretical Ca
2+Concentration
Ca
1 2+The concentration of-Jia Scale inhibitors, the Ca after the test
2+Concentration
Ca
2 2+-do not add the Ca of Scale inhibitors test solution (blank) under same test conditions
2+Concentration
Prepare the water conditioner of effective concentration 30% according to embodiment 2 proportionings, be applied to a crude oil and urge cracking unit, it possesses water yield 800m
3, internal circulating load 2000m
3, interchanger is carbon steel, and there is a spot of oil leakage in system.Make up water water quality situation sees Table 4.
Table 4: Analysis Results of Water Quality
| Project | PH | Specific conductivity μ S/cm | Total alkali mg/L | Total hard mg/L | Calcium ion mg/L | Chlorion mg/L | Total molten solid mg/L | Turbidity mg/L |
| Analytical value | 8.3 | 520 | 165 | 272 | 126 | 21 | 320 | 3.5 |
Under natural enrichment stage, the pH scope is in 8.0～9.0, and cycles of concentration is 3.1～3.2, and the heterotrophic bacterium number is less than 1 * 10
5Individual/ml, working concentration is 50mg/L, and corrosion speed sees Table 5.
Table 5: corrosion speed unit: mm/a
Prepare the water conditioner of effective concentration 30% according to embodiment 6 proportionings, be applied to fertilizer plant's circulating water of producing 300000 tons of synthetic ammonia per year, it possesses water yield 10000m
3, internal circulating load is 30000m
3, material has a little copper and white steel based on carbon steel, and its make up water water quality is with table 4.
Under natural enrichment stage, the pH scope is in 8.0～9.0, and cycles of concentration is 3.3～3.5, and turbidity is less than 10, and the heterotrophic bacterium number is less than 1 * 10
5Individual/ml, working concentration is 50mg/L, and corrosion speed and adhesion speed see Table 6
Table 6: the adhesion speed and the corrosion speed of each material
Claims (6)
1. a polynary composite water disposal agent is mainly formed by containing sulfonic group terpolymer, organic phospho acid, zinc salt and metal inhibitor, and the weight ratio that it is characterized in that them is 20～40: 1～10: 0.5～4: 0～3, and wherein the weight of zinc salt is in zinc.
2. polynary composite water disposal agent according to claim 1 is characterized in that the described sulfonic group terpolymer that contains comprises vinylformic acid/2-acrylamide-2-methyl-propyl sulfonic acid/2-acrylamide-2-methyl-propyl phosphonic acids, vinylformic acid/2-acrylamide-2-methyl-propyl sulfonic acid/acrylamide, vinylformic acid/2-acrylamide-2-methyl-propyl sulfonic acid/Propylene glycol monoacrylate, vinylformic acid/2-acrylamide-2-methyl-propyl sulfonic acid/styrene sulfonic acid.
3. polynary composite water disposal agent according to claim 1 is characterized in that described organic phospho acid comprises hydroxy ethylene diphosphonic acid, Amino Trimethylene Phosphonic Acid, 2-phosphinylidyne butane-1,2,4 tricarboxylic acid, ethylene diamine tetramethylene phosphonic acid.
4. polynary composite water disposal agent according to claim 1 is characterized in that described zinc salt comprises zinc sulfate, zinc chloride.
5. polynary composite water disposal agent according to claim 1 is characterized in that described metal inhibitor comprises mercaptobenzothiazole, benzotriazole, methyl benzotriazazole.
6. polynary composite water disposal agent according to claim 1, the weight ratio that it is characterized in that containing sulfonic group terpolymer, organic phospho acid, zinc salt and metal inhibitor is 25～35: 1～10: 0.5～1: 0～2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031376037A CN1273394C (en) | 2003-06-18 | 2003-06-18 | Polynary composite water treatment agent |
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|---|---|---|---|
| CNB031376037A CN1273394C (en) | 2003-06-18 | 2003-06-18 | Polynary composite water treatment agent |
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| CN1565994A true CN1565994A (en) | 2005-01-19 |
| CN1273394C CN1273394C (en) | 2006-09-06 |
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|---|---|---|---|
| CNB031376037A Expired - Fee Related CN1273394C (en) | 2003-06-18 | 2003-06-18 | Polynary composite water treatment agent |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357331C (en) * | 2005-06-15 | 2007-12-26 | 北京博泰盛合科技有限公司 | Copolymer and its preparation method and reverse osmosis membrane protective agent comprising the copolymer and its uses |
| CN100404438C (en) * | 2005-05-31 | 2008-07-23 | 北京洁利尼水处理工程有限公司 | Water treatment agent and preparation method thereof |
| CN101279797B (en) * | 2007-04-02 | 2010-07-21 | 北京洁利尼水处理工程有限公司 | Treatment agent for life drinking water, preparation and application thereof |
| CN101698542B (en) * | 2009-11-17 | 2012-01-04 | 上海依科绿色工程有限公司 | Composite corrosion and scale inhibitor for open type cooling water system made of galvanized pipe, preparation method and application thereof |
| CN102351326A (en) * | 2011-08-29 | 2012-02-15 | 山东天庆科技发展有限公司 | Method for preparing micro-phosphor anti-scaling corrosion inhibitor |
| CN101353581B (en) * | 2008-09-05 | 2012-05-30 | 西安陕鼓动力股份有限公司 | Special scale inhibitor for wet-type dust removing blast furnace gas energy recovery turbine installation |
| CN102701471A (en) * | 2012-06-15 | 2012-10-03 | 山东省泰和水处理有限公司 | High-harness water corrosion and scale inhibitor |
| CN102732218A (en) * | 2012-07-06 | 2012-10-17 | 兰州英潍诺化工科技有限公司 | Method for preparing special high-efficiency composite corrosion inhibitor for coal or mineral powder transportation anti-freezing liquid |
| CN103241846A (en) * | 2013-05-09 | 2013-08-14 | 北京市龙源科创石油技术有限公司 | Composite scale and corrosion inhibitor |
| CN105543853A (en) * | 2015-12-18 | 2016-05-04 | 昆明理工大学 | Corrosion inhibitor for aluminum corrosion control |
| CN109467200A (en) * | 2019-01-08 | 2019-03-15 | 成都工业学院 | MVR use in waste water treatment antisludging agent and its preparation method and application |
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| CN102198983B (en) * | 2010-03-23 | 2013-07-17 | 上海梅山钢铁股份有限公司 | Corrosion inhibition antisludging agent for reclaimed water circulating water system and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100404438C (en) * | 2005-05-31 | 2008-07-23 | 北京洁利尼水处理工程有限公司 | Water treatment agent and preparation method thereof |
| CN100357331C (en) * | 2005-06-15 | 2007-12-26 | 北京博泰盛合科技有限公司 | Copolymer and its preparation method and reverse osmosis membrane protective agent comprising the copolymer and its uses |
| CN101279797B (en) * | 2007-04-02 | 2010-07-21 | 北京洁利尼水处理工程有限公司 | Treatment agent for life drinking water, preparation and application thereof |
| CN101353581B (en) * | 2008-09-05 | 2012-05-30 | 西安陕鼓动力股份有限公司 | Special scale inhibitor for wet-type dust removing blast furnace gas energy recovery turbine installation |
| CN101698542B (en) * | 2009-11-17 | 2012-01-04 | 上海依科绿色工程有限公司 | Composite corrosion and scale inhibitor for open type cooling water system made of galvanized pipe, preparation method and application thereof |
| CN102351326A (en) * | 2011-08-29 | 2012-02-15 | 山东天庆科技发展有限公司 | Method for preparing micro-phosphor anti-scaling corrosion inhibitor |
| CN102701471A (en) * | 2012-06-15 | 2012-10-03 | 山东省泰和水处理有限公司 | High-harness water corrosion and scale inhibitor |
| CN102732218A (en) * | 2012-07-06 | 2012-10-17 | 兰州英潍诺化工科技有限公司 | Method for preparing special high-efficiency composite corrosion inhibitor for coal or mineral powder transportation anti-freezing liquid |
| CN102732218B (en) * | 2012-07-06 | 2014-10-15 | 兰州英潍诺化工科技有限公司 | Method for preparing special high-efficiency composite corrosion inhibitor for coal or mineral powder transportation anti-freezing liquid |
| CN103241846A (en) * | 2013-05-09 | 2013-08-14 | 北京市龙源科创石油技术有限公司 | Composite scale and corrosion inhibitor |
| CN105543853A (en) * | 2015-12-18 | 2016-05-04 | 昆明理工大学 | Corrosion inhibitor for aluminum corrosion control |
| CN109467200A (en) * | 2019-01-08 | 2019-03-15 | 成都工业学院 | MVR use in waste water treatment antisludging agent and its preparation method and application |
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| Publication number | Publication date |
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| CN1273394C (en) | 2006-09-06 |
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