CN102452721A - Phosphorus-free composite scale-inhibiting corrosion-retarding agent and application thereof in water treatment - Google Patents
Phosphorus-free composite scale-inhibiting corrosion-retarding agent and application thereof in water treatment Download PDFInfo
- Publication number
- CN102452721A CN102452721A CN2010105124464A CN201010512446A CN102452721A CN 102452721 A CN102452721 A CN 102452721A CN 2010105124464 A CN2010105124464 A CN 2010105124464A CN 201010512446 A CN201010512446 A CN 201010512446A CN 102452721 A CN102452721 A CN 102452721A
- Authority
- CN
- China
- Prior art keywords
- acid
- corrosion inhibitor
- multipolymer
- water
- phosphorus
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
The invention relates to a phosphorus-free composite scale-inhibiting corrosion-retarding agent and an application thereof. The phosphorus-free composite scale-inhibiting corrosion-retarding agent comprises a water-soluble borate and at least one scale-inhibiting dispersant, wherein the scale-inhibiting dispersant is a carboxylic-group-containing phosphorus-free polymer. The comprehensive property of the phosphorus-free composite scale-inhibiting corrosion-retarding agent is good. The agent has good CaCO3 scale inhibiting performance, good stabilizing performance upon Zn<2+> in water, and good corrosion retarding performance. The agent can be used in treating circulating cooling water. With the agent, harm of phosphorus discharging to the environment can be solved.
Description
Technical field
The present invention relates to a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter and application thereof, relate more specifically to a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter of boracic hydrochlorate and application in recirculated cooling water is handled thereof.
Background technology
In recirculating cooling water system, mainly exist fouling, corrosion and mikrobe to endanger three aspect problems.Anti-locking system fouling is in recirculated cooling water, to add corrosion inhibiting and descaling agent with corrosion most convenient and effective means.Mostly the at present domestic prescription that is usually used in the recirculated cooling water processing is phosphine system prescription, and its host is for containing phosphonate group (PO
3H
2) the direct corrosion inhibiting and descaling agent that links to each other with carbon atom, often be referred to as organic phospho acid.They mainly comprise: HEDP (HEDP), ATMP (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic (DEPTMP) etc.
Organic phospho acid has made water technology and technology that considerable progress arranged since the later stage in the sixties is developed and is applied to the recirculated cooling water processing.Compare with the inorganic polyphosphate in the early stage phosphorus line formulation, organic phospho acid have good chemicalstability, not facile hydrolysis, can anti-comparatively high temps, dosing is little, and has inhibition concurrently and scale inhibition is difunctional.Organic phospho acid is one type of cathode type inhibiter, is again one type of equivalent Scale inhibitors non-chemically simultaneously, has significantly to dissolve the limit effect.They are to many metals ions such as Ca
2+, Mg
2+, Cu
2+, Zn
2+Deng all having good sequestering power, even to the inorganic salts such as the CaCO of some metals
3, CaSO
4, MgSiO
3Deng deactivation is preferably also arranged.But organic phosphine commonly used can not suppress calcium phosphate scale and zinc dirt effectively and solve the iron oxide precipitation problem, and itself is prone to be formed with the machine phosphonic acid dirt.In addition, P contained compound makes people recognize the importance of control P contained compound discharging gradually to the pollution of water body and the eutrophication problem that causes.
A lot of rivers, lake cause aquatic plants growth out of control because of entering a large amount of phosphorus in the world wide, and dissolved oxygen in water exhausts, final water quality deterioration, aquatic animals and plants disappearance.The red tide that China's Coastal Areas took place frequently and on a large scale in recent years is also relevant with nutraceutical discharging such as a large amount of phosphorus, has caused huge disaster to aquatic products breed and natural, ecological.In recent years, forced sale of Taihu Lake, Dianchi Lake Basin, reservoir area of Three Gorges and use non-phosphorus detergent, after the Shandong Province, Liaoning Province announces to prohibit phosphorus recently comprehensively, in the hope of the phosphorus discharging of minimizing in natural water.Now, low-phosphorous, phosphate-free water treatment agent has become the focus of research.Along with the raising of environmental consciousness, the further strictness of environmental regulation, many countries have begun the discharging of phosphorus restriction, and the for example German discharging that has required phosphorus has promoted development low-phosphorous, without phosphorus prescription smaller or equal to 1mg/L.
At present domestic without phosphorus water treatment formulating many is to be the corrosion inhibiting and descaling agent that master's Scale inhibitors is equipped with inhibiter compositions such as molybdate, silicate, tungstate, zinc salt, borate with SAP 73 or poly-epoxy succinic acid or xylogen, tannin etc.
CN101638272A discloses a kind of green non-phosphate inhibitor, and it comprises xylogen, tannin, also can with compounded corrosion inhibiting and descaling agents such as vinylformic acid, trolamine, borate.Its shortcoming is that corrosion mitigating effect differs greatly to different hardness water quality, and corrosiorate meter can be controlled in 0.0723mm/a when the high-hardness water working concentration was 40mg/L; To soft water quality, when working concentration was brought up to 60mg/L, erosion rate was still very high, is 0.1073mm/a.
CN101353205A discloses a kind of method that prevents the soft water etching apparatus, and its characteristics are, in softening water, add borate and copper inhibitor, and the borate dosage is between 1200-2000mg/L, and the copper inhibitor dosage is between 1-2mg/L.At blast furnace furnace wall, when the hotblast stove recirculated cooling water adopts softening water, can prevent softening water to corrosion on Equipment, its shortcoming is that the borate consumption is too big.
Summary of the invention
The contriver discovers: borate with contain that carboxylic acid group polymer's dirt dispersion agent is compound can be suppressed calcium phosphate scale, zinc dirt effectively and disperse the lime carbonate performance, be applied to circulating water treatment and can solve organic phosphine medicament commonly used because of the high harm of phosphorus content to environment.
The object of the present invention is to provide a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter.
Another object of the present invention is that composite scale-inhibiting corrosion inhibitor of the present invention is applied to recirculated cooling water to be handled.
For achieving the above object, the invention provides a kind of non-Phosphorus composite anti incrustation eorrosion snhibiter, it comprises a kind of water-soluble borate and at least a dirt dispersion agent, and said dirt dispersion agent is the without phosphorus polymkeric substance that contains the carboxylic acid group.
Borate of the present invention is selected from Sodium Tetraborate and potassium borate, and sylvite is higher than the sodium salt price, considers from economic angle, preferably from Sodium Tetraborate, more preferably from sodium borate decahydrate, five hydration sodium tetraborates and four hydrations, eight Sodium Tetraboratees.
The carboxylic acid group's of containing according to the invention without phosphorus polymkeric substance is selected from homopolymer, copolymer and terpolymer, preferably from SAP 73, poly-epoxy succinic acid, ROHM, HPMA, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, propenoate/styrene sulfonic acid multipolymer, toxilic acid (acid anhydride)/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.Wherein said propenoate is preferably from vinylformic acid C
1-8Ester is more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate.
Initiator system when usually binary and ternary contain the carboxylic acid-based copolymer and synthesize has two types, and one type is phosphorous initiator system, like phosphorated inferior sodium phosphate and ammonium persulphate initiator system; Another kind of is without phosphorus initiator system, like without phosphorus Sodium Pyrosulfite and ammonium persulphate initiator system.When adopting last type of initiator system, in multipolymer, can introduce the phosphorus about 1%; Then without phosphorus when adopting back one type of initiator system, both synthesis conditions are basic identical.For thoroughly avoiding phosphorous in the polymkeric substance, binary of the present invention and ternary contain carboxylic acid-based copolymer's synthetic initiator system and are preferably not phosphorated initiator system, like Sodium Pyrosulfite and ammonium persulphate initiator system.Homopolymer synthetic initiator system generally selects without phosphorus ammonium persulphate etc.
Composite scale-inhibiting corrosion inhibitor is with respect to pending aqueous solution total amount, and the effective concentration of each component is: borate is (with B
4O
7 2-Meter) be 20-100mg/L, preferred 40-60mg/L, the without phosphorus polymer concentration that contains the carboxylic acid group is 2-20mg/L.
When in recirculating cooling water system, using copper material equipment; Composite scale-inhibiting corrosion inhibitor also can contain heterogeneous ring compound as copper material corrosion inhibitor; Described copper material corrosion inhibitor is preferably mercaptobenzothiazole and benzotriazole, and the effective concentration of copper material corrosion inhibitor is 0.5-1.5mg/L.
When composite scale-inhibiting corrosion inhibitor of the present invention is used for recirculated cooling water, also can contain zinc salt as inhibiter, said zinc salt is elected zinc sulfate or zinc chloride as.With respect to pending aqueous solution total amount, the effective concentration of zinc salt is (with Zn
2+Meter) be 0.5-3.0mg/L.
Available ordinary method prepares composite scale-inhibiting corrosion inhibitor; The reinforced order of each component is unimportant; For example can make required non-Phosphorus composite anti incrustation eorrosion snhibiter with containing carboxylic acid group polymer, borate, zinc salt (if any) and copper material corrosion inhibitor (if any) and water by predetermined mixed.
Composite scale-inhibiting corrosion inhibitor good combination property of the present invention, it has good resistance CaCO
3The dirt performance also has Zn in the good stabilize water
2+Ability and corrosion inhibition, be applicable to that recirculated cooling water handles, solve the harm of phosphorus discharging to environment.
Non-Phosphorus composite anti incrustation eorrosion snhibiter of the present invention can be applicable to recirculated cooling water and handles, and is particularly suitable for being applied to the processing of the not adjust pH recirculated cooling water of medium hardness that calcium hardness and total alkalinity sum are 100-300mg/L, moderate alkalinity water quality.
For calcium hardness and total alkalinity sum is the high firmness more than the 300mg/L, high basicity water quality, when it is used for recirculated cooling water, for preventing fouling; Often adopt to add sour adjust pH, reduce the basicity in the water, at this moment; The inhibition problem should be the major issue that will solve; When composite scale-inhibiting corrosion inhibitor of the present invention is used for the processing of recirculated cooling water, can increase the good component of corrosion inhibition, like zinc salt etc.
For calcium hardness and total alkalinity sum is the soft below the 100mg/L, low basicity water quality; When it is used for recirculated cooling water; The major issue that solves also is the inhibition problem, and is same, when composite scale-inhibiting corrosion inhibitor of the present invention is used for the processing of recirculated cooling water; Also should increase the good component of corrosion inhibition, like zinc salt etc.
Embodiment
Following embodiment will help to explain the present invention, but not limit to its scope.
The used test raw water quality of following embodiment 1-9 and Comparative Examples 1-4 is seen table 1.
Table 1 test raw water quality
| Water quality | Ca 2+ | Total alkalinity | Total hardness | Cl - | SO 4 2- | pH | Specific conductivity | Total dissolving admittedly |
| Former water 1 | 102 | 152 | 179 | 15 | 37 | 7.8 | 213 | 318 |
| Former water 2 | 257 | 384 | 365 | 81 | 123 | 7.8 | 1020 | 759 |
| Former water 3 | 23 | 34 | 39 | 8 | 13 | 7.4 | 122 | 71 |
Annotate: 1) pH does not have unit, and specific conductivity is μ s/cm, and its counit is mg/L, Ca
2+, total alkalinity, total hardness be all with CaCO
3Meter, down together;
2), Ca
2+Represent calcium hardness, down together.
The measuring method of water quality is with reference to as follows:
Ca
2+: GB/T 6910-2006 " the mensuration complexometry of BW and water coolant analytical procedure calcium "
Total alkalinity: GB/T 15451-2006 " mensuration of industrial circulating cooling water total alkali and phenolphthalein alkalinity "
Total hardness: GB/T 6909-2008 " mensuration of BW river water coolant analytical procedure hardness "
Cl
-: GB/T 15453-2008 " mensuration of cl ions in industrial circulating cooling water and the BW "
SO
4 2-: GB/T 14642-2009 " the mensuration ion chromatography of fluorine, chlorine, phosphate radical, nitrite anions, nitrate radical and sulfate radical in industrial circulating cooling water and the feedwater "
PH value: GB/T 6920-1986 " the mensuration glass electrode method of water pH value "
Specific conductivity: GB/T 6908-2008 " mensuration of BW river water coolant analytical procedure specific conductivity "
Total dissolving admittedly: GB/T 14415-2007 " mensuration of solid matter in industrial circulating cooling water and the BW "
Zn
2+: GB/T 10656-2008 " the mensuration zincon spectrophotometry of BW and water coolant analytical procedure zine ion "
The assessment of performance method of the composite scale-inhibiting corrosion inhibitor of following embodiment gained is following:
The test water distribution concentrates behind the corresponding multiple laboratory according to raw water quality and prepares voluntarily and obtain, and test water distribution water quality is seen table 2.
Table 2 test water distribution water quality
| Water quality | Ca 2+ | Total alkalinity | Total hardness | Cl - | SO 4 2- |
| Test water distribution 1 (concentrating 5 times) | 510 | 760 | 950 | 75 | 185 |
| Test water distribution 2 (concentrating 3 times) | 771 | 1152 | 1095 | 243 | 369 |
| Test water distribution 3 (concentrating 5 times) | 115 | 170 | 195 | 40 | 65 |
Resistance calcium carbonate scale performance is got the test water distribution, adds by the drug concentration that embodiment added, and in 80 ± 1 ℃ of waters bath with thermostatic control, leaves standstill 10h with the volumetric flask method, remains Ca in the sampling analysis water after cooling
2+Concentration, do blank simultaneously, and calculate scale inhibition performance.
The scale inhibition performance calculation formula is: scale inhibition performance=(C-C
0)/(C
1-C
0) * 100%
C: actual measurement Ca
2+Concentration (mg/L)
C
0: the Ca of blank
2+Concentration (mg/L)
C
1: the Ca in the test water distribution
2+Concentration (mg/L)
Stablize the zinc salt performance and get zero(ppm) water preparation Ca
2+Concentration is 250mg/L, and basicity is 250mg/L and Zn
2+Be the test water of 5mg/L, add medicament, in 80 ± 1 ℃ of waters bath with thermostatic control, leave standstill 10h, remain Zn in the sampling analysis water by the drug concentration that embodiment added
2+Concentration, do blank simultaneously, and calculate resistance zinc rate.
Resistance zinc rate calculation formula is: resistance zinc rate=(C-C
0)/(C
1-C
0) * 100%
C: actual measurement Zn
2+Concentration (mg/L)
C
0: the Zn of blank
2+Concentration (mg/L)
C
1: the Zn in the former water
2+Concentration (mg/L)
Resistance zinc rate is high more, and the stability of zinc salt in water is good more, and it is good more to explain that medicament is stablized the performance of zinc salt.
Corrosion inhibition is fixed on the test piece of 20# qualitative carbon steel on the lacing film appearance; Put into the test water that is added with the drug concentration that adds by embodiment, 45 ± 1 ℃ of steady temperatures keep rotating speed 75rpm rotation 72h; The weight of test piece is calculated average corrosion rate before and after the record test.
The average corrosion rate calculation formula is: F=(C * Δ W)/(A * T * ρ)
C: computational constant, when being unit with mm/a (millimeter/year), C=8.76 * 10
7
Δ W: the corrosion weight loss of test specimen (g)
A: the area (cm of test specimen
2)
T: corrosion test time (h)
ρ: the density (kg/m of material for test
3)
When measuring scale-inhibiting properties, following embodiment and Comparative Examples are used all adjust pHs not of any test water quality; When measuring corrosion inhibition, need adjust pH when following embodiment and the water distribution 2 of Comparative Examples use-testing.
Embodiment 1
Take by weighing the 98.3g sodium borate decahydrate and (contain B
4O
7 2-40.7%), the 25.0g solid content is that 40% SAP 73 (number-average molecular weight 3000) joins in the 76.7g water, shakes up, and promptly obtains the 200.0g medicament of required preparation.
When adding in test water distribution 1 by the drug concentration of 200mg/L with the medicament for preparing, B in the water
4O
7 2-, SAP 73 effective concentration be respectively 40mg/L, 10mg/L.
Embodiment 2
Take by weighing 66.3 four hydrations, eight Sodium Tetraboratees and (contain B
4O
7 2-37.7%) and the 45.0g solid content be that 40% poly-epoxy succinic acid (number-average molecular weight 1000) joins in the 88.7g water, shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When adding in test water distribution 1 by the drug concentration of 200mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, poly-epoxy succinic acid effective concentration be respectively 25mg/L, 18mg/L.
Embodiment 3
Take by weighing 83.3g five water potassium tetraborates and (contain B
4O
7 2-48.0%) and the 53.3g solid content be that 30% ROHM (number-average molecular weight is 3000) is dissolved in the 63.4g water, shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When adding in test water distribution 1 by the drug concentration of 200mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, polyacrylic effective concentration is respectively 40mg/L, 16mg/L.
Embodiment 4
Take by weighing 84.4g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%) and the 20g solid content be that 50% HPMA (number-average molecular weight 1000) is dissolved in the 95.6g water, shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When adding in test water distribution 1 by the drug concentration of 200mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, HPMA effective concentration be respectively 45mg/L, 10mg/L.
Embodiment 5
Take by weighing the 122.9g sodium borate decahydrate and (contain B
4O
7 2-40.7%), the 20.0g solid content is that (limit viscosity number is 0.072d l/g 30 ℃ the time for vinylformic acid (AA)/Propylene glycol monoacrylate (HPA) multipolymer of 30%; AA/HPA=70/30 (weight ratio; Down with)) and the 1.2g benzotriazole be dissolved in the 55.9g water; Shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When adding in test water distribution 1 by the drug concentration of 200mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, T225 and benzotriazole effective concentration be respectively 50mg/L, 12mg/L, 1.2mg/L.
Embodiment 6
Take by weighing 125.0g five hydration potassium tetraborates and (contain B
4O
7 2-48.0%) and the 33.3g solid content be that (limit viscosity number is 0.072dl/g 30 ℃ the time for vinylformic acid/Propylene glycol monoacrylate/methyl acrylate (MA) multipolymer of 30%; AA/HPA/MA=70/15/15) be dissolved in the 41.7g water; Shake up, promptly obtain the 200.0g liquid medicine of required preparation.When adding in test water distribution 1 by the drug concentration of 200mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer effective concentration be respectively 60mg/L, 10mg/L.
Embodiment 7
Take by weighing 106.1g four hydrations eight Sodium Tetraboratees and (contain B
4O
7 2-53.3%), the 53.3g solid content be acrylic acid (AM)/2-methyl-2 of 30% '-(limit viscosity number is 0.072dl/g to acrylamido propane sulfonic acid (AMPS) multipolymer 30 ℃ the time; AA/AM/AMPS=70/15/15) and the 11.0g Zinc Sulphate Heptahydrate; Be dissolved in the 40.6g water; Shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When adding in test water distribution 2 (using the sulfuric acid adjust pH is 8.1) by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and Zn
2+Effective concentration be respectively 40mg/L, 16mg/L, 2.5mg/L.
Embodiment 8
Take by weighing 178.2g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%), the 16.7g solid content is that (limit viscosity number is 0.072dl/g 30 ℃ the time for maleic anhydride/styrene sulfonic acid multipolymer of 30%; Maleic anhydride/styrene sulfonic acid=70/30) and the 2.1g Zinc Chloride Anhydrous; Be dissolved in the 53.0g water, shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water distribution 3 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, maleic anhydride/styrene sulfonic acid multipolymer and Zn
2+Effective concentration be respectively 95mg/L, 5mg/L, 1mg/L.
Embodiment 9
Take by weighing 112.6g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%), the 30.0g solid content is that (limit viscosity number is 0.072dl/g 30 ℃ the time for methyl acrylate/styrene sulfonic acid multipolymer of 30%; MA/ styrene sulfonic acid=80/20), the 30.0g solid content is that (limit viscosity number is 0.072d l/g 30 ℃ the time for toxilic acid/allyl sulphonic acid multipolymer of 30%; Toxilic acid/allyl sulphonic acid=60/40) and the 3.2g Zinc Chloride Anhydrous; Join in the 74.2g water, shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water distribution 2 (using the sulfuric acid adjust pH is 7.9) and 3 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, methyl acrylate/styrene sulfonic acid multipolymer, toxilic acid/allyl sulphonic acid multipolymer and Zn
2+Effective concentration be respectively 60mg/L, 9mg/L, 9mg/L, 1.5mg/L.
Embodiment 10
Take by weighing 93.8g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%), the 13.3g solid content is that (limit viscosity number is 0.072dl/g 30 ℃ the time for vinylformic acid/allyl sulphonic acid multipolymer of 30%; AA/ allyl sulphonic acid=70/30) and the 13.3g solid content be that (limit viscosity number is 0.072dl/g 30 ℃ the time for vinylformic acid/vinyl sulfonic acid multipolymer of 30%; AA/ vinyl sulfonic acid=70/30) joins in the water of 79.6g; Shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When adding in test water distribution 1 by the drug concentration of 200mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, vinylformic acid/allyl sulphonic acid multipolymer vinylformic acid/vinyl sulfonic acid multipolymer and Zn
2+Effective concentration be respectively 50mg/L, 4mg/L, 4mg/L.
Embodiment 11
Take by weighing the 73.7g sodium borate decahydrate and (contain B
4O
7 2-40.7%), the 12.5g solid content is that 40% SAP 73 (number-average molecular weight 3000), 16.7g solid content are that (limit viscosity number is 0.072dl/g 30 ℃ the time for vinylformic acid (AA)/Propylene glycol monoacrylate (HPA) multipolymer of 30%; AA/HPA=70/30), the 16.7g solid content be vinylformic acid/toxilic acid/2-methyl-2 of 30% '-(limit viscosity number is 0.072dl/g to acrylamido propane sulfonic acid multipolymer 30 ℃ the time; AA/MA/AMPS=70/15/15) and 0.8g sulfydryl benzotriazole; Be dissolved in the 79.6g water; Shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When adding in test water distribution 1 by the drug concentration of 200mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, SAP 73, vinylformic acid (AA)/Propylene glycol monoacrylate (HPA) multipolymer, vinylformic acid/toxilic acid/2-methyl-2 '-effective concentration of acrylamido propane sulfonic acid multipolymer and sulfydryl benzotriazole is respectively 30mg/L, 5mg/L, 5mg/L, 5mg/L, 0.8mg/L.
Embodiment 12
Take by weighing the 122.9g sodium borate decahydrate and (contain B
4O
7 2-40.7%), the 12.5g solid content is that 40% poly-epoxy succinic acid, 16.7g solid content are that (limit viscosity number is 0.072dl/g 30 ℃ the time for vinylformic acid/Propylene glycol monoacrylate/methyl acrylate (MA) multipolymer of 30%; AA/HPA/MA=70/15/15), the 16.7g solid content is that (limit viscosity number is 0.072dl/g 30 ℃ the time for toxilic acid/allyl sulphonic acid multipolymer of 30%; Toxilic acid/allyl sulphonic acid=60/40) and the 4.2g Zinc Chloride Anhydrous; Be dissolved in the 77.0g water; Shake up, promptly obtain the 250.0g liquid medicine of required preparation.
When adding in test water distribution 1 by the drug concentration of 250mg/L with the liquid medicine for preparing, B in the water
4O
7 2-, poly-epoxy succinic acid, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid/allyl sulphonic acid multipolymer and Zinc Chloride Anhydrous effective concentration be respectively 50mg/L, 5mg/L, 5mg/L, 5mg/L, 2mg/L.
Comparative Examples 1
(limit viscosity number is 0.078dl/g 30 ℃ the time to take by weighing the 20.0g solid content and be vinylformic acid/2-methyl-2 ' acrylamido propane sulfonic acid/Propylene glycol monoacrylate terpolymer of 30%; Weight ratio is AA/AMPS/HPA=60/20/20), the 9.0g active ingredient is 50% 2-phosphonate group-1; 2,4-butane tricarboxylate (PBTCA), 9.0g HEDP (HEDP) add in the 62.0g water; Shake up, promptly obtain the 100.0g liquid medicine of required preparation.
When in test water distribution 1, adding by the drug concentration of 100mg/L with the liquid medicine for preparing, the effective concentration of the terpolymer of AA/AMPS/HPA, PBTCA, HEDP is respectively 6mg/L, 4.5mg/L, 4.5mg/L.
Comparative Examples 2
Take by weighing 150.1g five hydration sodium tetraborates and (contain B
4O
7 2-53.3%) is dissolved in the 38.5g water, promptly obtains the 100.0g liquid medicine of required preparation.When adding in test water distribution 1 and test water distribution 3 by the drug concentration of 99.9mg/L with the liquid medicine for preparing, B
4O
7 2-Effective concentration is 80mg/L.
Comparative Examples 3
(limit viscosity number is 0.078dl/g 30 ℃ the time to take by weighing the 20.0g solid content and be 40% SAP 73 (number-average molecular weight 3000), 16.0g solid content and be 50% HPMA (number-average molecular weight 1000), 20.0g solid content and be vinylformic acid/2-methyl-2 ' acrylamido propane sulfonic acid/Propylene glycol monoacrylate terpolymer of 30%; Weight ratio is AA/AMPS/HPA=60/20/20) be dissolved in the 144.0g water; Shake up, promptly obtain the 200.0g liquid medicine of required preparation.
When in test water distribution 1 and test water distribution 2 (using the sulfuric acid adjust pH is 8.0), adding by the drug concentration of 200mg/L with the liquid medicine for preparing, the effective concentration of SAP 73, HPMA, AA/AMPS/HPA is respectively 8mg/L, 8mg/L, 6mg/L in the water.
Carry out static test by the above-mentioned concentration that adds, inhibition and scale inhibition effect are seen table 3.
The inhibition of table 3 medicament and scale inhibition effect
Table 3 data declaration, composite scale-inhibiting corrosion inhibitor good combination property of the present invention, it has good resistance CaCO
3The dirt function also has Zn in the satisfactory stability water
2+Ability and corrosion inhibition.
Embodiment 11 and Comparative Examples 4
For simulated field, carried out dynamic analog test.The dynamic analog test method is undertaken by the chemical industry standard HG/T2160-2008 of the People's Republic of China, and controlled variable is following.
Cycles of concentration control is controlled with calcium hardness+total alkalinity value:
Concentrate the A tower: 950 ± 50mg/L B tower, 950 ± 50mg/L
Flow velocity: 1.0m/s
Medicament: A tower: the compound of Comparative Examples 1
The compound of B tower: embodiment 10
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
The test raw water quality is seen the former water 1 of table 1.
Dynamic analog test test tube result sees table 4.
Table 4 dynamic analog test test tube result
Stipulate that the corrosion speed of the carbon steel tube wall of open type system is less than or equal to 0.125mm/a among standard GB 50050-2007 " Code for design of industrial recirculating cooling water treatment " 3.1.6; " the small-sized experimental analogic method of testing laboratory " regulation corrosion of Carbon Steel speed is " fine " level at 0-0.028mm/a in " the water coolant analysis and the TP " of production department of China PetroChemical Corporation and development division establishment; 0.028-0.056mm/a between be " good " level, 0.056-0.070mm/a for " can allow " level; Adhesion speed is " fine " level at 0-6mcm, is " good " level at 6-15mcm, is " can allow " level at 15-20mcm.
This shows; Using non-Phosphorus composite anti incrustation eorrosion snhibiter of the present invention is under the situation of 950 ± 50mg/L in calcium hardness and total alkalinity sum; The erosion rate of test tube is 0.028mm/a, reaches China Petrochemical Industry's " good level " standard, adheres to speed 10.4mcm; Reach " good level " standard, have inhibition and the scale inhibition effect of phosphorus prescription when calcium hardness+total alkalinity is 950 ± 50mg/L suitable with contrast.
Claims (10)
1. non-Phosphorus composite anti incrustation eorrosion snhibiter, it comprises a kind of water-soluble borate and at least a dirt dispersion agent, and said dirt dispersion agent is the without phosphorus polymkeric substance that contains the carboxylic acid group.
2. anti-incrustation corrosion inhibitor according to claim 1 is characterized in that said borate is selected from Sodium Tetraborate and potassium borate, preferably from Sodium Tetraborate, more preferably from sodium borate decahydrate, five hydration sodium tetraborates and four hydrations, eight Sodium Tetraboratees.
3. anti-incrustation corrosion inhibitor according to claim 1 and 2; It is characterized in that the without phosphorus polymkeric substance that contains the carboxylic acid group is selected from homopolymer, copolymer and terpolymer, preferably from SAP 73, poly-epoxy succinic acid, ROHM, HPMA, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, propenoate/styrene sulfonic acid multipolymer, toxilic acid (acid anhydride)/allyl sulphonic acid multipolymer, vinylformic acid/allyl sulphonic acid multipolymer, vinylformic acid/vinyl sulfonic acid multipolymer, vinylformic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer and vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.Wherein said propenoate is preferably from vinylformic acid C
1-8Ester is more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate.
4. according to each described anti-incrustation corrosion inhibitor of claim 1-3, it is characterized in that said anti-incrustation corrosion inhibitor also contains heterogeneous ring compound as copper material corrosion inhibitor, described copper material corrosion inhibitor is preferably from mercaptobenzothiazole and benzotriazole.
5. according to each described anti-incrustation corrosion inhibitor of claim 1-4, it is characterized in that said anti-incrustation corrosion inhibitor also contains zinc salt.
6. according to each described anti-incrustation corrosion inhibitor of claim 5, it is characterized in that said zinc salt is selected from zinc sulfate and zinc chloride.
7. according to each described anti-incrustation corrosion inhibitor of claim 1-6, it is characterized in that with respect to the effective concentration of pending each component of aqueous solution total amount being: borate is (with B
4O
7 2-Meter) be 20-100mg/L, preferred 40-60mg/L; The concentration that contains carboxylic acid group's without phosphorus polymkeric substance is 2-20mg/L.
8. anti-incrustation corrosion inhibitor according to claim 4 is characterized in that the effective concentration with respect to pending aqueous solution total amount copper material corrosion inhibitor is 0.5-1.5mg/L.
9. anti-incrustation corrosion inhibitor according to claim 5 is characterized in that effective concentration with respect to pending aqueous solution total amount zinc salt is with Zn
2+Count 0.5-3.0mg/L.
10. the application of each described anti-incrustation corrosion inhibitor of claim 1-9 is characterized in that each described anti-incrustation corrosion inhibitor of claim 1-9 is applicable to the recirculated cooling water processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105124464A CN102452721A (en) | 2010-10-20 | 2010-10-20 | Phosphorus-free composite scale-inhibiting corrosion-retarding agent and application thereof in water treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105124464A CN102452721A (en) | 2010-10-20 | 2010-10-20 | Phosphorus-free composite scale-inhibiting corrosion-retarding agent and application thereof in water treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102452721A true CN102452721A (en) | 2012-05-16 |
Family
ID=46036464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010105124464A Pending CN102452721A (en) | 2010-10-20 | 2010-10-20 | Phosphorus-free composite scale-inhibiting corrosion-retarding agent and application thereof in water treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102452721A (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102774969A (en) * | 2012-07-24 | 2012-11-14 | 浙江浙能能源技术有限公司 | Biodegradable non-phosphorous anti-scale corrosion inhibitor and preparation method thereof |
| CN103523936A (en) * | 2013-11-01 | 2014-01-22 | 中国海洋石油总公司 | Non-phosphorus corrosion and scale inhibitor for low-hardness water system industrial recycling cooling water |
| CN103803716A (en) * | 2012-11-09 | 2014-05-21 | 中国石油化工股份有限公司 | Method for recycling reclaimed water in circulating cooling water system |
| CN106242085A (en) * | 2016-08-25 | 2016-12-21 | 山东天庆科技发展有限公司 | A kind of circularly-cooling sea water non-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN106809963A (en) * | 2017-03-06 | 2017-06-09 | 王仲贤 | It is without phosphorus without sodium water-treating agent of boiler |
| CN106830376A (en) * | 2017-03-06 | 2017-06-13 | 王仲贤 | Without phosphorus low sodium water-treating agent of boiler |
| CN107032509A (en) * | 2017-03-14 | 2017-08-11 | 成都云图控股股份有限公司 | A kind of terpolymer concentration slow-release scale inhibitor and preparation method thereof |
| CN107055821A (en) * | 2017-06-01 | 2017-08-18 | 北京市龙源科创石油技术有限公司 | Recirculated cooling water non-phosphorus scale and corrosion inhibitor and its application method |
| CN111003823A (en) * | 2019-12-30 | 2020-04-14 | 山东天庆科技发展有限公司 | Novel efficient non-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN111573858A (en) * | 2020-04-24 | 2020-08-25 | 包头钢铁（集团）有限责任公司 | Corrosion inhibitor for treated coking phenol-cyanogen wastewater |
| CN112499777A (en) * | 2020-11-25 | 2021-03-16 | 山东天庆科技发展有限公司 | High-efficiency low-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN115140849A (en) * | 2022-06-22 | 2022-10-04 | 北京师范大学 | Linear release type long-acting phosphorus-free scale inhibitor |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248438A (en) * | 1992-01-28 | 1993-09-28 | Betz Laboratories, Inc. | Methods of controlling scale formation in aqueous systems |
| CN1621362A (en) * | 2003-11-26 | 2005-06-01 | 北京燕化兴业技术开发公司 | Non-phosphorus compound scale and corrosion inhibitor for treatment of circulating cooling water |
| CN1785853A (en) * | 2004-12-10 | 2006-06-14 | 中国石化北京燕化石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application in water treatment |
| CN1796307A (en) * | 2004-12-30 | 2006-07-05 | 中国石化北京燕化石油化工股份有限公司 | Method for treating circulating cooling water |
| CN101066811A (en) * | 2007-06-15 | 2007-11-07 | 武汉金坡化工科技有限公司 | No-phosphate corrosion and scale inhibitor and its application |
-
2010
- 2010-10-20 CN CN2010105124464A patent/CN102452721A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248438A (en) * | 1992-01-28 | 1993-09-28 | Betz Laboratories, Inc. | Methods of controlling scale formation in aqueous systems |
| CN1621362A (en) * | 2003-11-26 | 2005-06-01 | 北京燕化兴业技术开发公司 | Non-phosphorus compound scale and corrosion inhibitor for treatment of circulating cooling water |
| CN1785853A (en) * | 2004-12-10 | 2006-06-14 | 中国石化北京燕化石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application in water treatment |
| CN1796307A (en) * | 2004-12-30 | 2006-07-05 | 中国石化北京燕化石油化工股份有限公司 | Method for treating circulating cooling water |
| CN101066811A (en) * | 2007-06-15 | 2007-11-07 | 武汉金坡化工科技有限公司 | No-phosphate corrosion and scale inhibitor and its application |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102774969A (en) * | 2012-07-24 | 2012-11-14 | 浙江浙能能源技术有限公司 | Biodegradable non-phosphorous anti-scale corrosion inhibitor and preparation method thereof |
| CN103803716A (en) * | 2012-11-09 | 2014-05-21 | 中国石油化工股份有限公司 | Method for recycling reclaimed water in circulating cooling water system |
| CN103803716B (en) * | 2012-11-09 | 2015-10-21 | 中国石油化工股份有限公司 | A kind of Treated sewage reusing is in the method for recirculating cooling water system |
| CN103523936A (en) * | 2013-11-01 | 2014-01-22 | 中国海洋石油总公司 | Non-phosphorus corrosion and scale inhibitor for low-hardness water system industrial recycling cooling water |
| CN103523936B (en) * | 2013-11-01 | 2014-09-17 | 中国海洋石油总公司 | Non-phosphorus corrosion and scale inhibitor for low-hardness water system industrial recycling cooling water |
| CN106242085A (en) * | 2016-08-25 | 2016-12-21 | 山东天庆科技发展有限公司 | A kind of circularly-cooling sea water non-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN106809963A (en) * | 2017-03-06 | 2017-06-09 | 王仲贤 | It is without phosphorus without sodium water-treating agent of boiler |
| CN106830376A (en) * | 2017-03-06 | 2017-06-13 | 王仲贤 | Without phosphorus low sodium water-treating agent of boiler |
| CN107032509A (en) * | 2017-03-14 | 2017-08-11 | 成都云图控股股份有限公司 | A kind of terpolymer concentration slow-release scale inhibitor and preparation method thereof |
| CN107055821A (en) * | 2017-06-01 | 2017-08-18 | 北京市龙源科创石油技术有限公司 | Recirculated cooling water non-phosphorus scale and corrosion inhibitor and its application method |
| CN111003823A (en) * | 2019-12-30 | 2020-04-14 | 山东天庆科技发展有限公司 | Novel efficient non-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN111573858A (en) * | 2020-04-24 | 2020-08-25 | 包头钢铁（集团）有限责任公司 | Corrosion inhibitor for treated coking phenol-cyanogen wastewater |
| CN112499777A (en) * | 2020-11-25 | 2021-03-16 | 山东天庆科技发展有限公司 | High-efficiency low-phosphorus scale and corrosion inhibitor and preparation method thereof |
| CN115140849A (en) * | 2022-06-22 | 2022-10-04 | 北京师范大学 | Linear release type long-acting phosphorus-free scale inhibitor |
| CN115140849B (en) * | 2022-06-22 | 2023-10-13 | 北京师范大学 | Linear release type long-acting phosphorus-free scale inhibitor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102452721A (en) | Phosphorus-free composite scale-inhibiting corrosion-retarding agent and application thereof in water treatment | |
| CN102730847B (en) | Non-phosphorus composite anti- incrustation corrosion inhibiter and its application in water treatment | |
| CN102452724B (en) | Composite corrosion and scale inhibitor and its application in water treatment | |
| CN102730848B (en) | Composite anti-incrustation corrosion inhibiter and its application in water treatment | |
| CN102452725A (en) | Composite scale and corrosion inhibitor and its application | |
| CN100379690C (en) | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application in water treatment | |
| CN100434376C (en) | Low phosphate green composite corrosion and scale inhibitor for treating circular cooling water and its usage | |
| CN104556420B (en) | The corrosion-proofing and antisludging method of without phosphorus composite slow-corrosion scale resistor and preparation method thereof and recirculated cooling water | |
| CN104556428B (en) | A kind of corrosion-mitigation scale-inhibition compositions and application thereof | |
| CN104891684B (en) | Without phosphorus composite slow-corrosion scale resistor for bitter recirculated water and preparation method thereof | |
| CN101967024B (en) | Phosphorus-free corrosion and scale inhibitor | |
| CN105366823B (en) | Phosphate-free corrosion inhibition antisludging agent composition and phosphate-free corrosion inhibition antisludging agent and its application and application of the copolymer in inhibition | |
| CN103570153B (en) | A kind of Treated sewage reusing is in the method for recirculating cooling water system | |
| CN102674570A (en) | Composite low-phosphorus corrosion and scale inhibitor and application thereof | |
| CN102452722B (en) | Non-phosphorus composite anti-scale corrosion inhibitor and application thereof in water treatment | |
| CN103771596A (en) | Phosphorus-free composite scale and corrosion inhibitor, applications thereof, and processing method for circulating water | |
| CN104261575A (en) | High-COD special non-phosphorus corrosion and scale inhibitor and preparation method thereof | |
| CN103449618B (en) | Non-phosphorus composite corrosion and scale inhibitor suitable for industrial circulating cooling water | |
| CN107777789A (en) | Low-phosphor efficient anti-incrustation corrosion inhibitor for circulating water treatment and preparation method thereof | |
| CN105036367A (en) | Phosphorus-free corrosion and scale inhibitor with sterilizing effect and preparation method and application thereof | |
| CN103771598A (en) | Phosphorus-free composite scale and corrosion inhibitor, applications thereof, and processing method for circulating water | |
| CN103771597A (en) | Phosphorus-free composite scale and corrosion inhibitor, applications thereof, and processing method for circulating water | |
| CN106242085A (en) | A kind of circularly-cooling sea water non-phosphorus scale and corrosion inhibitor and preparation method thereof | |
| CN106430653B (en) | A kind of composite slow-corrosion scale resistor and its application | |
| CN109748400B (en) | Phosphorus-free composite corrosion and scale inhibitor, application thereof and treatment method of circulating cooling water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120516 |