CN1199885C - Composite scale resistant corrosion inhibitor and its use in reusing ammonia-nitrogen containing waste water in circulating cooling water - Google Patents
Composite scale resistant corrosion inhibitor and its use in reusing ammonia-nitrogen containing waste water in circulating cooling water Download PDFInfo
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- CN1199885C CN1199885C CN 02145917 CN02145917A CN1199885C CN 1199885 C CN1199885 C CN 1199885C CN 02145917 CN02145917 CN 02145917 CN 02145917 A CN02145917 A CN 02145917A CN 1199885 C CN1199885 C CN 1199885C
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Abstract
The present invention relates to a composite scale resistant corrosion inhibiting agent and an application thereof in reusing ammonia nitrogen containing waste water as circulating cooling water. The present invention is characterized in that when nitrogen containing waste water is reused as circulating cooling water, acid is added to control the pH value in water within the range of 6.5 to 8.5, and a method of the combined action of the scale resistant corrosion inhibiting agent and a sterilizing agent is adopted to control the problems of corrosion, scale formation and bacterium growth in the process of reusing waste water, wherein the composite scale resistant corrosion inhibiting agent comprises phosphate, polyphosphate, organic phosphonic acid, copolymers with carboxylic acid groups, zinc salt, etc. The composite scale resistant corrosion inhibiting agent and the method are suitable for reusing ammonia nitrogen containing waste water as circulating cooling water.
Description
Technical field
The present invention relates to a kind of composite scale-inhibiting corrosion inhibitor and be back to application in the recirculated cooling water containing ammonia-nitrogen sewage, more particularly, the present invention relates to a kind of composite scale-inhibiting corrosion inhibitor and after secondary biochemical treatment, containing ammonia-nitrogen sewage as the application in the recirculating cooling water system moisturizing.
Background technology
Usually the used crude oil of refinery contains nitrogenous compound, in crude oil purified process, can produce the streams that contains ammonia nitrogen, though this streams has reclaimed most of useful ammonia through technology for refining ammonia, but still some ammonia has entered sink drainage inevitably and formed the sewage that contains ammonia nitrogen.At present, this part sewage that contains ammonia nitrogen generally is to send sewage work to carry out discharging after the secondary biochemical treatment, also fails to reclaim and be back to recirculated cooling water, and this is current water scarcity, is a kind of great waste.If can further handle and be back to recirculated cooling water to the sewage that contains ammonia nitrogen will be an effective way that solves enterprise's shortage of water resources.To solve problems such as inhibition, scale inhibition and microorganism and foundry loam control in the reuse process.
Chinese patent application CN1258649A discloses a kind of Recompounded multielement antisludging corrosion inhibitor, this anti-incrustation corrosion inhibitor mainly includes machine phosphonic acid, contains sulfonic group multipolymer and zinc salt, can be used for the processing to the petrochemical wastewater of process secondary biochemical treatment, its shortcoming is that this Recompounded multielement antisludging corrosion inhibitor can only be used for the circulating water treatment of the petrochemical wastewater of ammonia-nitrogen content few (0.14-1.88mg/L) as moisturizing.
Chinese patent application CN1067230A discloses nitrogen fertilizer plant's ammonia-containing water and has contained ammonia circulating water treatment technology, and the anti-incrustation corrosion inhibitor of this technology is for the series of phosphorated humic acids not HAS water quality stabilizer, and is all different with source of sewage of the present invention and anti-incrustation corrosion inhibitor.
Summary of the invention
The object of the present invention is to provide a kind of composite scale-inhibiting corrosion inhibitor, this composite scale-inhibiting corrosion inhibitor is particularly suitable for containing the processing that ammonia-nitrogen sewage is back to recirculated cooling water.
Another object of the present invention is to provide a kind of method that contains the reusing sewage of ammonia nitrogen in recirculated cooling water, and promptly method of the present invention is applicable to that the ammonia-nitrogen sewage that contains after secondary biochemical treatment handles as the recirculating cooling water system of moisturizing.
For achieving the above object, the invention provides a kind of composite scale-inhibiting corrosion inhibitor that ammonia-nitrogen sewage is back to circulating water treatment that is suitable for containing, comprising phosphoric acid salt, poly-phosphate, organic phospho acid, contain carboxylic acid-based copolymer and zinc salt.
Phosphoric acid salt of the present invention is sodium or the sylvite that contains phosphate radical, hydrogen phosphate or dihydrogen phosphate.
Poly-phosphate of the present invention is Sodium hexametaphosphate 99 or tripoly phosphate sodium STPP.
Organic phospho acid of the present invention is at least a 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), the 2-phosphonate group-1 of being selected from, 2,4-butane tricarboxylate (PBTCA), hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA), ethylene diamine tetra methylene phosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic acids.Wherein amino acid two methene phosphonic acids add phosphorus trichloride (PCl afterwards again by amino acid (as glycine, L-glutamic acid) and formaldehyde (HCHO) solution is simultaneously soluble in water
3) reaction obtain; Perhaps, add the concentrated hydrochloric acid reaction again and obtain by amino acid (as glycine, L-glutamic acid), phosphorous acid and formaldehyde solution is simultaneously soluble in water.
The carboxylic acid-based copolymer of containing of the present invention is selected from vinylformic acid (AA)/Propylene glycol monoacrylate (HPA) multipolymer, vinylformic acid/Propylene glycol monoacrylate (HPA)/acrylate copolymer, toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/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 (AMPS) multipolymer, acrylic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, acrylic acid/esters/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.Wherein said acrylate is preferably from vinylformic acid C
1-8Ester is more preferably from methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate (HPA).
Zinc salt of the present invention is selected from zinc sulfate, zinc chloride and zinc carbonate, preferably sulfuric acid zinc and zinc chloride.
During as use copper material equipment in the circulation cooling water system, composite scale-inhibiting corrosion inhibitor of the present invention also contains heterogeneous ring compound as copper material corrosion inhibitor, and preferred mercaptobenzothiazole and benzotriazole (BTA) are as copper material corrosion inhibitor.
Phosphoric acid salt of the present invention is 2-7mg/L with respect to the effective concentration of pending aqueous solution total amount
Poly-phosphate of the present invention is 2-15mg/L with respect to the effective concentration of pending aqueous solution total amount.
Organic phospho acid of the present invention is 2-15mg/L with respect to the effective concentration of pending aqueous solution total amount.
The carboxylic acid-based copolymer of containing of the present invention is 8-15mg/L with respect to the effective concentration of pending aqueous solution total amount.
Zinc salt of the present invention is 1.5-5mg/L in zine ion with respect to the effective concentration of pending aqueous solution total amount.
Copper material corrosion inhibitor of the present invention is 0.5-1.5mg/L with respect to the effective concentration of pending aqueous solution total amount.
Prepare composite scale-inhibiting corrosion inhibitor of the present invention, need be made into two kinds of solution, but the reinforced order of component is unimportant in every kind of solution.Poly-phosphate, phosphoric acid salt and water are made into a kind of liquid medicine by predetermined mixed, are called A liquid; And organic phospho acid, contain carboxylic acid-based copolymer, zinc salt and copper material corrosion inhibitor (if any) and water and be made into another kind of liquid medicine by predetermined mixed, be called B liquid, in the preparation process of B liquid, also can add a spot of acid (as dilute sulphuric acid, dense or dilute hydrochloric acid etc.), to promote the dissolving of zinc salt etc., needing to obtain the uniform solution of concentration as early as possible, so just make required composite scale-inhibiting corrosion inhibitor.Two kinds of liquid medicines added simultaneously by equal proportion when composite scale-inhibiting corrosion inhibitor added in recirculated water.
The present invention also provides a kind of method that ammonia-nitrogen sewage is back to recirculated cooling water that contains, comprise that the reusing sewage that will contain ammonia nitrogen when recirculated cooling water, adds composite scale-inhibiting corrosion inhibitor of the present invention, and adding acid control pH value is 6.5～8.5, be preferably 7.3～8.0, add sterilant afterwards again.
Sewage of the present invention is the ammonia-nitrogen sewage that contains from refinery, and its ammonia nitrogen concentration is 2-50mg/L.
Acid of the present invention is sulfuric acid, nitric acid etc., and its add-on is so that the pH value is adjusted to 6.5～8.5, is preferably 7.3～8.0 to be as the criterion.
The disclosed sterilant of prior art all can be used for the present invention, is the single or compound disinfectant of oxidized form or non-oxide type as sterilant; Oxidative bactericide is selected from chlorine, (Puritabs, trichloroisocyanuric acid (strong chlorine oil), dioxide peroxide, clorox, organic bromine are (as 2 for Surchlor GR 60,2-two bromo-3-nitrilo propionic acid amides, bromine Chlorodimethyl glycolylurea, dibromo dimethyl hydantoin etc.), active bromine (be generally in Sodium Bromide and the tensio-active agent and add auxiliary agent), be 5～200mg/L, preferred 5-100mg/L with respect to pending its effective concentration of aqueous solution total amount; Non-oxidative bactericide is selected from isothiazolinone, quaternary ammonium salt, quaternary phosphonium salt, glutaraldehyde, dithiocyano-methane, chlorophenols, is 5～300mg/L, preferred 30-150mg/L, more preferably 50-100mg/L with respect to pending its effective concentration of aqueous solution total amount.
Quaternary ammonium salt sterilant of the present invention is dodecyl benzyl dimethyl ammonium chloride (" 1227 "), dodecyl dimethyl benzyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride (" 1427 "), dialkyl quaternary ammonium salt or polyquaternium, is 10～150mg/L with respect to pending its effective concentration of aqueous solution total amount.
Compound disinfectant of the present invention is selected from quaternary ammonium salt and isothiazolinone, quaternary ammonium salt and glutaraldehyde, quaternary ammonium salt and dithiocyano-methane, quaternary ammonium salt and chlorophenols, is 20～300mg/L with respect to pending its effective concentration of aqueous solution total amount.
Sterilant among the present invention can add in the usual way, as adding continuously or impact adds.To the recirculated water field of chlorination facility is arranged, preferably adopt the way of chlorination, adding frequency is to add 1-4 time every day, be preferably 2-4 time, and chlorine residue is 0.5-1.0mg/L in the maintenance water, cooperates simultaneously to add non-oxidative bactericide, adding frequency decides on the bacterial number in temperature and the recirculated water, during summer, add frequency and be generally and added once in 7-15 days, added once for 15-30 days winter; To there not being the recirculated water field of chlorination facility, oxidative bactericide preferably adds continuously, cooperates simultaneously to add non-oxidative bactericide, adding frequency decides on the bacterial number in temperature and the recirculated water, during summer, add frequency and be generally and added once in 7-15 days, added once for 15-30 days winter.
The present invention adopts and adds the composite scale-inhibiting corrosion inhibitor that contains phosphoric acid salt, poly-phosphate, organic phospho acid, contains carboxylic acid-based copolymer and zinc salt, adds acid control pH value 6.5～8.5 simultaneously, is the sewage of 2～50mg/L to handle the ammonia nitrogen concentration scope.Containing ammonia-nitrogen sewage, to be back to a recirculated cooling water important difficult problem to be solved after biochemical treatment be exactly etching problem, contain the higher sewage of ammonia nitrogen amount especially, the present invention controls pH value in the water by adding acid, and controls burn into fouling and the bacterial growth problem that contains in the ammonia-nitrogen sewage reuse process with composite scale-inhibiting corrosion inhibitor, the symphyogenetic method of sterilant.
Method of the present invention is applicable to that the recirculated cooling water when containing ammonia-nitrogen sewage as the make up water of recirculating cooling water system handles.
Embodiment
The following examples will help to illustrate the present invention, but not limit to its scope.
" tosca method " and " rotary hanging plate weight-loss method " carries out static-state scale inhibition test and rotary hanging plate corrosion test in " water coolant analysis and the test method " that the following examples 1～6 are all write according to production department of China PetroChemical Corporation and development division (1993, general petrochemical works, Anqing information center publishes).The former water of test concentrates 3 times in " tosca method "; Test temperature is 40 ℃ in " rotary hanging plate weight-loss method ", and the test piece rotating speed is 120 rev/mins (rpm), and test period is 72h, and the lacing film material is a carbon steel, and test water is for concentrating 2 times the former water of test, and to add acid control pH value be 7.5～8.0.The former water of the test of following embodiment for from refinery contain ammonia-nitrogen sewage according to a conventional method through secondary biochemical treatment (as activated sludge process), and remove suspended substance (as with the filtration of high-efficiency fiber beam filter device) through flocculating settling [as can at room temperature polymerize aluminum chloride (concentration is 40mg/L) and cationic polyacrylamide (concentration is 2mg/L) successively being added wherein as flocculation agent, sedimentation is 0.5 hour again], secondary filter after sewage.The test raw water quality sees Table 1.
Table 1 test water quality
| Ca 2+ | Total alkalinity | Total hardness | Cl - | SO 4 2- | PH | Specific conductivity | Total molten solid | Ammonia nitrogen | COD Cr | |
| Maximum value | 200 | 380 | 280 | 140 | 200 | 8.4 | 1639 | 756 | 50 | 80 |
| Minimum value | 130 | 97 | 100 | 85 | 30 | 7.4 | 1120 | 576 | 2 | 23 |
Annotate: 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.
The COD of water quality
CrMeasuring method is classical chromium method, " water coolant analysis and the test method " that remaining is write with reference to production department of China PetroChemical Corporation and development division.
Embodiment 1
Process for preparation: preparation composite scale-inhibiting corrosion inhibitor A liquid, each 80g of B liquid
Take by weighing the 10.4g sodium phosphate and be dissolved in the 67.6g water, stirring and dissolving adds the 2g Sodium hexametaphosphate 99 then, shakes up dissolving, promptly obtains the 80g A liquid of required preparation.
Taking by weighing the 40g solid content and be 30% AA/AMPS/HPA, to contain carboxylic acid group and sulfonic group terpolymer (weight ratio is AA/AMPS/HPA=70/15/15), active ingredient be 50% PBTCA 6g, be dissolved in the 16.5g water, 10 in the sulfuric acid that adds 17.5g Zinc vitriol and 1: 3 at last, it is fully dissolved, shake up, promptly obtain the 80g B liquid of required preparation.
When adding in test water by the drug concentration of 80mg/L simultaneously with the A liquid for preparing, B liquid, sodium phosphate is (with PO in the water
4 3-Meter), Sodium hexametaphosphate 99, contain carboxylic acid group and sulfonic group terpolymer, PBTCA, Zn
2+Effective concentration be respectively 6mg/L, 2mg/L, 12mg/L, 3mg/L, 4mg/L.
The test raw water quality is: ammonia nitrogen 40mg/L, Ca
2+140mg/L, total alkalinity 250mg/L, Cl
-86.5mg/L, SO
4 2-150mg/L, pH8.4, COD
Cr55mg/L.
Embodiment 2
Process for preparation: preparation composite scale-inhibiting corrosion inhibitor A liquid, each 80g of B liquid
Take by weighing the 3g Sodium phosphate dibasic and be dissolved in the 71g water, stirring and dissolving adds the 6g Sodium hexametaphosphate 99 then, shakes up dissolving, promptly obtains the 80g A liquid of required preparation.
Taking by weighing the 27g solid content and be 30% AA/MA/HPA, to contain carboxylic acid group's terpolymer (weight ratio is AA/MA/HPA=60/8/32), active ingredient be 50% PBTCA 8g, be dissolved in the 27.5g water, 10 in the sulfuric acid that adds 17.5g Zinc vitriol and 1: 3 at last, it is fully dissolved, shake up, promptly obtain the 80g B liquid of required preparation.
When adding in test water by the drug concentration of 80mg/L simultaneously with the A liquid for preparing, B liquid, Sodium phosphate dibasic is (with PO in the water
4 3-Meter), Sodium hexametaphosphate 99, contain carboxylic acid group's terpolymer, PBTCA, Zn
2+Effective concentration be respectively 2mg/L, 6mg/L, 8.1mg/L, 4mg/L, 4mg/L.
The test raw water quality is: ammonia nitrogen 28mg/L, Ca
2+155mg/L, total alkalinity 183mg/L, Cl
-105.6mg/L, SO
4 2-124mg/L, pH8.0, COD
Cr43mg/L.
Embodiment 3
Process for preparation: preparation composite scale-inhibiting corrosion inhibitor A liquid, each 80g of B liquid
Take by weighing the 3.8g SODIUM PHOSPHATE, MONOBASIC and be dissolved in the 72.2g water, stirring and dissolving adds the 4g Sodium hexametaphosphate 99 then, shakes up dissolving, promptly obtains the 80g A liquid of required preparation.
Taking by weighing the 30g solid content and be 30% AA/AMPS/HPA, to contain carboxylic acid group and sulfonic group terpolymer (weight ratio is AA/AMPS/HPA=60/20/20), active ingredient be 50% HEDP 8g, be dissolved in the 33.7g water, add 5 of 8.3g Zinc Chloride Anhydrous and concentrated hydrochloric acids at last, it is fully dissolved, shake up, promptly obtain the 80g B liquid of required preparation.
When adding in containing test water by the drug concentration of 80mg/L simultaneously with the A liquid for preparing, B liquid, SODIUM PHOSPHATE, MONOBASIC is (with PO in the water
4 3-Meter), Sodium hexametaphosphate 99, contain carboxylic acid group and sulfonic group terpolymer, HEDP, Zn
2+Effective concentration be respectively 3mg/L, 4mg/L, 9mg/L, 4mg/L, 4mg/L.
The test raw water quality is: ammonia nitrogen 10mg/L, Ca
2+194mg/L, total alkalinity 135mg/L, Cl
-125.3mg/L, SO
4 2-139mg/L, pH8.1, COD
Cr33mg/L.
Embodiment 4
Process for preparation: preparation composite scale-inhibiting corrosion inhibitor A liquid, each 80g of B liquid
Take by weighing the 2.6g SODIUM PHOSPHATE, MONOBASIC and be dissolved in the 68.1g water, stirring and dissolving adds the 10g Sodium hexametaphosphate 99 then, shakes up dissolving, promptly obtains the 80g A liquid of required preparation.
Taking by weighing the 30g solid content and be 30% AA/MA/HPA contains carboxylic acid group's terpolymer (weight ratio is AA/MA/HPA=60/8/32), copper material corrosion inhibitor BTA 1g, active ingredient and is 50% PBTCA 16g, is dissolved in the 26.75g water, add 5 of 6.25g Zinc Chloride Anhydrous and concentrated hydrochloric acids at last, it is fully dissolved, shake up, promptly obtain the 80g B liquid of required preparation.
When adding in containing test water by the drug concentration of 80mg/L simultaneously with the A liquid for preparing, B liquid, SODIUM PHOSPHATE, MONOBASIC is (with PO in the water
4 3-Meter), Sodium hexametaphosphate 99, contain carboxylic acid group's terpolymer, copper material corrosion inhibitor, PBTCA, Zn
2+Effective concentration be respectively 2mg/L, 10mg/L, 9mg/L, 1mg/L, 8mg/L, 3mg/L.
The test raw water quality is seen embodiment 1.
Embodiment 5
Process for preparation: preparation composite scale-inhibiting corrosion inhibitor A liquid, each 80g of B liquid
Take by weighing the 6.9g sodium phosphate and be dissolved in the 69.1g water, stirring and dissolving adds the 4g tripoly phosphate sodium STPP then, shakes up dissolving, promptly obtains the 80g A liquid of required preparation.
Taking by weighing the 40g solid content and be 30% AA/AMPS, to contain carboxylic acid group and sulfonic group copolymer (weight ratio is AA/AMPS=70/30), active ingredient be 50% HEDP 26g, 10 in the sulfuric acid that adds 14g Zinc vitriol and 1: 3 at last, it is fully dissolved, shake up, promptly obtain the 80g B liquid of required preparation.
When adding in test water by the drug concentration of 80mg/L simultaneously with the A liquid for preparing, B liquid, sodium phosphate is (with PO in the water
4 3-Meter), tripoly phosphate sodium STPP, contain carboxylic acid group and sulfonic group copolymer, HEDP, Zn
2+Effective concentration be respectively 4mg/L, 4mg/L, 12mg/L, 13mg/L, 3.2mg/L.
The test raw water quality is seen embodiment 2.
Embodiment 6
Process for preparation: preparation composite scale-inhibiting corrosion inhibitor A liquid, each 80g of B liquid
Take by weighing the 3g Sodium phosphate dibasic and be dissolved in the 65g water, stirring and dissolving adds the 12g Sodium hexametaphosphate 99 then, shakes up dissolving, promptly obtains the 80g A liquid of required preparation.
Taking by weighing the 40g solid content and be 30% AA/HPA, to contain carboxylic acid group's copolymer (weight ratio is AA/HPA=80/20), active ingredient be 50% PBTCA 24g, be dissolved in the 11.8g water, add 5 of 4.2g Zinc Chloride Anhydrous and concentrated hydrochloric acids at last, it is fully dissolved, shake up, promptly obtain the 80g B liquid of required preparation.
When adding in test water by the drug concentration of 80mg/L simultaneously with the A liquid for preparing, B liquid, Sodium phosphate dibasic is (with PO in the water
4 3-Meter), Sodium hexametaphosphate 99, contain carboxylic acid group's copolymer, PBTCA, Zn
2+Effective concentration be respectively 2mg/L, 12mg/L, 12mg/L, 12mg/L, 2mg/L.
The test raw water quality is seen embodiment 3.
Carry out static-state scale inhibition test and rotary hanging plate corrosion test by the above-mentioned concentration that adds, resistance calcium carbonate scale rate and corrosion speed see Table 2.
The scale inhibitor effect of table 2 corrosion inhibiting and descaling agent
| Embodiment | Resistance calcium carbonate scale rate (%) | Corrosion of carbon steel speed (mm/a) | Copper material corrosion speed (mm/a) |
| Embodiment 1 | 98.5 | 0.025 | |
| Embodiment 2 | 95.1 | 0.036 | |
| Embodiment 3 | 98.4 | 0.033 |
| Embodiment 4 | 98.1 | 0.030 | 0.0027 |
| Embodiment 5 | 99.0 | 0.028 | |
| Embodiment 6 | 97.8 | 0.020 |
Embodiment 7
For simulated field, carried out dynamic analog test.The dynamic analog test method is undertaken by the chemical industry standard HG/T2160-91 of the People's Republic of China (PRC), and controlled variable is as follows.
Cycles of concentration: 4.0 ± 0.2 flow velocitys: 1.0m/s
Medicament: (concentration is with PO for SODIUM PHOSPHATE, MONOBASIC
4 3-Meter)+and Sodium hexametaphosphate 99+PBTCA+AA/MA/HPA multipolymer (weight ratio is 61/7/32)+zinc salt, effective concentration is respectively 2,6,4,9,3mg/l.
Total phosphorus (PO
4 3-Meter): B tower 8.0 ± 0.2mg/l
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
The test raw water quality sees Table 1
1, operation process: adding sulfuric acid in the sewage is 7.5～7.8 with control pH value.
Sterilant adds kind, concentration and bacterial control and the results are shown in Table 3.
Number of bacteria in the table 3 dynamic simulation process
| Time | Heterotrophic bacterium (individual/ml) | Iron bacteria (individual/ml) | Sulphate reducing bacteria (individual/ml) | Remarks |
| The 1st day | ＞10 7 | 4.5 * 10 2 | 1.4 * 10 2 | Adding of germicide not |
| The 2nd day | 3.0 * 10 3 | Do not measure | 1 | Add the secondary Babysafe every day, concentration is 50mg/l. |
| The 8th day | 2.2 * 10 5 | 25 | 9 | |
| The 14th day | ＜10 3 | Do not measure | Measure | Add Babysafe every day three times, concentration is 100mg/l. |
| The 15th day | ＜10 3 | Do not measure | Do not measure |
Data show in the table, add twice or three Babysafes the growth of three kinds of bacteriums of energy better controlled every day.
Dynamic analog test test piece and test tube the results are shown in Table 4.
Test piece of table 4 dynamic analog test and test tube result
| Test conditions | The test tube result | ||
| Drug concentration (mg/l) | Working time | Erosion rate (mm/a) | Adhere to speed (mcm) |
| 160 | 15 days | 0.0524 | 5.7 |
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 50050-95 " 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 " good " level between 0.028-0.056mm/a in " the water coolant analysis and the test method " of production department of China PetroChemical Corporation and development division establishment, is " can allow " level at 0.056-0.070mm/a; Adhesion speed is " fine " level at 0-6mcm, is " good " level at 6-15mcm, is " can allow " level at 15-20mcm.
The erosion rate that this shows test tube is 0.0524mm/a, reaches China Petrochemical Industry's " good level " standard, adheres to speed and reaches " fine level " standard.
Comparative Examples 1-3
Method by Chinese patent application CN1258649A, be formulated as follows the component shown in the table and carry out static-state scale inhibition test and rotary hanging plate corrosion test with the scale inhibitor solution that adds concentration, experimental technique is identical with embodiment 2 with experiment water quality, and resistance calcium carbonate scale rate and erosion rate see Table 5.
The scale inhibition of table 5 nitric wastewater and inhibition experimental result
| Comparative Examples | The composition of corrosion inhibiting and descaling agent | Proportioning (in effective concentration) | Corrosion of carbon steel speed (mm/a) | Resistance calcium carbonate scale rate (%) |
| 1 | HEDP+ATMP+Zn 2+Contain the sulfonic group multipolymer | 6∶3∶3∶6 | 1.421 | 99.1 |
| 2 | HEDP+ATMP+Zn 2++ contain the sulfonic group multipolymer | 4∶5∶2∶4 | 1.720 | 99.2 |
| 3 | HEDP+PBTCA+Zn 2++ contain the sulfonic group multipolymer | 3∶6∶4∶6 | 0.115 | 99.4 |
Annotate: containing the sulfonic group multipolymer is AA/AMPS/HPA multipolymer (each monomeric weight ratio is that 70/10/20,30 ℃ of intrinsic viscosity is 0.085dl/g)
By the data of the foregoing description and Comparative Examples as can be seen: it is strong to contain ammonia-nitrogen sewage corrodibility, when the anti-incrustation corrosion inhibitor of selecting Chinese patent application CN1258649A for use carries out the corrosion-mitigation scale-inhibition test, erosion rate is excessive, and the anti-incrustation corrosion inhibitor that CN1258649A is described not too is fit to contain ammonia-nitrogen sewage and is back to recirculated cooling water and handles; And carry out corrosion-mitigation scale-inhibition when test with composite scale-inhibiting corrosion inhibitor of the present invention, its scale-inhibiting properties and corrosion inhibition are all fine, illustrate that being suitable for containing ammonia-nitrogen sewage with composite scale-inhibiting corrosion inhibitor of the present invention is back to the processing that recirculated cooling water promptly is used as the make up water of recirculating cooling water system.
Claims (17)
1, a kind ofly is suitable for containing the composite scale-inhibiting corrosion inhibitor that ammonia-nitrogen sewage is back to circulating water treatment, comprising phosphoric acid salt, poly-phosphate, organic phospho acid, contain carboxylic acid-based copolymer and zinc salt.
2, anti-incrustation corrosion inhibitor according to claim 1 is characterized in that described phosphoric acid salt is sodium or the sylvite that contains phosphate radical, hydrogen phosphate or dihydrogen phosphate.
3, anti-incrustation corrosion inhibitor according to claim 1 is characterized in that described poly-phosphate is Sodium hexametaphosphate 99 or tripoly phosphate sodium STPP.
4, according to each described anti-incrustation corrosion inhibitor of claim 1-3, it is characterized in that described organic phospho acid is at least a 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, the 2-phosphonate group-1 of being selected from, 2,4-butane tricarboxylate, hydroxyethylidene diphosphonic acid guanidine-acetic acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to two phosphono and sulfonics, glycine two methene phosphonic acids, L-glutamic acid two methene phosphonic acids, thionamic acid two methene phosphonic acids, taurine two methene phosphonic acids.
5, according to each described anti-incrustation corrosion inhibitor of claim 1-3, it is characterized in that the described carboxylic acid-based copolymer of containing is selected from vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/methyl acrylate copolymer, toxilic acid/styrene sulfonic acid multipolymer, maleic anhydride/styrene sulfonic acid multipolymer, vinylformic acid/styrene sulfonic acid multipolymer, acrylate/styrene sulfonic acid multipolymer, toxilic acid/allyl sulphonic acid multipolymer, maleic 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, vinylformic acid/toxilic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer, vinylformic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2 '-acrylamido propane sulfonic acid multipolymer.
6,, it is characterized in that described zinc salt is selected from zinc sulfate, zinc chloride and zinc carbonate according to each described anti-incrustation corrosion inhibitor of claim 1-3.
7,, it is characterized in that also containing in the described composite scale-inhibiting corrosion inhibitor heterogeneous ring compound as copper material corrosion inhibitor according to each described anti-incrustation corrosion inhibitor of claim 1-3.
8, anti-incrustation corrosion inhibitor according to claim 7 is characterized in that described heterogeneous ring compound is mercaptobenzothiazole or benzotriazole.
9, according to each described anti-incrustation corrosion inhibitor of claim 1-3, it is characterized in that with respect to the effective concentration of pending each component of aqueous solution total amount being: phosphoric acid salt is 2-7mg/L, poly-phosphate is 2-15mg/L, the organic phospho acid total concn is 2-15mg/L, carboxylate-containing copolymer concentration 8-15mg/L, zinc salt is counted 1.5-5mg/L with zine ion.
10, anti-incrustation corrosion inhibitor according to claim 7 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.
11, a kind ofly contain the method that ammonia-nitrogen sewage is back to recirculated cooling water, comprise that the reusing sewage that will contain ammonia nitrogen is when recirculated cooling water, add each described composite scale-inhibiting corrosion inhibitor of claim 1-9, and to add acid control pH value be 6.5～8.5, add sterilant afterwards again.
12, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 11 is described, it is characterized in that adding acid control pH value is 7.3～8.0.
13, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 11 is described, it is characterized in that the ammonia nitrogen concentration scope is 2～50mg/L in the described sewage.
14, each describedly contains the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 11-13, it is characterized in that described acid is sulfuric acid or nitric acid, and its add-on is so that the pH value is adjusted in the described scope of claim 10 is as the criterion.
15, each describedly contains the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 11-13, it is characterized in that described sterilant is the single or compound disinfectant of oxidized form or non-oxide type; Oxidative bactericide is selected from chlorine, Surchlor GR 60, trichloroisocyanuric acid, clorox, dioxide peroxide, organic bromine, active bromine, is 5～200mg/L with respect to pending its effective concentration of aqueous solution total amount; Non-oxidative bactericide is selected from isothiazolinone, quaternary ammonium salt, quaternary phosphonium salt, glutaraldehyde, dithiocyano-methane, chlorophenols, is 5～300mg/L with respect to pending its effective concentration of aqueous solution total amount.
16, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 15 is described, it is characterized in that described quaternary ammonium salt sterilant is dodecyl benzyl dimethyl ammonium chloride, dodecyl dimethyl benzyl ammonium bromide, tetradecyl dimethyl benzyl ammonium chloride, dialkyl quaternary ammonium salt or polyquaternium, is 10～150mg/L with respect to pending its effective concentration of aqueous solution total amount.
17, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 15 is described, it is characterized in that described compound disinfectant is selected from quaternary ammonium salt and isothiazolinone, quaternary ammonium salt and glutaraldehyde, quaternary ammonium salt and dithiocyano-methane, quaternary ammonium salt and chlorophenols, is 20～300mg/L with respect to pending its effective concentration of aqueous solution total amount.
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| CN 02145917 CN1199885C (en) | 2002-10-23 | 2002-10-23 | Composite scale resistant corrosion inhibitor and its use in reusing ammonia-nitrogen containing waste water in circulating cooling water |
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