CN1417139A - Method for reusing ammonia nitrogen containing effluent as circular cooling water - Google Patents
Method for reusing ammonia nitrogen containing effluent as circular cooling water Download PDFInfo
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- CN1417139A CN1417139A CN 01134703 CN01134703A CN1417139A CN 1417139 A CN1417139 A CN 1417139A CN 01134703 CN01134703 CN 01134703 CN 01134703 A CN01134703 A CN 01134703A CN 1417139 A CN1417139 A CN 1417139A
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Abstract
The method of reusing ammonia nitrogen containing effluent as circular cooling water is characterized by the addition of alkali, bicarbonate, carbonate, hydrophosphate, dihydric phosphate or phosphate to increase the scaling factor of water and the cooperation with scale-inhibiting corrosion inhibitor and bactericide to control corrosion, scaling and bacterial growth in the reused effluent. The method of the present invention is suitable for reusing ammonia nitrogen containing effluent as circular cooling water.
Description
Technical field
The present invention relates to a kind of method that ammonia-nitrogen sewage is back to recirculated cooling water that contains, more particularly, the present invention relates to after secondary biochemical treatment, containing the circulating water treatment method of ammonia-nitrogen sewage as 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 multicomponent compound anti-scale 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 multicomponent compound anti-scale 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 the method for a kind of reusing sewage of high ammonia-nitrogen content in recirculated cooling water, promptly method of the present invention is applicable to that the high ammonia-nitrogen content sewage after secondary biochemical treatment handles as the recirculating cooling water system of moisturizing.
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, higher to ammonia-nitrogen content especially sewage, we find when experiment, also do not deposit hardly for concentrated 4 times even the calcium ion in the sewage of high ammonia-nitrogen content does not add water stabilizer, but corrosion is comparatively serious.Measure the basicity that concentrates in the sewage of back, find that basicity is lower, the fouling factor in the water is less.The present invention is by increasing the fouling factor in the water, for example improve the pH value or add the methods raising fouling factors such as supercarbonate, carbonate, hydrophosphate, dihydrogen phosphate or phosphoric acid salt, and control 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 by adding alkali.
The invention provides a kind of method that ammonia-nitrogen sewage is back to recirculated cooling water that contains, be characterized at the reusing sewage that contains ammonia nitrogen during in recirculated cooling water, successively add composite scale-inhibiting corrosion inhibitor and alkali, supercarbonate, carbonate, hydrophosphate, dihydrogen phosphate or phosphoric acid salt, add sterilant afterwards, wherein composite scale-inhibiting corrosion inhibitor comprises poly-phosphate, organic phospho acid, contains sulfonic group multipolymer and zinc salt.
Sewage of the present invention is the ammonia-nitrogen sewage that contains from refinery, and its ammonia nitrogen concentration is 20-120mg/L.
Alkali of the present invention is sodium hydroxide, potassium hydroxide, and its add-on is so that the pH value is adjusted to 7.6～9.5, is preferably 8.5～9.5 to be as the criterion.
Supercarbonate of the present invention is sodium bicarbonate or saleratus; Described carbonate is yellow soda ash or salt of wormwood; Described hydrophosphate is sodium hydrogen phosphate or potassium hydrogen phosphate; Described dihydrogen phosphate is SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate; Described phosphoric acid salt is sodium phosphate or potassiumphosphate.The concentration of described supercarbonate, carbonate is that 50～300mg/L is (with CaCO
3Meter); The concentration of described phosphoric acid salt, hydrophosphate or dihydrogen phosphate is that 2～30mg/L is (with PO
4 3-Meter).
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 sulfonic group multipolymer that contains of the present invention is selected from toxilic acid (acid anhydride)/styrene sulfonic acid multipolymer, vinylformic acid (AA)/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.
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.
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 co-polymer of sulfonate that contains of the present invention is 4-15mg/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.
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, 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 (being generally Sodium Bromide or Sodium Bromide, tensio-active agent and optional adjuvants), 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 2-3 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, the method that adopts oxidisability and non-oxidative bactericide to be used alternatingly added frequency and 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.
Available ordinary method prepares composite scale-inhibiting corrosion inhibitor of the present invention, the reinforced order of each component is unimportant, for example can be with poly-phosphate, organic phospho acid, contain sulfonic group multipolymer, zinc salt and copper material corrosion inhibitor (if any) and water by predetermined mixed, can make required composite scale-inhibiting corrosion inhibitor.In the preparation process of composite scale-inhibiting corrosion inhibitor, also can add a spot of acid (as dilute sulphuric acid, dense or dilute hydrochloric acid etc.), promoting the dissolving of zinc salt, poly-phosphate etc., with the uniform solution of the composite scale-inhibiting corrosion inhibitor that needing to obtain concentration as early as possible.
Usually poly-phosphate zincification water treatment scheme adopts the method that the pH value is turned down when handling the sewage of high basicity, contains ammonia-nitrogen sewage and can handle under high basicity condition with composite scale-inhibiting corrosion inhibitor of the present invention, has increased the use range of this composite scale-inhibiting corrosion inhibitor.Characteristics of the present invention are must be increasing fouling this invention of the factor and composite scale-inhibiting corrosion inhibitor and sterilant combined action, could handle ammonia nitrogen concentration at the reusing sewage of 20-120mg/L in recirculated water.
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.
" water coolant analysis and the test method " that the present invention writes according to production department of China PetroChemical Corporation and development division (1993, the publication of general petrochemical works, Anqing information center) " tosca method " and " rotary hanging plate weight-loss method " carries out static-state scale inhibition test and rotary hanging plate corrosion test in, and 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 to concentrate 2 times the former water of test.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.The COD of water quality
CrMeasuring method is classical chromium method, and all the other measure " the water coolant analysis and the test method " of writing according to production department of China PetroChemical Corporation and development division
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 | ??190 | ????380 | ????277 | ????142 | ????639 | ????8.4 | ????1639 | ????756 | ??102 | ????137 |
| Minimum value | ??120 | ????97 | ????164 | ????84 | ????147 | ????7.4 | ????1120 | ????576 | ??26 | ????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.
Embodiment 1
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 12g Sodium hexametaphosphate 99 is dissolved in the 26.5g water, stirring and dissolving, add the 20g solid content then respectively and be 30% AA/AMPS/HPA sulfonate terpolymer (weight ratio is AA/AMPS/HPA=60/20/20) and 4g active ingredient and be 50% PBTCA, 10 of dilute sulphuric acids that add 17.5g Zinc vitriol and 1: 3 (volume ratio of the vitriol oil and water) at last, fully dissolving, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L with the liquid medicine for preparing, Sodium hexametaphosphate 99, AA/AMPS/HPA sulfonate terpolymer, PBTCA, Zn in the water
2+Effective concentration be respectively 12mg/L, 6mg/L, 2mg/L, 4mg/L.Regulating also with 4%NaOH again, the pH of stabilizing solution is 8.5-9.0.
The test raw water quality is: ammonia nitrogen 26mg/L, Ca
2+185mg/L, total alkalinity 343mg/L, Cl
-125.3mg/L, SO
4 2-352mg/L, pH8.1, COD
Cr35mg/L.
Embodiment 2
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 6g tripoly phosphate sodium STPP is dissolved in the 32.5g water, stirring and dissolving, add the 20g solid content then respectively and be 30% AA/AMPS/HPA sulfonate terpolymer (weight ratio is AA/AMPS/HPA=60/20/20) and 4g active ingredient and be 50% PBTCA, 10 of dilute sulphuric acids that add 17.5g Zinc vitriol and 1: 3 (volume ratio of the vitriol oil and water) at last, it is fully dissolved, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L with the liquid medicine for preparing, tripoly phosphate sodium STPP, AA/AMPS/HPA sulfonate terpolymer, PBTCA, Zn in the water
2+Effective concentration be respectively 6mg/L, 6mg/L, 2mg/L, 4mg/L.Regulating also with 4%KOH again, the pH of stabilizing solution is 9.0-9.5.
The test raw water quality is: ammonia nitrogen 26mg/L, Ca
2+185mg/L, total alkalinity 343mg/L, Cl
-125.3mg/L, SO
4 2-352mg/L, pH8.1, COD
Cr35mg/L.
Embodiment 3
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 14g Sodium hexametaphosphate 99 is dissolved in the 35.75g water, stirring and dissolving, add the 20g solid content then respectively and be 30% AA/AMPS sulfonate copolymer (weight ratio is AA/AMPS=60/40) and 4g active ingredient and be 50% HEDP, add the 6.25g Zinc Chloride Anhydrous at last, fully dissolving, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in containing test water by the drug concentration of 80mg/L with the liquid medicine for preparing, Sodium hexametaphosphate 99, AA/AMPS sulfonate copolymer, HEDP, Zn in the water
2+Effective concentration be respectively 14mg/L, 6mg/L, 2mg/L, 3mg/L.In water, add NaHCO again
3(with CaCO
3Meter) 250mg/L.
The test raw water quality is: ammonia nitrogen 102mg/L, Ca
2+174mg/L, total alkalinity 103mg/L, Cl
-99.3mg/L, SO
4 2-435mg/L, pH8.3, COD
Cr56mg/L.
Embodiment 4
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 6g Sodium hexametaphosphate 99 is dissolved in the 17.5g water, stirring and dissolving, add the 15g solid content then respectively and be 30% AA/AMPS/HPA sulfonate terpolymer (weight ratio is AA/AMPS/HPA=70/15/15), active ingredient and be 50% PBTCA 8g and HEDP16g, 15 of dilute sulphuric acids that add 17.5g Zinc vitriol and 1: 3 (volume ratio of the vitriol oil and water) at last, fully dissolving, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L, Sodium hexametaphosphate 99 in the water, contain AMPS sulfonate terpolymer, PBTCA, HEDP, Zn with the liquid medicine for preparing
2+Effective concentration be respectively 6mg/L, 4.5mg/L, 4mg/L, 8mg/L, 4mg/L.In water, add Na again
2CO
3(with CaCO
3Meter) 100mg/L.
The test raw water quality is: ammonia nitrogen 43mg/L, Ca
2+123mg/L, total alkalinity 125mg/L, Cl
-135.4mg/L, SO
4 2-535mg/L, pH7.8, COD
Cr105mg/L.
Embodiment 5
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 4g tripoly phosphate sodium STPP is dissolved in the 17.7g water, stirring and dissolving, add the 20g solid content then respectively and be 30% AA/AMPS sulfonate copolymer (weight ratio is AA/AMPS=55/45), active ingredient and be 50% PBTCA24g and glycine two methene phosphonic acids 6g, add 5 of 8.3g Zinc Chloride Anhydrous and concentrated hydrochloric acids at last, it is fully dissolved, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L with the liquid medicine for preparing, tripoly phosphate sodium STPP, AA/AMPS sulfonate copolymer, PBTCA, glycine two methene phosphonic acids, Zn
2+Effective concentration be respectively 4mg/L, 6mg/L, 12mg/L, 3mg/L, 4mg/L.In water, add sodium hydrogen phosphate 10mg/L again (with PO
4 3-Meter).
The test raw water quality is seen embodiment 4.
Embodiment 6
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 2g Sodium hexametaphosphate 99 is dissolved in the 19.7g water, stirring and dissolving, add the 20g solid content then respectively and be 30% AA/AMPS sulfonate copolymer (weight ratio is AA/AMPS=55/45), active ingredient and be 50% PBTCA24g and glycine two methene phosphonic acids 6g, add 5 of 8.3g Zinc Chloride Anhydrous and concentrated hydrochloric acids at last, it is fully dissolved, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L with the liquid medicine for preparing, Sodium hexametaphosphate 99, AA/AMPS sulfonate copolymer, PBTCA, glycine two methene phosphonic acids, Zn
2+Effective concentration be respectively 2mg/L, 6mg/L, 12mg/L, 3mg/L, 4mg/L.In water, add potassium primary phosphate 3mg/L again (with PO
4 3-Meter).
The test raw water quality is seen embodiment 3.
Embodiment 7
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 2g tripoly phosphate sodium STPP is dissolved in the 19.7g water, stirring and dissolving, add the 20g solid content then respectively and be 30% AA/AMPS sulfonate copolymer (weight ratio is AA/AMPS=55/45), active ingredient and be 50% PBTCA 24g and glycine two methene phosphonic acids 6g, add the 8.3g Zinc Chloride Anhydrous at last, it is fully dissolved, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L with the liquid medicine for preparing, tripoly phosphate sodium STPP, AA/AMPS sulfonate copolymer, PBTCA, glycine two methene phosphonic acids, Zn
2+Effective concentration be respectively 2mg/L, 6mg/L, 12mg/L, 3mg/L, 4mg/L.In water, add sodium phosphate 15mg/L again (with PO
4 3-Meter).
The test raw water quality is seen embodiment 3.
Embodiment 8
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 3g Sodium hexametaphosphate 99 is dissolved in the 18.85g water, stirring and dissolving, add the 40g solid content then respectively and be 30% AA/AMPS/HPA sulfonate terpolymer (weight ratio is AA/AMPS/HPA=70/15/15), active ingredient and be 50% PBTCA 8g and thionamic acid two methene phosphonic acids 6g, add the 4.15g Zinc Chloride Anhydrous at last, fully dissolving, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L with the liquid medicine for preparing, Sodium hexametaphosphate 99, AA/AMPS/HPA sulfonate terpolymer, PBTCA, thionamic acid two methene phosphonic acids, Zn in the water
2+Effective concentration be respectively 3mg/L, 12mg/L, 4mg/L, 3mg/L, 2mg/L.In water, add KHCO again
3(with CaCO
3Meter) 100mg/L.
The test raw water quality is seen embodiment 4.
Embodiment 9
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 4g Sodium hexametaphosphate 99 is dissolved in the 14.5g water, stirring and dissolving, add the 30g solid content then respectively and be that 30% AA/AMPS/HPA sulfonate terpolymer (weight ratio is AA/AMPS/HPA=70/15/15), active ingredient are 50% PBTCA 8g and to two phosphono and sulfonic 6g, add the 17.5g Zinc vitriol at last, fully dissolving, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L with the liquid medicine for preparing, Sodium hexametaphosphate 99 in the water, AA/AMPS/HPA sulfonate terpolymer, PBTCA, to two phosphono and sulfonics, Zn
2+Effective concentration be respectively 4mg/L, 9mg/L, 4mg/L, 3mg/L, 4mg/L.In water, add NaHCO again
3(with CaCO
3Meter) 50mg/L.
The test raw water quality is seen embodiment 4.
Embodiment 10
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 6g Sodium hexametaphosphate 99 is dissolved in the 21.5g water, stirring and dissolving, add the 20g solid content then respectively and be 30% AA/AMPS/HPA sulfonate terpolymer (weight ratio is AA/AMPS/HPA=60/20/20), copper material corrosion inhibitor BTA 1g, active ingredient and be 50% PBTCA 8g, HEDP 6g, 10 of dilute sulphuric acids that add 17.5g Zinc vitriol and 1: 3 (volume ratio of the vitriol oil and water) at last, fully dissolving, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L, Sodium hexametaphosphate 99 in the water, contain AMPS sulfonate terpolymer, BTA, PBTCA, HEDP, Zn with the liquid medicine for preparing
2+Effective concentration be respectively 6mg/L, 6mg/L, 1mg/L, 4mg/L, 3mg/L, 4mg/L.In water, add KHCO again
3(with CaCO
3Meter) 250mg/L.
The test raw water quality is seen embodiment 4.
Embodiment 11
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 3g tripoly phosphate sodium STPP is dissolved in the 17.5g water, stirring and dissolving, add the 20g solid content then respectively and be 30% AA/AMPS/HPA sulfonate terpolymer (weight ratio is AA/AMPS/HPA=50/25/25), active ingredient and be 50% PBTCA 16g and HEDP 6g, 10 of dilute sulphuric acids that add 17.5g Zinc vitriol and 1: 3 (volume ratio of the vitriol oil and water) at last, fully dissolving, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in containing ammonia nitrogen 26mg/L recirculated cooling water by the drug concentration of 80mg/L, tripoly phosphate sodium STPP in the water, contain AMPS sulfonate terpolymer, PBTCA, HEDP, Zn with the liquid medicine for preparing
2+Effective concentration be respectively 3mg/L, 6mg/L, 8mg/L, 3mg/L, 4mg/L.In water, add KHCO again
3(with CaCO
3Meter) 50mg/L.
The test raw water quality is seen embodiment 4.
Embodiment 12
Process for preparation: preparation 80g liquid medicine
Taking by weighing the 4.5g Sodium hexametaphosphate 99 is dissolved in the 14g water, stirring and dissolving, add the 30g solid content then respectively and be 30% AA/AMPS/HPA sulfonate terpolymer (weight ratio is AA/AMPS/HPA=70/15/15), active ingredient and be 50% PBTCA 8g and HEDP 6g, add the 17.5g Zinc vitriol at last, fully dissolving, shake up, promptly obtain the 80g liquid medicine of required preparation.
When adding in test water by the drug concentration of 80mg/L, Sodium hexametaphosphate 99 in the water, contain AMPS sulfonate terpolymer, PBTCA, HEDP, Zn with the liquid medicine for preparing
2+Effective concentration be respectively 4.5mg/L, 9mg/L, 4mg/L, 3mg/L, 4mg/L.In water, add NaHCO again
3(with CaCO
3Meter) 50mg/L.
The test raw water quality is seen embodiment 4.
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 anti-incrustation corrosion inhibitor
| Embodiment | Resistance calcium carbonate scale rate (%) | Corrosion of carbon steel speed (mm/a) | Copper material corrosion speed (mm/a) |
| Embodiment 1 | ??????98.2 | ????0.036 | |
| Embodiment 2 | ??????97.8 | ????0.025 | |
| Embodiment 3 | ??????97.5 | ????0.042 | |
| Embodiment 4 | ??????97.8 | ????0.029 | |
| Embodiment 5 | ??????96.4 | ????0.031 | |
| Embodiment 6 | ??????97.2 | ????0.033 | |
| Embodiment 7 | ??????96.8 | ????0.029 | |
| Embodiment 8 | ??????98.6 | ????0.043 | |
| Embodiment 9 | ??????99.1 | ????0.034 | |
| Embodiment 10 | ??????97.4 | ????0.031 | ????0.0030 |
| Embodiment 11 | ??????98.3 | ????0.030 | |
| Embodiment 12 | ??????97.9 | ????0.028 |
Embodiment 13-18
For investigating the fungicide effect of sterilant, carried out the static bactericidal assay of sterilant, sterilant kind, concentration and effect see Table 3, and test water is without crossing the former water of spissated test, testing raw water quality and see embodiment 3.
The sterilization effect of table 3 sterilant
| Embodiment | Type | Concentration (mg/l) | Sterilizing rate (%) | |||
| ????1h | ????24h | ????48h | ????72h | |||
| ????13 | Isothiazolinone | ????10 | ????31.8 | ????80.0 | ????71.9 | ????43.1 |
| ????30 | ????/ | ????91.4 | ????76.3 | ????/ | ||
| ????50 | ????34.2 | ????97.3 | ????90.5 | ????/ | ||
| ????14 | Babysafe | ????10 | ????99.9 | ????99.9 | ????99.9 | ????99.9 |
| ????30 | ????99.9 | ????99.9 | ????99.9 | ????99.9 | ||
| ????50 | ????99.9 | ????99.9 | ????99.9 | ????99.9 | ||
| ????15 | ??1227 | ????10 | ????97.9 | ????/ | ????/ | ????/ |
| ????30 | ????99.9 | ????/ | ????/ | ????/ | ||
| ????50 | ????99.9 | ????/ | ????/ | ????/ | ||
| ????16 | Compound disinfectant | ????10 | ????61.7 | ????/ | ????/ | ????/ |
| ????30 | ????95.4 | ????86.4 | ????/ | ????/ | ||
| ????50 | ????95.7 | ????99.9 | ????99.9 | ????87.5 | ||
| ????17 | Novel quaternary ammonium salt | ????10 | ????99.7 | ????99.9 | ????99.9 | ????/ |
| ????30 | ????99.9 | ????99.9 | ????99.9 | ????/ | ||
| ????50 | ????99.9 | ????99.9 | ????99.9 | ????99.9 | ||
| ????18 | Organic bromine | ????10 | ????99.8 | ????99.8 | ????99.9 | ????/ |
| ????30 | ????99.9 | ????99.9 | ????99.9 | ????/ | ||
| ????50 | ????99.9 | ????99.9 | ????99.9 | ????99.9 |
Annotate: the starter bacteria number is 1.2 * 10
6Individual/ml.Compound disinfectant be 1227 and and 1: 1 compound of thiazolinone; Novel quaternary ammonium salt bactericide is a tetradecyl dimethyl octyl group brometo de amonio; Organic bromine is 2,2-two bromo-3-nitrilo propionic acid amides.
The result as seen, the sterilization when present sterilant is suitable for the reusing sewage of high ammonia-nitrogen content, with not obvious to tap water sterilization effect difference, the function Characteristics of each sterilant is also identical to the sewage sterilization effect for each sterilant.
Embodiment 19
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: 3.0 ± 0.2 flow velocitys: 1.0m/s
Medicament: Sodium hexametaphosphate 99+glycine two methenes phosphonic acids+PBTCA+AA/AMPS/HPA multipolymer (weight ratio is 70/10/20)+zinc salt, effective concentration are respectively 4,3,4,6,4mg/l.
Total phosphorus (PO
4 3-Meter): B tower 5.2 ± 0.1mg/l
Temperature in: 32 ± 1 ℃ of temperature difference: 10 ℃
The test raw water quality sees Table 1
Operation process: the HCO that adds 100mg/l in the sewage
3 -(by NaHCO
3Provide, with CaCO
3Meter)
Sterilant adds kind, concentration and bacterial control and the results are shown in Table 4.
Number of bacteria in the table 4 dynamic simulation process
| Time | Heterotrophic bacterium (individual/ml) | Iron bacteria (individual/ml) | Sulphate reducing bacteria (individual/ml) | Remarks |
| The 1st day | 7.5 * 10 6 | 1.4 * 10 3 | 1.4 * 10 2 | Adding of germicide not |
| The 2nd day | 3.9 * 10 6 | 4.5 * 10 2 | 1.1 * 10 2 | |
| The 5th day | 6.3 * 10 6 | 1.4 * 10 3 | 1.1 * 10 2 | Add the secondary Babysafe every day, concentration is 100mg/l. |
| The 6th day | 1.0 * 10 3 | 11 | Do not measure | |
| The 7th day | 1.6 * 10 4 | 45 | Do not measure | |
| The 8th day | 1.7 * 10 4 | 20 | Do not measure | |
| The 11st day | 5.5 * 10 2 | Do not measure | Do not measure | |
| The 12nd day | ＜10 3 | Do not measure | Do not measure | Add Babysafe every day three times, concentration is 100mg/l. |
| The 13rd day | ＜10 2 | Do not measure | Do not measure | |
| The 14th day | ＜10 2 | Do not measure | Do not measure | |
| 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.
The dynamic analog test test tube the results are shown in Table 5.
Table 5 dynamic analog test test tube result
| Test conditions | The test tube result | |||
| Drug concentration (mg/l) | Working time | Erosion rate (mm/a) | Adhere to speed (mcm) | Fouling resistance (m 2H ℃/kilocalorie) |
| ????90 | 16 days | ?????0.0521 | ??????19.3 | ????1.19×10 -4 |
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 " good " level at 6-15mcm, is " can allow " level at 15-20mcm; Fouling resistance is in (1-2) * 10
-4m
2H ℃/kilocalorie is " good " level, in (2-3) * 10
-4m
2H ℃/kilocalorie is " can allow level ".
The erosion rate that this shows test tube is 0.0521mm/a, reaches China Petrochemical Industry's " good level " standard, adheres to speed and reaches " allowing level " standard, and fouling resistance reaches " good " grade standard.Comparative Examples 1
Remove the HCO that does not add 100mg/l in the sewage
3 -Outward, other dynamic analog test method and condition are with embodiment 19.
Table 6 dynamic analog test test tube result
| Test conditions | The test tube result | |||
| Drug concentration (mg/l) | Working time | Erosion rate (mm/a) | Adhere to speed (mcm) | Fouling resistance (m 2H ℃/kilocalorie) |
| ????90 | 14.94 my god | ?????0.2281 | ?????23.3 | ?????1.56×10 -4 |
Data show in the table: only add the anti-incrustation corrosion inhibitor among the present invention, and do not increase the fouling factor, when dynamic simulation, erosion rate exceeds standard.
The data declaration of the foregoing description and Comparative Examples is fit to the processing of the sewage of high ammonia-nitrogen content as the make up water of recirculating cooling water system with method of the present invention.
Claims (16)
1, a kind ofly contains the method that ammonia-nitrogen sewage is back to recirculated cooling water, it is characterized in that at the reusing sewage that contains ammonia nitrogen during in recirculated cooling water, successively add composite scale-inhibiting corrosion inhibitor and alkali, supercarbonate, carbonate, hydrophosphate, dihydrogen phosphate or phosphoric acid salt, add sterilant afterwards again, wherein composite scale-inhibiting corrosion inhibitor comprises poly-phosphate, organic phospho acid, contains sulfonic group multipolymer and zinc salt.
2, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1 is described, it is characterized in that the ammonia nitrogen concentration scope is 20～120mg/L in the described sewage.
3, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1 is described, it is characterized in that described alkali is sodium hydroxide, potassium hydroxide, its add-on is so that the pH value is adjusted to 7.6～9.5, is preferably 8.5～9.5 to be as the criterion.
4, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1 is described, it is characterized in that described supercarbonate is sodium bicarbonate or saleratus; Described carbonate is yellow soda ash or salt of wormwood; Described hydrophosphate is sodium hydrogen phosphate or potassium hydrogen phosphate; Described dihydrogen phosphate is SODIUM PHOSPHATE, MONOBASIC or potassium primary phosphate; Described phosphoric acid salt is sodium phosphate or potassiumphosphate.
5, describedly contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1,2 or 4, the concentration that it is characterized in that described carbonate or supercarbonate is that 50～300mg/L is (with CaCO
3Meter); The concentration of described phosphoric acid salt, hydrophosphate or dihydrogen phosphate is that 2～30mg/L is (with PO
4 3-Meter).
6, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1 is described, it is characterized in that described poly-phosphate is Sodium hexametaphosphate 99 or tripoly phosphate sodium STPP.
7, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1 is described, 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.
8, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1 is described, it is characterized in that the described sulfonic group multipolymer that contains is selected from 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 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.
9, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1 is described, it is characterized in that described zinc salt is selected from zinc sulfate, zinc chloride and zinc carbonate.
10, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1 is described, it is characterized in that also containing in the described composite scale-inhibiting corrosion inhibitor heterogeneous ring compound as copper material corrosion inhibitor.
11, want 10 describedly to contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to right, it is characterized in that described copper material corrosion inhibitor selected from mercapto benzothiazole and benzotriazole.
12, each describedly contains the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1-10, it is characterized in that with respect to the effective concentration of pending each component of aqueous solution total amount being: poly-phosphate is 2-15mg/L, the organic phospho acid total concn is 2-15mg/L, contain co-polymer of sulfonate concentration 4-15mg/L, zinc salt is counted 1.5-5mg/L with zine ion.
13, describedly contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 10 or 11, it 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.
14, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 1 is described, 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, (Puritabs, trichloroisocyanuric acid (strong chlorine oil), dioxide peroxide, organic bromine, active bromine are 5～200mg/L with respect to pending its effective concentration of aqueous solution total amount to Surchlor GR 60; 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.
15, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 14 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.
16, contain the method that ammonia-nitrogen sewage is back to recirculated cooling water according to claim 14 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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|---|---|---|---|
| CNB011347031A CN1176863C (en) | 2001-11-08 | 2001-11-08 | Method for reusing ammonia nitrogen containing effluent as circular cooling water |
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