CN1631814A - Scale removal method adapted for circulating and cooling water system - Google Patents
Scale removal method adapted for circulating and cooling water system Download PDFInfo
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- CN1631814A CN1631814A CN 200310121875 CN200310121875A CN1631814A CN 1631814 A CN1631814 A CN 1631814A CN 200310121875 CN200310121875 CN 200310121875 CN 200310121875 A CN200310121875 A CN 200310121875A CN 1631814 A CN1631814 A CN 1631814A
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- descaling method
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- 239000000498 cooling water Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000005260 corrosion Methods 0.000 claims abstract description 39
- 230000007797 corrosion Effects 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000003112 inhibitor Substances 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 15
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 13
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 150000007524 organic acids Chemical class 0.000 claims abstract description 9
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 19
- 229910019142 PO4 Inorganic materials 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 15
- 229920001577 copolymer Polymers 0.000 claims description 15
- -1 hexadecylaminoethylglycine Chemical compound 0.000 claims description 15
- 239000010452 phosphate Substances 0.000 claims description 15
- 239000011701 zinc Substances 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 14
- 239000007800 oxidant agent Substances 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- 230000001590 oxidative effect Effects 0.000 claims description 10
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical group [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 9
- 229960001763 zinc sulfate Drugs 0.000 claims description 9
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 9
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 8
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims description 8
- 239000002280 amphoteric surfactant Substances 0.000 claims description 8
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 7
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical group [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 7
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 7
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 7
- 229920000388 Polyphosphate Polymers 0.000 claims description 6
- 239000001205 polyphosphate Substances 0.000 claims description 6
- 235000011176 polyphosphates Nutrition 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 229920006243 acrylic copolymer Polymers 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000003134 recirculating effect Effects 0.000 claims description 4
- 150000003751 zinc Chemical class 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- UPFFQWNDECRHRY-UHFFFAOYSA-N 2-[2-(dodecylamino)ethylamino]acetic acid Chemical group CCCCCCCCCCCCNCCNCC(O)=O UPFFQWNDECRHRY-UHFFFAOYSA-N 0.000 claims description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical class [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- KWKOTMDQAMKXQF-UHFFFAOYSA-N [2-methyl-2-(prop-2-enoylamino)propyl]phosphonic acid Chemical compound OP(=O)(O)CC(C)(C)NC(=O)C=C KWKOTMDQAMKXQF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002978 peroxides Chemical group 0.000 claims description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 2
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical compound OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 239000002253 acid Substances 0.000 abstract description 7
- 230000002829 reductive effect Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 3
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000005406 washing Methods 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 2
- 230000003628 erosive effect Effects 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract 1
- 239000001117 sulphuric acid Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 29
- 238000004140 cleaning Methods 0.000 description 21
- 238000005094 computer simulation Methods 0.000 description 10
- 238000001035 drying Methods 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 239000008399 tap water Substances 0.000 description 7
- 235000020679 tap water Nutrition 0.000 description 7
- 239000004471 Glycine Substances 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- URHAKDFUJWRPEH-UHFFFAOYSA-N 2-[2-aminoethyl(dodecyl)amino]acetic acid Chemical compound CCCCCCCCCCCCN(CCN)CC(O)=O URHAKDFUJWRPEH-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 244000005700 microbiome Species 0.000 description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 2
- 235000019799 monosodium phosphate Nutrition 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- SFVFIFLLYFPGHH-UHFFFAOYSA-M stearalkonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 SFVFIFLLYFPGHH-UHFFFAOYSA-M 0.000 description 2
- 229920001897 terpolymer Polymers 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- DBAMUTGXJAWDEA-UHFFFAOYSA-N Butynol Chemical compound CCC#CO DBAMUTGXJAWDEA-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 241001415288 Coccidae Species 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- OCBHHZMJRVXXQK-UHFFFAOYSA-M benzyl-dimethyl-tetradecylazanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 OCBHHZMJRVXXQK-UHFFFAOYSA-M 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000010962 carbon steel Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention relates to a descaling method suitable for cycling water cooling system, which includes: simultaneously or by steps add organic acid or sulphuric acid, corrosion inhibitor, surfactants and hydrazine hydrate of strong reductive agent into the cycling cooling water, then add 4 .The 5 reacts with 4, generating nitrogen, which can combine the chemical washing method and bobble method, increasing the descaling efficiency. Besides, the PH value is controlled by acid between 4-6, by which the quantity of acid can be reduced, so that decrease erosion to the equipment and pipeline of the system.
Description
Technical Field
The invention relates to a descaling method suitable for a circulating cooling water system. In particular to a method for removing microorganism scale and soft scale (sediment scale generated by calcium salt in the presence of a water treatment agent) on equipment and pipelines in a circulating water system.
Background
At present, most circulating water systems adopt an alkaline water treatment process, and after the systems run for a long period, the cooling effect of a cooler is reduced due to scaling, corrosion and accumulation of microorganisms, and the cooling system is usually required to be cleaned. The conventional cleaning method comprises two steps, wherein the first step is to add the quaternary ammonium salt slime stripping agent for stripping, and a white sticky object is often seen below a cooling water tower, because the conventional polyacrylic acid scale inhibition and dispersion agent in the water treatment agent reacts with the quaternary ammonium salt slime stripping agent. The peeled slime increases the turbidity of water, so a large amount of fresh water is needed for replacement, when the turbidity is reduced to 10mg/L, sulfuric acid or sulfamic acid and a pickling inhibitor are added for descaling in the second step, and after the acid is added, the pH is controlled to be 3-4, if the pickling inhibitor is not selected well, the corrosion rate of a cooler and a pipeline is high, and the safety is slightly poor.
Chinese patent application CN1318524A discloses a high-efficiency descaling agent for a water-cooled heat exchanger, which consists of organic acid, anionic surfactant and corrosion inhibitor, wherein the organic acid is a mixture of two or more of sulfamic acid, tartaric acid, ethylene diamine tetraacetic acid, maleic acid and citric acid, the anionic surfactant is a mixture of one or more of soap, sodium alkylsulfonate, sodium alkylaryl sulfonate, sodium alkylsulfate, secondary alkyl sodium sulfate, sodium p-methoxyfatty amido benzene sulfonate and polyacrylate, and the corrosion inhibitor is one or more of thiourea, hexamethylenetetramine, hydroxy ethylidene diphosphonic acid, octadecyl dimethyl benzyl ammonium chloride, lignin and butynol. The disadvantage is that the corrosion inhibitors used are different from the corrosion inhibitors which are customary for recirculating cooling water systems and, when octadecyldimethylbenzyl ammonium chloride is used as corrosion inhibitor, it reacts with anionic polyacrylates.
Disclosure of Invention
The invention aims to provide a descaling method suitable for a circulating cooling water system, which has high descaling efficiency and low corrosion rate.
In order to achieve the above object, the present invention provides a descaling method suitable for a recirculating cooling water system, comprising adding an organic acid or sulfuric acid, a corrosion inhibitor, an amphoteric surfactant and a strong reducing agent hydrazine hydrate to recirculating cooling water simultaneously or stepwise, and then adding an oxidizing agent.
The method of the invention preferably adds the corrosion inhibitor into the circulating cooling water, and uses organic acid or sulfuric acid to adjust the pH value to 4-6, then adds the amphoteric surfactant and the strong reducing agent hydrazine hydrate at the same time, and finally adds the oxidant. This minimizes acid corrosion of equipment and piping.
The strong reducing agent and the oxidant in the method can react to generate nitrogen gas:
therefore, the chemical cleaning method and the bubble method can be organically combined together, and the descaling efficiency can be improved. In addition, the method controls the pH value of the acid to be 4-6, so that the use amount of the acid can be reduced, and the corrosion to equipment and pipelines of a circulating cooling water system can be reduced.
The amphoteric surfactant is dodecyl amino ethyl glycine and/or hexadecyl amino ethyl glycine. The effective concentration of the amphoteric surfactant in circulating cooling water is 20-80 mg/L.
Hydrazine hydrate (with N) according to the invention2H4Meter) in circulating water is 200-1000 mg/L.
The organic acid is at least one compound selected from glycolic acid and sulfamic acid.
The corrosion inhibitor comprises phosphate and/or polyphosphate, acrylic copolymer and zinc salt, and the effective concentration of the corrosion inhibitor in circulating cooling water is as follows: 20-80mg/L phosphate and/or polyphosphate (as PO)4 3-Calculated as Zn), 50-100mg/L of copolymer containing carboxylic acid group and 5-20mg/L of zinc salt2+Meter). The phosphate is sodium or potassium salt containing phosphate radical, hydrogen phosphate radical or dihydrogen phosphate radical; the polyphosphate is sodium hexametaphosphate or sodium tripolyphosphate(ii) a The acrylic copolymer is selected from acrylic acid/allyl sulfonic acid copolymer, acrylic acid/2-methyl-2 '-acrylamidopropanesulfonic Acid (AMPS) copolymer, acrylic acid/acrylamide/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, acrylic acid/acrylic ester/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer, acrylic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, acrylic acid/acrylic ester copolymer, wherein the propylene isThe acid ester is preferably selected from methyl acrylate, ethyl acrylate, hydroxypropyl acrylate (HPA); the zinc salt is zinc sulfate, zinc chloride and zinc carbonate.
The oxidant is peroxide, preferably at least one compound selected from peracetic acid or hydrogen peroxide, and the effective concentration of the oxidant in circulating cooling water is 400-3000 mg/L.
The invention has the advantages that the cationic quaternary ammonium salt stripping agent which has the function with the anionic polycarboxylate dispersant in the water treatment agent is not used, the amphoteric surfactant is used as the stripping agent, and the combination of a bubble method and a chemical cleaning method is adopted, so that the descaling effect is improved. In addition, the corrosion inhibitor used in the method is consistent with the corrosion inhibitor commonly used in the circulating cooling water system, so that the consumption of the corrosion inhibitor commonly used in the circulating cooling water system can be saved. The method of the invention not only can remove dirt on equipment and pipelines of a circulating cooling water system, especially on coolers with slow flow rate and serious dirt, but also is easy to remove the dirt, and the method of the invention has the advantages of small corrosion rate, safety and reliability, and is suitable for cleaning large circulating water systems.
The test water comes from Beijing surface water and is added with CaCl2、NaHCO3And the like. The water quality is as follows: the calcium ion concentration is 300-320mg/L (calculated by calcium carbonate), and the alkalinity is 380-480 mg/L.
When surface water or underground water is used as make-up water of circulating cooling water system under natural operation condition (high alkalinity), the method of the present invention can be used for on-line descaling of equipment and pipeline of circulating cooling water system. The on-line cleaning time of the circulating cooling water system in the method is 24-48 hours.
Detailed Description
The following examples will help illustrate the invention without limiting its scope.
The following examples were conducted in accordance with a dynamic simulation apparatus in the analysis and test method for cooling water (1993, published by the information center of the central office of the institute of petrochemical engineering, Anqing), which was written by the Ministry of production and development of the general chemical industries of China.
Test Water for the following examples CaCl was added to surface water from Beijing2And NaHCO3And the like. The water quality of the test water is as follows: ca2+(with CaCO)3Calculated as follows) 300-320mg/L, total alkalinity (as CaCO)3Calculated as follows) 380--63-142mg/L，SO4 2-46-139mg/L, and the conductivity is 900-. The measurement of the water quality index refers to the analysis and test method of cooling water (1993, published by the information center of the general petrochemical plant in Anqing) compiled by the Ministry of production and development of the general petrochemical company of China.
The preparation method of the scale sample comprises the following steps: the generation of the scale of the test tube adopts the plating of phi 10 multiplied by 1mm outer wall chrome of 20#Seamless carbon steel pipe circulationThe dynamic simulation test device for the ring cooling water is carried out. Before the scale formation, the test tube is dried, weighed and measured, and the scale formation condition is as follows: steam temperature of 100 + -1 deg.C, flow rate of 0.5m/s in test tube, inlet temperature of 30 + -1 deg.C, adding enriched bacteria to make heterotrophic bacteria in water greater than 1 × 106One per ml. Maintaining the concentration of hydroxyethylidene diphosphonic acid (HEDP) of the scale and corrosion inhibitor at 4mg/L and the copolymer of acrylic acid and hydroxypropyl acrylate at 4mg/L, not discharging pollution, running for 5 days, running four test tubes in parallel, drying two test tubes to constant weight, taking an average value, and directly carrying out a dynamic dirt removal test without treatment on two test tubes.
Cleaning the test tube by using a dynamic simulation device, controlling the inlet temperature to be 30 +/-1 ℃, the steam temperature to be 100 ℃, controlling the flow rate in the test tube to be 0.5m/s, adding a cleaning medicament into a water tank of a movable mold device at the beginning of an experiment, cleaning for 14-48 hours, and after cleaning is finished, taking down the test tube to perform post-treatment such as drying, weighing, measuring volume, calculating and the like.
Example 1
Installing the scaled test tube, adding test water, adding corrosion inhibitor to make sodium hexametaphosphate (PO)4 3-Calculated as AA/AMPS/HPA terpolymer (weight ratio AA/AMPS/HPA: 68/17/15, limiting viscosity number 0.085dl/g (30 ℃)), zinc sulfate (expressed as Zn)2+Calculated) the effective concentration of the circulating cooling water is 60mg/L, 80mg/L and 15 mg/L. Starting a dynamic simulation device, adding glycolic acid to adjust the pH value to 5-6, and adding a hydrazine hydrate strong reducing agent (N is used as a strong reducing agent) of 500mg/L2H4Metering) and 50mg/L of dodecylaminoethylglycine, circulating for 1 hour, adding 1500mg/L of oxidant hydrogen peroxide, operating for 24hours, replacing the turbidity in water by tap water until the turbidity is less than 10mg/L, and after cleaning, taking down the pipe for post-treatment such as drying, weighing, measuring volume, calculating and the like.
The cleaning results are shown in table 1:
TABLE 1
| Amount of fouling of tubes, g | 5.24 | 5.24 |
| Amount of scale removed from pipe g | 2.67 | 2.57 |
| The rate of scale removal% | 51％ | 49％ |
| Corrosion rate of pipe, mm/a | 0.09 | 0.09 |
Example 2
The test tube with the scale is mounted, the test water is added, and 50mg/L of dodecyl aminoethylGlycine and 400mg/L hydrazine hydrate strong reducing agent (as N)2H4Metering), starting the dynamic simulation device, circulating for 1 hour, adding the corrosion inhibitor to make sodium hexametaphosphate (PO)4 3-Calculated as Zn), AA/HPA bipolymer (weight ratio AA/HPA: 68/32, limiting viscosity number 0.080dl/g (30 ℃)), zinc sulfate (calculated as Zn)2+Calculated) the effective concentration of the circulating cooling water is 80mg/L, 100mg/L and 20 mg/L. Adjusting pH to 4-5 with sulfamic acid, adding 1800mg/L peroxyacetic acid oxidant, operating for 24 hr, replacing with tap water until turbidity in water is less than 10mg/L, and after cleaning, taking off the tube, oven drying, weighing, measuring volume, calculating, etc. The cleaning results were as follows:
TABLE 2
| Amount of fouling of tubes, g | 4.41 | 4.41 |
| Amount of scale removed from pipe g | 2.25 | 2.43 |
| The rate of scale removal% | 51％ | 55％ |
| Corrosion rate of pipe, mm/a | 0.13 | 0.13 |
Example 3
Installing the scaled test tube, adding test water, adding sodium dihydrogen Phosphate (PO) as corrosion inhibitor4 3-Calculated as Zn), AA/HPA bipolymer (weight ratio AA/HPA: 68/32, limiting viscosity number 0.080dl/g (30 ℃)), zinc sulfate (calculated as Zn)2+Calculated) the effective concentration of the circulating cooling water is 40mg/L, 80mg/L and 10 mg/L. Starting a dynamic simulation device, adjusting the pH value to 4-5 by using sulfuric acid, adding 60mg/L of dodecyl amino ethyl glycine and 400mg/L of hydrazine hydrate strong reducing agent (N is used as the reducing agent)2H4Metering), circulating for 1 hour, adding peroxyacetic acid oxidant with the dosage of 2000mg/L, circulating for 30 hours, replacing with tap water until the turbidity in water is less than 10mg/L, and after cleaning, taking down the pipe to perform post-treatment such as drying, weighing, measuring volume, calculating and the like. The cleaning results were as follows:
TABLE 3
| Amount of fouling of tubes, g | 4.65 | 4.65 |
| Amount of scale removed from pipe g | 2.42 | 2.51 |
| The rate of scale removal% | 52％ | 54％ |
| Corrosion rate of pipe, mm/a | 0.13 | 0.15 |
Example 4
Installing the scaled test tube, adding test water, adding corrosion inhibitor such as sodium hexametaphosphate and sodium hydrogen Phosphate (PO)4 3-Calculated), AA/HPA dipolymer (heavy)The quantity ratio of AA/HPA is 68/32, the limiting viscosity number is 0.080dl/g (30 ℃), zinc sulfate (as Zn)2+Calculated) the effective concentration of the circulating cooling water is 60mg/L, 20mg/L, 90mg/L and 20 mg/L. Starting a dynamic simulation device, adjusting the pH value to 4-5 by sulfamic acid, and adding a strong hydrazine hydrate reducing agent (N is used as a stronghydrazine hydrate reducing agent) of 600mg/L2H4Metering) and 60mg/L of dodecylaminoethylglycine, circulating for 0.5 hour, adding 1700mg/L of hydrogen peroxide oxidant, circulating for 24 hours, replacing the turbidity in water with tap water until the turbidity is less than 10mg/L, and after cleaning, taking down the pipe for post-treatment such as drying, weighing, measuring volume, calculating and the like.
The cleaning results were as follows:
TABLE 4
| Amount of fouling of tubes, g | 4.91 | 4.91 |
| Amount of scale removed from pipe g | 2.71 | 2.70 |
| The rate of scale removal% | 55％ | 55％ |
| Corrosion rate of pipe, mm/a | 0.14 | 0.14 |
Example 5
Installing the scaled test tube, adding test water, sulfamic acid, corrosion inhibitor, dodecyl aminoethylglycine and hydrazine hydrate as strong reducer to make sodium hexametaphosphate and sodium hydrogen Phosphate (PO)4 3-Calculated as Zn), AA/HPA bipolymer (weight ratio AA/HPA: 68/32, limiting viscosity number 0.080dl/g (30 ℃)), zinc sulfate (calculated as Zn)2+Calculated as N), dodecyl amino ethyl glycine, hydrazine hydrate strong reducing agent (calculated as N)2H4Metering) when the effective concentration of the circulating cooling water is 40mg/L, 20mg/L, 80mg/L, 15mg/L, 70mg/L and 450mg/L, the pH value of the circulating cooling water is controlled to be 4-5, a dynamic simulation device is started, the circulating is carried out for 1 hour, 1500mg/L hydrogen peroxide oxidant is added, the circulating is carried out for 24 hours, tap water is used for replacing the turbidity of the circulating cooling water until the turbidity of the circulating cooling water is less than 10mg/L, and after the cleaning is finished, a pipe is taken down for carrying out post-treatment such as drying, weighing, volume measuring, calculating and the like.
The cleaning results were as follows:
TABLE 5
| Amount of fouling of tubes, g | 5.21 | 5.21 |
| Amount of scale removed from pipe g | 2.71 | 2.81 |
| The rate of scale removal% | 52％ | 54％ |
| Corrosion rate of pipe, mm/a | 0.14 | 0.16 |
Comparative example 1
Installing the scaled test tube, adding test water, adding corrosion inhibitor to make sodium hexametaphosphate (PO)4 3-Calculated), AA/AMPS/HPA terpolymer (weight ratio AA/AMPS/HPA: 68/17/15, limiting viscosity number)0.085dl/g (30 ℃), zinc sulfate (in Zn)2+Calculated) the effective concentration of the circulating cooling water is 60mg/L, 80mg/L and 15 mg/L. Starting a dynamic simulation device, adding glycolic acid to adjust the pH value to 5-6, adding 1427 (tetradecyl dimethyl benzyl ammonium chloride) with the concentration of 50mg/L, stripping for 24 hours, replacing with tap water until the turbidity in water is less than 10mg/L, and after cleaning, taking down a pipe to perform post-treatment such as drying, weighing, measuring volume, calculating and the like.
The cleaning results were as follows:
TABLE 6
| Amount of fouling of tubes, g | 4.98 | 4.98 |
| Amount of scale removed from pipe g | 2.09 | 1.92 |
| The rate of scale removal% | 42％ | 38％ |
| Corrosion rate of pipe, mm/a | 0.11 | 0.11 |
Comparative example 2:
installing the scaled test tube, adding test water, adding sodium dihydrogen Phosphate (PO) as corrosion inhibitor4 3-Calculated as Zn), AA/HPA bipolymer (weight ratio AA/HPA: 68/32, limiting viscosity number 0.080dl/g (30 ℃)), zinc sulfate (calculated as Zn)2+Calculated) the effective concentration of the circulating cooling water is 40mg/L, 80mg/L and 10 mg/L. Starting a dynamic simulation device, adjusting the pH value to 4-5 by using sulfuric acid, adding 60mg/L of dodecyl amino ethyl glycine, running for 30 hours, replacing the mixture with tap water until the turbidity of water is less than 10mg/L, and cleaningAfter washing, the tube is taken down for post-treatment such as drying, weighing, volume measuring, calculating and the like, and the washing result is as follows:
TABLE 7
| Amount of fouling of tubes, g | 4.43 | 4.43 |
| Amount of scale removed from pipe g | 1.82 | 1.96 |
| The rate of scale removal% | 41％ | 44％ |
| Corrosion rate of pipe, mm/a | 0.15 | 0.17 |
The test results are shown in Table 8.
TABLE 8 comparison of the effects of the examples with those of the comparative examples
| Examples | Average scale removal rate,% | Pipe corrosion speed (mm/a) |
| Example 1 | 50 | 0.09 |
| Example 2 | 53 | 0.13 |
| Example 3 | 53 | 0.14 |
| Example 4 | 55 | 0.14 |
| Example 5 | 53 | 0.15 |
| Comparative example 1 | 40 | 0.11 |
| Comparative example 2 | 43 | 0.16 |
From the data of the above examples andcomparative examples it can be seen that: the method has good descaling effect and low corrosion rate.
Claims (9)
1. A descaling method for the circulating cooling water system includes adding organic acid or sulfuric acid, corrosion inhibitor, amphoteric surfactant and hydrazine hydrate as strong reducer to the circulating cooling water simultaneously or step by step, and adding oxidant.
2. A descaling method according to claim 1, wherein the corrosion inhibitor is added to the circulating cooling water, the pH is adjusted to 4-6 with an organic acid or sulfuric acid, and then the amphoteric surface active and strong reducing agent hydrazine hydrate is added simultaneously, and finally the oxidizing agent is added.
3. The descaling method according to claim 1 or 2, characterized in that the amphoteric surfactant is dodecylaminoethylglycine and/or hexadecylaminoethylglycine.
4. A descaling method according to claims 1-3, characterized in that the effective concentration of the amphoteric surfactant in the recirculating cooling water is 20-80 mg/L.
5. A descaling method according to any of claims 1-4, characterized in that said hydrazine hydrate (as N)2H4Meter) in circulating water is 200-1000 mg/L.
6. A descaling method according to any of claims 1-5, wherein the organic acid is at least one compound selected from glycolic acid and sulfamic acid.
7. A descaling method accordingto any of claims 1-6, characterized in that the corrosion inhibitor comprises phosphates and/or polyphosphates, acrylic copolymers and zinc salts, which are recycledThe effective concentration in the cooling water is as follows: 20-80mg/L phosphate and/or polyphosphate (as PO)4 3-Calculated as Zn), 50-100mg/L of copolymer containing carboxylic acid group and 5-20mg/L of zinc salt2+Meter).
8. The descaling method according to claim 7, wherein the phosphate is a sodium or potassium salt containing phosphate, hydrogen phosphate or dihydrogen phosphate; the polyphosphate is sodium hexametaphosphate or sodium tripolyphosphate; the acrylic copolymer is selected from acrylic acid/allylsulfonic acid copolymer, acrylic acid/2-methyl-2 '-acrylamidopropanesulfonic Acid (AMPS) copolymer, acrylic acid/acrylamide/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, acrylic acid/acrylic ester/2-methyl-2 '-acrylamidopropanesulfonic acid copolymer, acrylic acid/2-acrylamido-2-methylpropanephosphonic acid/2-methyl-2' -acrylamidopropanesulfonic acid copolymer, acrylic acid/acrylic ester copolymer, wherein the acrylic ester is preferably selected from methyl acrylate, ethyl acrylate, hydroxypropyl acrylate (HPA); the zinc salt is zinc sulfate, zinc chloride and zinc carbonate.
9. Descaling method according to any of claims 1-8, characterized in that the oxidizing agent is a peroxide, preferably at least one compound selected from the group consisting of peracetic acid or hydrogen peroxide, having an effective concentration in the circulating cooling water of 400-3000 mg/L.
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| CN103508570A (en) * | 2012-06-25 | 2014-01-15 | 上海思曼泰化工科技有限公司 | Environmental protection and high efficiency corrosion inhibitor for inhibiting salt water corrosion on carbon steel, preparation method and use method thereof |
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| CN2154260Y (en) * | 1993-03-06 | 1994-01-26 | 于洪伟 | Water treatment device with electronic anti-filth and filth-eliminate |
| CN2237176Y (en) * | 1994-08-29 | 1996-10-09 | 朱志发 | Electromagnetic descaling device |
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| CN110803781B (en) * | 2018-08-06 | 2021-07-30 | 中国石油化工股份有限公司 | Composite corrosion and scale inhibitor containing polyphosphate, application thereof and method for inhibiting corrosion of circulating cooling water containing sulfur |
| CN110803781A (en) * | 2018-08-06 | 2020-02-18 | 中国石油化工股份有限公司 | Composite corrosion and scale inhibitor containing polyphosphate, application thereof and method for inhibiting corrosion of circulating cooling water containing sulfur |
| CN110484731A (en) * | 2019-08-18 | 2019-11-22 | 贵州鸿璟稀有金属开发应用科技有限公司 | A kind of method of wet-treating Heavy Metals in Coal Gangue element and rare element |
| CN110484731B (en) * | 2019-08-18 | 2021-01-05 | 贵州鸿璟稀有金属开发应用科技有限公司 | Method for wet treatment of heavy metal elements and rare elements in coal gangue |
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