CN1618743A - Composite corrosion and scale inhibitor and its application in treating circulating cooling water - Google Patents
Composite corrosion and scale inhibitor and its application in treating circulating cooling water Download PDFInfo
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- CN1618743A CN1618743A CNA2003101150277A CN200310115027A CN1618743A CN 1618743 A CN1618743 A CN 1618743A CN A2003101150277 A CNA2003101150277 A CN A2003101150277A CN 200310115027 A CN200310115027 A CN 200310115027A CN 1618743 A CN1618743 A CN 1618743A
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- Prior art keywords
- acid
- multipolymer
- vinylformic
- corrosion
- methyl
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- 239000002131 composite material Substances 0.000 title claims abstract description 29
- 239000000498 cooling water Substances 0.000 title claims abstract description 20
- 238000005260 corrosion Methods 0.000 title claims description 82
- 230000007797 corrosion Effects 0.000 title description 57
- 239000002455 scale inhibitor Substances 0.000 title 1
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 229920001519 homopolymer Polymers 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 30
- -1 phospho Chemical class 0.000 claims description 14
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 13
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 12
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 10
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 9
- AGBXYHCHUYARJY-UHFFFAOYSA-N 2-phenylethenesulfonic acid Chemical compound OS(=O)(=O)C=CC1=CC=CC=C1 AGBXYHCHUYARJY-UHFFFAOYSA-N 0.000 claims description 9
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 150000008065 acid anhydrides Chemical class 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 9
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 229920000642 polymer Polymers 0.000 claims description 8
- 229920001897 terpolymer Polymers 0.000 claims description 8
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 claims description 6
- LBHZKEWZASOKKW-UHFFFAOYSA-N C(C)(=O)O.NC(=N)N.OCC(P(O)(O)=O)P(O)(O)=O Chemical compound C(C)(=O)O.NC(=N)N.OCC(P(O)(O)=O)P(O)(O)=O LBHZKEWZASOKKW-UHFFFAOYSA-N 0.000 claims description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- 229940120146 EDTMP Drugs 0.000 claims description 4
- 229920006243 acrylic copolymer Polymers 0.000 claims description 4
- 239000001273 butane Substances 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 125000005396 acrylic acid ester group Chemical group 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 3
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 claims description 3
- 229920001444 polymaleic acid Polymers 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims description 3
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 claims description 3
- 239000003112 inhibitor Substances 0.000 abstract description 8
- IQEKRNXJPCBUAT-UHFFFAOYSA-N 2-[hydroperoxy(hydroxy)phosphoryl]acetic acid Chemical compound OOP(O)(=O)CC(O)=O IQEKRNXJPCBUAT-UHFFFAOYSA-N 0.000 abstract 2
- SZHQPBJEOCHCKM-UHFFFAOYSA-N 2-phosphonobutane-1,2,4-tricarboxylic acid Chemical compound OC(=O)CCC(P(O)(O)=O)(C(O)=O)CC(O)=O SZHQPBJEOCHCKM-UHFFFAOYSA-N 0.000 abstract 1
- KBGHCNOQBKTDTH-UHFFFAOYSA-N OC(=O)P(=O)=O Chemical compound OC(=O)P(=O)=O KBGHCNOQBKTDTH-UHFFFAOYSA-N 0.000 abstract 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 59
- 238000012360 testing method Methods 0.000 description 43
- 239000003795 chemical substances by application Substances 0.000 description 24
- 230000002401 inhibitory effect Effects 0.000 description 23
- 238000002360 preparation method Methods 0.000 description 18
- 239000004480 active ingredient Substances 0.000 description 16
- 230000005764 inhibitory process Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 11
- 239000003814 drug Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- 229940079593 drug Drugs 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 239000011575 calcium Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 229910000975 Carbon steel Inorganic materials 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- 239000010962 carbon steel Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 239000002826 coolant Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 2
- 239000012964 benzotriazole Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000000116 mitigating effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021538 borax Inorganic materials 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 150000002462 imidazolines Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 230000003134 recirculating effect Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000004328 sodium tetraborate Substances 0.000 description 1
- 235000010339 sodium tetraborate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 208000016261 weight loss Diseases 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F14/00—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes
- C23F14/02—Inhibiting incrustation in apparatus for heating liquids for physical or chemical purposes by chemical means
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
A composite corrosion-retardant scaling inhibitor contains organic phosphoic acid, organic phosphocarboxylic acid which may be the hydroxyphosphonoacetic acid or the mixture of hydroxyphosphonoacetic acid and 2-phosphono-1,2,4-butane tricarboxylate, and the homopolymer or copolymer containing carboxyl. It is specially suitable for treating the circulated cooling water containing sulfur.
Description
Technical field
The present invention relates to a kind of composite slow-corrosion scale resistor and application thereof, relate to a kind of composite slow-corrosion scale resistor and the application in recirculated cooling water is handled thereof particularly.
Background technology
Usually oil refining apparatus be because of the strong high-sulpur crude of processing corrodibility can cause the corrosion failure of equipment, and the phenomenon of material from leakage in the recirculated water takes place; The sulfurous gas that produces of device (as hydrogen sulfide etc.) can leak in the atmosphere if poorly sealed or handle badly in addition, causes further by the absorption that water coolant dissolves near the water cooling tower.After S-contained substance enters recirculating cooling water system, water quality deterioration, conventional water treatment agent were lost efficacy, increased the weight of the corrosion and the fouling of circulating water system cold exchange device, and then the aggravation of the leakiness of material, vicious cycle formed.Along with China's processing import high-sulfur crude oil amount is increasing, equipment corrosion and material from leakage were gone into the recirculated water phenomenon and were become increasingly conspicuous, and the threat of production equipment safety, long-term operation were had the trend of increase in recent years.Therefore, searching is applicable to that the corrosion inhibiting and descaling agent of circulating cooling water containing sulfur is very necessary.
Sulfur-bearing recirculated water has two characteristics to the corrosion of equipment, and the one, harm is big, and the metallic surface is subjected to heteropical galvanic corrosion, forms lamellated peeling off and partial pitting corrosion, serious made equipment generation stress corrosion and ftractureing; The 2nd, corrosion speed is fast, and especially initial corrosion speed is fast, and speed just slows down after 400 hours, and this is relevant with the FeS protective film that produces.
US2466517 successfully adopts the imidazolines inhibiter to suppress H first
2S class material is to the corrosion of hardware; this class inhibiter is absorption membranous type inhibiter; by electronegativity bigger be that the polar group at center is adsorbed in the metallic surface with the nitrogen-atoms; change the structure of electrostatic double layer; improve the activation energy of metal ion polarization process; non-polar group leaves the metallic surface and aligns formation hydrophobicity protective membrane, inhibition metallic corrosion simultaneously.Therefore, the smooth more inhibiter corrosion mitigating effect in metallic surface is excellent more.In addition, in acidic aqueous solution, add organic amine substance, also can suppress H preferably as amides, quaternary ammonium salts
2S class material is to the corrosion of hardware, but above-mentioned inhibiter all is not suitable for the rough alkaline circulating water system of heat exchanger surface.
Refinery mainly contains two to the treatment measures of the recirculated water of sulfur compound at present, and the one, add heavy dose of inhibiter with the increase corrosion mitigating effect, the 2nd, a large amount of blowdowns also replenish fresh water to reduce the concentration of sulfide in the recirculated water.Though these measures have certain effect,, certain limitation is arranged all because sulfur-bearing recirculated water corrosion speed is fast.For the corrosion inhibitor formula that contains zine ion, zine ion easily and the sulfonium ion in the water generate the zinc sulphide precipitation and lost efficacy, so the dosage that strengthens inhibiter not only can not reduce corrosion speed sometimes, can aggravate fouling on the contrary, reduced the cooling performance of cold exchange device.The water system of most refineries is subjected to the blowdown quantitative limitation in addition, can't cause the erosion rate of equipment still higher the thoroughly displacement in time of sulfur-bearing recirculated water, and simultaneously, the consumption of water treatment agent, the consumption of fresh water and quantity of wastewater effluent all rise by a relatively large margin.
Summary of the invention
The objective of the invention is to overcome the above-mentioned defective of prior art, a kind of composite slow-corrosion scale resistor is provided.
Another object of the present invention is composite slow-corrosion scale resistor of the present invention is used for the processing of recirculated cooling water, especially for the processing of circulating cooling water containing sulfur.
For achieving the above object, the invention provides a kind of composite slow-corrosion scale resistor, comprising organic phospho acid, organic phosphine carboxylic acid with contain the carboxylic acid group polymer, described organic phosphine carboxylic acid is hydroxyethylidene diphosphonic acid guanidine-acetic acid (HPAA) or HPAA and 2-phosphonate group-1,2,4-butane tricarboxylate's (PBTCA) mixture.
Composite slow-corrosion scale resistor of the present invention is applicable to the processing of the processing of recirculated cooling water, particularly circulating cooling water containing sulfur.In the described recirculated cooling water sulfonium ion concentration be 0 or>0~2.5mg/L.
Organic phospho acid of the present invention be at least aly be selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid (HEDP), Amino Trimethylene Phosphonic Acid (ATMP), ethylene diamine tetra methylene phosphonic acid (EDTMP), diethylene triamine pentamethylene phosphonic, to the compound of two phosphono and sulfonics.
Prior art homopolymer that contains the carboxylic acid group that is used for water treatment and multipolymer open or that sell in market all can be used for the present invention.The carboxylic acid group polymer of containing of the present invention is preferably the homopolymer that contains the carboxylic acid group, copolymer, terpolymer is more preferably from polyacrylic acid (PAA), polymaleic acid, vinylformic acid (AA)/Propylene glycol monoacrylate (HPA) multipolymer, vinylformic acid/Propylene glycol monoacrylate (HPA)/acrylate copolymer, toxilic acid (acid anhydride)/acrylic 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).
When using copper material equipment in the circulation cooling water system, composite slow-corrosion scale resistor of the present invention also contains heterogeneous ring compound as copper material corrosion inhibitor, and preferred mercaptobenzothiazole and/or benzotriazole (BTA) are as copper material corrosion inhibitor.
Organic phospho acid of the present invention is 3~15mg/L with respect to the effective concentration of pending aqueous solution total amount, is preferably 4~10mg/L.
HPAA of the present invention is 4~25mg/L with respect to the effective concentration of pending aqueous solution total amount, is preferably 5~15mg/L.PBTCA of the present invention is 0~10mg/L with respect to the effective concentration of pending aqueous solution total amount, is preferably 2~6mg/L.
The carboxylic acid group polymer of containing of the present invention is 4~15mg/L with respect to the effective concentration of pending aqueous solution total amount, is preferably 6~10mg/L.
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 corrosion inhibiting and descaling agent of the present invention, only need be made into a kind of solution, the reinforced order of component is unimportant, as can be with organic phospho acid, phosphine carboxylic acid, contain carboxylic acid-based copolymer and copper material corrosion inhibitor (if any) and water and be made into liquid medicine by predetermined mixed and just make required composite slow-corrosion scale resistor.
When composite scale-inhibiting corrosion inhibitor of the present invention was used for the cycle of treatment water coolant, inhibition and scale-inhibiting properties were all good.
Composite scale-inhibiting corrosion inhibitor of the present invention has the following advantages when being used to handle circulating cooling water containing sulfur:
1. can solve circulating cooling water containing sulfur to the corrosion that equipment causes, make Corrosion rate in Carbon Steel less than 0.1mm/a.
2. can not produce the equipment scaling that brings owing to the zinc sulphide precipitation.
3. need not system is thoroughly replaced after leaking, save medicament expense, fresh water rate and effluent charge.
4. simple to operate, convenient and swift, safe and effective.
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 rotary hanging plate corrosion test of following embodiment is write with reference to production department of China PetroChemical Corporation and development division (1993, the publication of general petrochemical works, Anqing information center) " rotary hanging plate weight-loss method " carries out in, test temperature is 45 ℃, the test piece rotating speed is 75 rev/mins (rpm), test period is 72h, the lacing film material is the 20# carbon steel, keeps the water yield constant in the test, replenishes with deionized water if any evaporation.Static-state scale inhibition is tested with reference to GB/T 16632-1996 " mensuration of water conditioner scale-inhibiting properties-tosca method ", but does not add borax buffer solution, and test water is the water distribution of on-the-spot fresh water.
Embodiment 1
Process for preparation: preparation composite slow-corrosion scale resistor 100g
Take by weighing the 22.9g active ingredient and be 50% ATMP, 17.9g active ingredient is 40% HPAA, 28.6g (mass ratio is AA/AMPS=70/30 to the AA/AMPS copolymer of solid content about 30%, limit viscosity number is 0.072dl/g in the time of 30 ℃), active ingredient is 50% PBTCA 11.4g, be dissolved in the 19.2g water, it is fully dissolved, shake up, promptly obtain the 100g corrosion inhibiting and descaling agent of required preparation.
When adding in test water by the drug concentration of 70mg/L with the corrosion inhibiting and descaling agent for preparing, the effective concentration of ATMP, HPAA, AA/AMPS copolymer, PBTCA is respectively 8mg/L, 5mg/L, 6mg/L, 4mg/L in the water.
Rotary hanging plate corrosion test test water quality is: Ca
2+400mg/L, total alkalinity 350mg/L, Cl
-415mg/L, S
2-0.5mg/L, Ca wherein
2+, total alkalinity is all with CaCO
3Meter, down together.
Static-state scale inhibition test test water quality is: Ca
2+550mg/L, total alkalinity 600mg/L, S
2-0.5mg/L.
Embodiment 2
Process for preparation: preparation composite slow-corrosion scale resistor 100g
Take by weighing the 17.1g active ingredient and be 50% HEDP, 21.4g active ingredient is 40% HPAA, 28.6g (Beijing Yanhua Xingye Technology Development Co., Ltd. produces the ZF-311 of solid content about 30%, be vinylformic acid/methyl acrylate/Propylene glycol monoacrylate terpolymer), solid content is 30%PAA (30 ℃ time the limit viscosity number be 0.068dl/g) 9.5g, be dissolved in the 23.4g water, it is fully dissolved, shake up, promptly obtain the 100g corrosion inhibiting and descaling agent of required preparation.
When adding in test water by the drug concentration of 70mg/L with the corrosion inhibiting and descaling agent for preparing, the effective concentration of HEDP, HPAA, ZF-311, PAA is respectively 6mg/L, 6mg/L, 6mg/L, 2mg/L in the water.
Rotary hanging plate corrosion test test water quality is: Ca
2+285mg/L, total alkalinity 340mg/L, Cl
-210mg/L, S
2-0.5mg/L.
Static-state scale inhibition test test water quality is with embodiment 1.
Embodiment 3
Process for preparation: preparation composite slow-corrosion scale resistor 100g
Take by weighing the 17.1g active ingredient and be 50% HEDP, 28.6g active ingredient is 40% HPAA, 38.1g (mass ratio is AA/AMPS/HPA=60/20/20 to the AA/AMPS/HPA terpolymer of solid content about 30%, limit viscosity number is 0.078dl/g in the time of 30 ℃), be dissolved in the 16.2g water, it is fully dissolved, shake up, promptly obtain the 100g corrosion inhibiting and descaling agent of required preparation.
When adding in test water by the drug concentration of 70mg/L with the corrosion inhibiting and descaling agent for preparing, the effective concentration of HEDP, HPAA, AA/AMPS/HPA terpolymer is respectively 6mg/L, 8mg/L, 8mg/L in the water.
Rotary hanging plate corrosion test test water quality is: Ca
2+385mg/L, total alkalinity 440mg/L, Cl
-390mg/L, S
2-1.0mg/L.
Static-state scale inhibition test test water quality is with embodiment 1.
Embodiment 4
Process for preparation: preparation composite slow-corrosion scale resistor 100g
Take by weighing the 11.4g active ingredient and be 50% HEDP, 35.7g active ingredient is 40% HPAA, 19.1g (Beijing Yanhua Xingye Technology Development Co., Ltd. produces the ZF-311 of solid content about 30%, be vinylformic acid/methyl acrylate/Propylene glycol monoacrylate terpolymer), the 5.7g active ingredient is 50% PBTCA, solid content is 30% PAA (30 ℃ time the limit viscosity number be 0.080dl/g) 9.5g, is dissolved in the 18.6g water, and it is fully dissolved, shake up, promptly obtain the 100g corrosion inhibiting and descaling agent of required preparation.
When adding in test water by the drug concentration of 70mg/L with the corrosion inhibiting and descaling agent for preparing, the effective concentration of HEDP, HPAA, ZF-311, PBTCA, PAA is respectively 4mg/L, 10mg/L, 4mg/L, 2mg/L, 2mg/L in the water.
Rotary hanging plate corrosion test and static-state scale inhibition test test water quality are with embodiment 3.
Embodiment 5
Process for preparation: preparation composite slow-corrosion scale resistor 100g
Take by weighing the 17.1g active ingredient and be 50% HEDP, 42.9g active ingredient is 40% HPAA, 28.6g (first promise rosy clouds peak, Changzhou Fine Chemical Co., Ltd produces the XF-322 of solid content about 30%, be maleic anhydride/acrylic copolymer), the 5.7g active ingredient is 50% PBTCA, be dissolved in the 5.7g water, it is fully dissolved, shake up, promptly obtain the 100g corrosion inhibiting and descaling agent of required preparation.
When adding in test water by the drug concentration of 70mg/L with the corrosion inhibiting and descaling agent for preparing, the effective concentration of HEDP, HPAA, XF-322, PBTCA is respectively 6mg/L, 12mg/L, 6mg/L, 2mg/L in the water.
Rotary hanging plate corrosion test test water quality is: Ca
2+385mg/L, total alkalinity 440mg/L, Cl
-390mg/L, S
2-2.0mg/L.
Static-state scale inhibition test test water quality is with embodiment 1.
Embodiment 6
Process for preparation: preparation composite slow-corrosion scale resistor 100g
Take by weighing the 25.7g active ingredient and be 50% ATMP, 17.9g active ingredient is 40% HPAA, 33.3g the PAA of solid content about 30% (30 ℃ time the limit viscosity number be 0.080dl/g), active ingredient are 50% PBTCA 14.3g, be dissolved in the 8.8g water, it is fully dissolved, shake up, promptly obtain the 100g corrosion inhibiting and descaling agent of required preparation.
When adding in test water by the drug concentration of 70mg/L with the corrosion inhibiting and descaling agent for preparing, the effective concentration of ATMP, HPAA, PAA, PBTCA is respectively 9mg/L, 5mg/L, 7mg/L, 5mg/L in the water.
Rotary hanging plate corrosion test test water quality is: Ca
2+400mg/L, total alkalinity 350mg/L, Cl
-415mg/L, S
2-0mg/L.
Static-state scale inhibition test test water quality is with embodiment 1.
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 1.
The anticorrosion-antiscaling effect of table 1 corrosion inhibiting and descaling agent
Embodiment | Corrosion of carbon steel speed (mm/a) | Resistance calcium carbonate scale rate (%) |
Embodiment 1 | ????0.070 | ????82 |
Embodiment 2 | ????0.035 | ????74 |
Embodiment 3 | ????0.034 | ????76 |
Embodiment 4 | ????0.030 | ????78 |
Embodiment 5 | ????0.055 | ????79 |
Embodiment 6 | ????0.010 | ????88 |
Comparative Examples 1-2
Use prescription 1 and prescription 2 as a comparison, add 70mg/L, carry out static-state scale inhibition test and rotary hanging plate corrosion test, experimental technique is identical with embodiment 3 with experiment water quality.
When prescription 1 drug concentration by 70mg/L adds in test water, the composition of each single agent and effective concentration are respectively HEDP 12mg/L, PBTCA 4mg/L, AA/AMPS copolymer (mass ratio is AA/AMPS=70/30, and limit viscosity number is 0.072dl/g in the time of 30 ℃) 6mg/L in the water.When prescription 2 drug concentrations by 70mg/L add in test water, the composition of each single agent and effective concentration are respectively HPAA 8mg/L, PBTCA 4mg/L, AA/AMPS/HPA terpolymer (mass ratio is AA/AMPS/HPA=60/20/20, and limit viscosity number is 0.078dl/g in the time of 30 ℃) 8mg/L in the water.The resistance calcium carbonate scale rate and the erosion rate of experiment see Table 2.
The inhibition of table 2 Comparative Examples and scale inhibition experimental result
Comparative Examples | Corrosion inhibiting and descaling agent | Add concentration (mg/L) | Corrosion of carbon steel speed (mm/a) | Resistance calcium carbonate scale rate (%) |
????1 | Prescription 1 | ????70 | ????0.583 | ????78 |
????2 | Prescription 2 | ????70 | ????0.678 | ????80 |
By the data of the foregoing description and Comparative Examples as can be seen: the corrodibility of circulating cooling water containing sulfur is strong, when selecting for use conventional corrosion inhibiting and descaling agent to carry out the corrosion-mitigation scale-inhibition test, erosion rate is excessive, illustrates that conventional corrosion inhibiting and descaling agent not too is fit to the processing of circulating cooling water containing sulfur; And carrying out corrosion-mitigation scale-inhibition when test with corrosion-mitigation scale-inhibition agent prescription of the present invention, its corrosion inhibition and scale-inhibiting properties are all better, and the processing that is suitable for circulating cooling water containing sulfur with corrosion-mitigation scale-inhibition agent prescription of the present invention is described.
Claims (9)
1, a kind of composite slow-corrosion scale resistor, comprising organic phospho acid, organic phosphine carboxylic acid with contain the carboxylic acid group polymer, described phosphine carboxylic acid is hydroxyethylidene diphosphonic acid guanidine-acetic acid or hydroxyethylidene diphosphonic acid guanidine-acetic acid and 2-phosphonate group-1,2,4-butane tricarboxylate's mixture.
2, composite slow-corrosion scale resistor according to claim 1, it is characterized in that described organic phospho acid be at least aly be selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to the compound of two phosphono and sulfonics.
3, composite slow-corrosion scale resistor according to claim 1 and 2, it is characterized in that the described carboxylic acid group polymer of containing is homopolymer, copolymer or terpolymer are preferably from polyacrylic acid, polymaleic acid, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/acrylate copolymer, toxilic acid (acid anhydride)/acrylic 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 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.
4, according to each described composite slow-corrosion scale resistor 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: organic phospho acid is 3~15mg/L, is preferably 4~10mg/L; The hydroxyethylidene diphosphonic acid guanidine-acetic acid is 4~25mg/L, is preferably 5~15mg/L; 2-phosphonate group-1,2, the 4-butane tricarboxylate is 0~10mg/L, is preferably 2~6mg/L; Containing the carboxylic acid group polymer is 4~15mg/L, is preferably 6~10mg/L.
5, the purposes of the described composite slow-corrosion scale resistor of claim 1 is characterized in that the described composite slow-corrosion scale resistor of claim 1 is used for the processing of recirculated cooling water.
6, the purposes of composite slow-corrosion scale resistor according to claim 5, wherein said recirculated cooling water are circulating cooling water containing sulfur, and wherein the sulfonium ion concentration range is>0~2.5mg/L.
7, according to the purposes of claim 5 or 6 described composite slow-corrosion scale resistors, it is characterized in that described organic phospho acid be at least aly be selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, Amino Trimethylene Phosphonic Acid, ethylene diamine tetra methylene phosphonic acid, diethylene triamine pentamethylene phosphonic, to the compound of two phosphono and sulfonics.
8, purposes according to each described composite slow-corrosion scale resistor of claim 5-7, it is characterized in that the described carboxylic acid group polymer of containing is homopolymer, copolymer or terpolymer are preferably from polyacrylic acid, polymaleic acid, vinylformic acid/Propylene glycol monoacrylate multipolymer, vinylformic acid/Propylene glycol monoacrylate/acrylate copolymer, toxilic acid (acid anhydride)/acrylic 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 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, according to the purposes of each described composite slow-corrosion scale resistor of claim 5-8, it is characterized in that with respect to the effective concentration of pending each component of aqueous solution total amount being: organic phospho acid is 3~15mg/L, is preferably 4~10mg/L; The hydroxyethylidene diphosphonic acid guanidine-acetic acid is 4~25mg/L, is preferably 5~15mg/L; 2-phosphonate group-1,2, the 4-butane tricarboxylate is 0~10mg/L, is preferably 2~6mg/L; Containing the carboxylic acid group polymer is 4~15mg/L, is preferably 6~10mg/L.
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