CN104909471A - Special corrosion and scale inhibitor for closed system, and preparation method thereof - Google Patents
Special corrosion and scale inhibitor for closed system, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a special corrosion and scale inhibitor for a closed system, and a preparation method thereof. The special corrosion and scale inhibitor comprises, by mass, 25-40% of sulfonicmethaneamino polyepoxysuccinic acid, 20-30% of a graphene oxide water dispersion, 12-30% of a maleic acid-acrylic acid copolymer, 3-5% of sodium molybdate, 3-6% of cocoanut fatty acid diethanolamide and 15-40% of an aqueous solution of zinc sulfate. The special corrosion and scale inhibitor for the closed system can realizes trace quantity elimination of pollutants through synergistic effect of all components, has greatly improved corrosion and scale inhibition performances after compounding the components, can effectively realize physical adsorption and chemical adsorption synergism of pollutants, can be used in water with a wide pH range and wide temperature, and has the advantages of simple production process, no discharge of three wastes, good stability and water solubility, biodegradable, nontoxic, phosphorus-free and corrosion-free main components, small dosage, and environmental protection.
Description
Technical field
The invention belongs to water-treatment technology field, relate to a kind of Scale inhibitors, be specifically related to a kind of closed system special corrosion and scale inhibitor and preparation method thereof.
Background technology
At present, in circulating water system inhibiter particularly in Closed Cycle water system metallic corrosion situation serious, owing to needing to use the intermediate material secondary refrigerant that the cold produced by refrigerator sends cooled object in Closed Cycle water system, secondary refrigerant stable in properties, miscible with water, the temperature of solidification of its solution becomes with concentration, usually with their aqueous solution as secondary refrigerant, but its aqueous solution is corrosive more, at high temperature run for a long time, to various corrosion of metal all very significantly and easily fouling, have a strong impact on the work-ing life of sealing and circulating water system, and be scarcely applicable to sealing and circulating water system for the water treatment agent with stronger corrosion inhibition of general recirculated water, water conditioner as having corrosion and scale inhibition performance at present is both at home and abroad mainly chromic salt, silicate, molybdate, nitrite, organophosphate and other mixture, chromic salt, nitrite pollution environment, silicate has fouling risk, and the phosphorous formula such as organophosphate, easily secondary pollution is caused to water body, do not meet environment protection requirement, and product performance are uneven, scale-inhibiting properties is not high, function singleness.Therefore, research and develop a kind of practical environment-friendly type closed system special corrosion and scale inhibitor to be widely used value.
Summary of the invention
The object of the invention is to the deficiency of the existence for prior art, the closed system special corrosion and scale inhibitor that a kind of environmental type is without phosphorus is provided.
Present invention also offers the preparation method of above-mentioned closed system special corrosion and scale inhibitor.
The present invention is achieved through the following technical solutions:
A kind of closed system special corrosion and scale inhibitor of the present invention, comprises the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 25 ~ 40%,
Graphene oxide aqueous dispersions 20 ~ 30%,
Maleic acid-acrylic acid copolymer 12 ~ 30%,
Sodium orthomolybdate 3 ~ 5%,
Cocoanut fatty acid diethanolamide 3 ~ 6%,
Zinc sulfate solution 15 ~ 40%.
Described graphene oxide aqueous dispersions, concentration is 1.5 ~ 2mg/ml, and the graphene oxide in graphene oxide aqueous dispersions is the modified graphene that carbon-coating surface has hydroxyl, carboxyl or carbonyl functional group, and the number of plies is 15 ~ 20 layers; Particle diameter is 5 ~ 10nm;
Described maleic acid-acrylic acid copolymer, solids content 45 ~ 55wt%, free monomer (in toxilic acid)≤9.0wt%;
Described zinc sulfate solution massfraction is 10 ~ 15%.
Above-mentioned closed system special corrosion and scale inhibitor, the component of preferred following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 30%,
Graphene oxide aqueous dispersions 22%,
Maleic acid-acrylic acid copolymer 16%,
Sodium orthomolybdate 4%,
Cocoanut fatty acid diethanolamide 5%,
Zinc sulfate solution 23%.
Closed system special corrosion and scale inhibitor of the present invention, working concentration is 10 ~ 150mg/L, preferably 10 ~ 50mg/l.
Closed system special corrosion and scale inhibitor of the present invention, its pH value scope of application is 7 ~ 13, and temperature applicable range is 0 ~ 120 DEG C; Preferred pH value scope 7 ~ 11.5, temperature range 20 ~ 80 DEG C.
The preparation method of above-mentioned closed system special corrosion and scale inhibitor is:
Sulfonic acid methylamino poly-epoxy succinic acid, graphene oxide aqueous dispersions, maleic acid-acrylic acid copolymer and Sodium orthomolybdate are mixed in proportion, be heated to 65 ~ 95 DEG C, drip zinc sulfate solution in 1.5 ~ 2.0h, supersound process 15 ~ 20min, is then warming up to 105 DEG C, add cocoanut fatty acid diethanolamide, backflow 0.5 ~ 1h, then material is cooled to 75 ~ 85 DEG C, filtered while hot, filtrate is lowered the temperature, and is closed system special corrosion and scale inhibitor of the present invention.
Sulfonic acid methylamino poly-epoxy succinic acid (SMA/PESA) is a kind of multifunctional airtight system-specific corrosion inhibiting and descaling agent of excellence, compared with PESA, scale-inhibiting properties and corrosion inhibition significantly improve, there is good composite synergistic effect, containing multiple hydrophilic radicals such as carboxyl, ether, amido, hydroxyl, sulfonic groups in structure, it not only can improve compound dissolution effectively, also can form coordination compound in metallic surface and chemisorption occur, thus enhancement is played to its scale-inhibiting properties, the synergistic effect of multiple functional group makes its corrosion and scale inhibition performance significantly improve.
Graphene oxide aqueous dispersions, is prepared by graphene oxide film and obtains, and can not precipitate, and graphene oxide is a kind of flexible material of non-traditional kenel, has polymkeric substance, colloid, film, and amphiphilic characteristic.Graphene oxide is regarded as hydroaropic substance for a long time, and it has superior dispersiveness in water, but, related experiment result shows, in fact graphene oxide has amphipathic, graphene oxide can as interfacial agent Presence of an interface, and reduce the energy between interface.Graphene oxide is similar to carbon nanotube structure, there is the functional group that higher specific surface area and surface are abundant, its specific surface area can reach 2600 meters squared per gram, its surperficial a large amount of active group is as carboxyl, carbonyl, hydroxyl, epoxy group(ing) etc., absorption for pollutent especially heavy metal provides sufficient avtive spot, the trace that can realize pollutent is eliminated, and the synergistic effect of multiple functional group can improve compound dissolution effectively simultaneously, and its scale-inhibiting properties is significantly improved.
Cocoanut fatty acid diethanolamide is a kind of nonionogenic tenside, soluble in water, have good foaming, steady bubble, function such as infiltration decontamination, anti-hard water etc., and stability is higher, is easy to biological degradation, and compatibleness is good, insensitive to hard water.
Maleic acid-acrylic acid copolymer (MA/AA), have very strong dissemination to carbonate etc., thermostability is high, can use, have good consistency and synergistic function with other water treatment agent under the mal-conditions such as 300 DEG C of high temperature.To the generation of the incrustation scale comprising phosphoric acid salt, there is good restraining effect, scale-inhibiting properties and resistance to elevated temperatures excellence.
Sodium orthomolybdate, it is a kind of New Type Water Treatment Chemicals that application is more at present, toxicity is lower, environmental pollution pollution level is low, normal with poly-phosphate, gluconate, zinc salt, the composite use of this sick triazole, the usage quantity of molybdate can be reduced, raising corrosion mitigating effect, molybdate thermostability is high, can be used for the circulating water system of the high and local superheating of heat flow density.
Zinc sulfate, ionizes out Zn in water
2+, with sulfonic acid methylamino poly-epoxy succinic acid and Sodium orthomolybdate composite, have synergistic function, corrosion inhibition rate significantly strengthens, and also can provide sterilization simultaneously.
In closed system special corrosion and scale inhibitor of the present invention, with sulfonic acid methylamino poly-epoxy succinic acid for corrosion inhibiting and descaling agent main component, Sodium orthomolybdate and maleic acid-acrylic acid copolymer are auxiliary corrosion inhibiting and descaling agent, add graphene oxide aqueous dispersions and cocoanut fatty acid diethanolamide, the closed system special corrosion and scale inhibitor that obtained a kind of environmental protection is without phosphorus simultaneously.Wherein sulfonic acid methylamino poly-epoxy succinic acid, Sodium orthomolybdate and maleic acid-acrylic acid copolymer anticorrosion-antiscaling effect are excellent, and the composite rear scale inhibition synergistic function of three is obvious, and has good degradation property, does not pollute environment.After adding zinc salt, sulfonic acid methylamino poly-epoxy succinic acid, Sodium orthomolybdate and Zn
2+there is good synergistic effect, the slowly-releasing scale inhibition effect of the metals such as carbon steel is obviously strengthened.Graphene oxide aqueous dispersions, good with sulfonic acid methylamino poly-epoxy succinic acid, Sodium orthomolybdate and maleic acid-acrylic acid copolymer compatibility, there is good absorption property simultaneously, can trace removal of pollutants.Mentioned component and tensio-active agent cocoanut fatty acid diethanolamide composite after, water-soluble and stability strengthens, and can realize long time stored, obvious to pollutent especially heavy metal compatibilization, especially to Ca
2+, CO
3 2-, SO
4 2-plasma scale inhibition effect is remarkable; closed system special corrosion and scale inhibitor of the present invention; can be adsorbed on metallic surface and form the very thin film of one deck; protection metal, from the corrosion of air and hazardous medium, can suppress carbon steel, copper effectively; stainless steel; the corrosions of metal such as aluminium, can use, be particularly useful for the corrosion-mitigation scale-inhibition of sealing and circulating water system in wider feedwater pH scope and temperature.
Compared with prior art, the beneficial effect of closed system special corrosion and scale inhibitor of the present invention and preparation method thereof is:
(1) synergistic effect of multiple functional group that each component contains can improve compound dissolution effectively, the trace that can realize pollutent is eliminated, its corrosion and scale inhibition performance is made significantly to improve after composite, effectively can realize the synergy of pollutent physical adsorption and chemisorption, can use in wider feedwater pH scope and temperature.
(2) production technique is simple, and without " three wastes " discharge, stability and good water solubility, main component is biodegradable, nontoxic, without phosphorus, pollution-free, non-corrosiveness, and less developer is environmentally friendly.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in detail.Following examples and comparative example will contribute to those skilled in the art and understand the present invention further, but not limit the present invention in any form.To those of ordinary skill in the art, the improvement made without departing from the inventive concept of the premise, all belongs to protection scope of the present invention.
The embodiment of the present invention each raw material used is bought by market and is obtained;
Graphene oxide aqueous dispersions used is that Nanjing Xian Feng Nono-material Science & Technology Ltd. produces, concentration is 1.5mg/ml, contained graphene oxide is the modified graphene that carbon-coating surface has hydroxyl, carboxyl or carbonyl functional group, and the number of plies is 15 ~ 20 layers, and particle diameter is 5 ~ 10nm;
Maleic acid-acrylic acid copolymer used, specification is: solids content 48wt%, free monomer (in toxilic acid) 9.0wt%, number-average molecular weight 450 ~ 700;
Embodiment 1
The present embodiment closed system special corrosion and scale inhibitor, comprises the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 30%,
Graphene oxide aqueous dispersions 22%,
Maleic acid-acrylic acid copolymer 16%,
Sodium orthomolybdate 4%,
Cocoanut fatty acid diethanolamide 5%,
Zinc sulfate solution 23%,
Described zinc sulfate solution massfraction is 12%.
The preparation method of the present embodiment closed system special corrosion and scale inhibitor is:
Take sulfonic acid methylamino poly-epoxy succinic acid, graphene oxide aqueous dispersions, maleic acid-acrylic acid copolymer and Sodium orthomolybdate in proportion respectively, add successively in container, mixing, be heated to 90 DEG C, drip zinc sulfate solution in 2.0h, supersound process 20min, is then warming up to 105 DEG C, add cocoanut fatty acid diethanolamide, backflow 1h, then material is cooled to 80 DEG C, filtered while hot, filtrate is lowered the temperature, and is the present embodiment closed system special corrosion and scale inhibitor.
Embodiment 2
The present embodiment closed system special corrosion and scale inhibitor, comprises the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 25%,
Graphene oxide aqueous dispersions 20%,
Maleic acid-acrylic acid copolymer 12%,
Sodium orthomolybdate 3%,
Cocoanut fatty acid diethanolamide 3%,
Zinc sulfate solution 37%,
Described zinc sulfate solution massfraction is 12%.
The preparation method of the present embodiment closed system special corrosion and scale inhibitor is:
Take sulfonic acid methylamino poly-epoxy succinic acid, graphene oxide aqueous dispersions, maleic acid-acrylic acid copolymer and Sodium orthomolybdate in proportion respectively, add successively in container, mixing, be heated to 80 DEG C, drip zinc sulfate solution in 1.5h, supersound process 15min, is then warming up to 105 DEG C, add cocoanut fatty acid diethanolamide, backflow 0.5h, then material is cooled to 75 DEG C, filtered while hot, filtrate is lowered the temperature, and is the present embodiment closed system special corrosion and scale inhibitor.
Embodiment 3
The present embodiment closed system special corrosion and scale inhibitor, comprises the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 40%,
Graphene oxide aqueous dispersions 22%,
Maleic acid-acrylic acid copolymer 15%,
Sodium orthomolybdate 4%,
Cocoanut fatty acid diethanolamide 4%,
Zinc sulfate solution 15%.
Described zinc sulfate solution massfraction is 12%.
The preparation method of the present embodiment closed system special corrosion and scale inhibitor is:
Take sulfonic acid methylamino poly-epoxy succinic acid, graphene oxide aqueous dispersions, maleic acid-acrylic acid copolymer and Sodium orthomolybdate in proportion respectively, add successively in container, mixing, be heated to 65 DEG C, drip zinc sulfate solution in 2.0h, supersound process 20min, is then warming up to 105 DEG C, add cocoanut fatty acid diethanolamide, backflow 1h, then material is cooled to 85 DEG C, filtered while hot, filtrate is lowered the temperature, and is the present embodiment closed system special corrosion and scale inhibitor.
Embodiment 4
The present embodiment closed system special corrosion and scale inhibitor, comprises the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 30%,
Graphene oxide aqueous dispersions 30%,
Maleic acid-acrylic acid copolymer 12%,
Sodium orthomolybdate 5%,
Cocoanut fatty acid diethanolamide 6%,
Zinc sulfate solution 17%,
Described zinc sulfate solution massfraction is 10%, and preparation method is with embodiment 1.
Embodiment 5
The present embodiment closed system special corrosion and scale inhibitor, comprises the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 25%,
Graphene oxide aqueous dispersions 20%,
Maleic acid-acrylic acid copolymer 30%,
Sodium orthomolybdate 4%,
Cocoanut fatty acid diethanolamide 5%,
Zinc sulfate solution 16%,
Described zinc sulfate solution massfraction is 15%, and preparation method is with embodiment 1.
Embodiment 6
The present embodiment closed system special corrosion and scale inhibitor, comprises the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 35%,
Graphene oxide aqueous dispersions 25%,
Maleic acid-acrylic acid copolymer 15%,
Sodium orthomolybdate 5%,
Cocoanut fatty acid diethanolamide 5%,
Zinc sulfate solution 15%,
Described zinc sulfate solution massfraction is 12%, and preparation method is with embodiment 1.
Comparative example 1
Sulfonic acid methylamino poly-epoxy succinic acid (MA/PESA) is replaced with reference to embodiment 1, SPESA.
Comparative example 2
With reference to embodiment 1, do not add graphene oxide aqueous dispersions, comprise the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 30%,
Sodium orthomolybdate 22%,
Maleic acid-acrylic acid copolymer 16%,
Cocoanut fatty acid diethanolamide 5%,
Zinc sulfate solution 27%.
Comparative example 3
A kind of corrosion inhibiting and descaling agent:
AL-one 70%，
AA/AHPS co-polymer of sulfonate 12%,
KOH 1%，
All the other are deionized water.
Preparation method: raw material adds in container in proportion successively, stirring at room temperature 1 ~ 1.5h.
Application test and result
1, test sample and grouping:
Experimental group 1 ~ 6, uses the closed system special corrosion and scale inhibitor that the present invention obtains, respectively corresponding embodiment 1 ~ 6;
Control group 1,2 and 3, use the corrosion inhibiting and descaling agent that comparative example 1,2 and 3 is obtained respectively, A is sulfonic acid methylamino poly-epoxy succinic acid, and B is Sodium orthomolybdate, and C is maleic acid-acrylic acid copolymer, and D is zinc sulfate solution.
2, CaCO is hindered
3performance measurement
Tosca method principle: be prepared into test solution with the preparation water containing a certain amount of bicarbonate radical and calcium ion and water conditioner.Calcium hydrogen carbonate accelerate decomposition is impelled to be CaCO in a heated condition
3.The Ca in test solution is measured after reaching balance
2+concentration, Ca
2+concentration is larger, and then this medicament scale-inhibiting properties is better.
Static resistance CaCO
3test conditions: with deionized water configuration 500ml concentration 15mg/L corrosion inhibiting and descaling agent, Ca
2+mass concentration 260mg/L, HCO
3-mass concentration 760mg/L, and regulate pH to be 9.0 with sodium hydroxide, be then statically placed in water bath with thermostatic control, temperature 80 DEG C, after insulation 10h, cooling, filters with the millipore filter of 0.22 μm, measures Ca by EDTA method
2+concentration, does blank test simultaneously.
Scale inhibition performance η calculates as follows:
η＝(C
1-C
0)/(C
2-C
0)×100%
C
1-add the calcium ion concn after test solution test after corrosion inhibiting and descaling agent, mg/L
C
0-do not add the calcium ion concn after the blank test solution test of corrosion inhibiting and descaling agent, mg/L
C
2calcium ion concn in the test solution prepared before-test, mg/L.
3, CaSO is hindered
4performance measurement
Test conditions: with deionized water configuration 500ml concentration 15mg/L corrosion inhibiting and descaling agent, Ca
2+mass concentration 260mg/L, SO
4 2-mass concentration 760mg/L, and regulate pH to be 9.0 with sodium hydroxide, be then statically placed in water bath with thermostatic control, temperature 80 DEG C, after insulation 10h, cooling, filters with the millipore filter of 0.22 μm, measures Ca by EDTA method
2+concentration, does blank test simultaneously.
Method of calculation are with reference to resistance CaCO
3performance measurement.
4, dispersing iron oxide performance measurement
Test conditions: with deionized water configuration 500ml concentration 15mg/L corrosion inhibiting and descaling agent, Ca
2+mass concentration 60mg/L, Fe
2+mass concentration 10mg/L, and regulate pH to be 9.0 with the borax of mass concentration 15%, and after stable, rapid stirring 15min, then be statically placed in water bath with thermostatic control, temperature 50 C, after insulation 10h, cooling, get supernatant liquid, measure transmittance (420nm) with spectrophotometric, transmittance is less, and dispersing iron oxide performance is better.
5, corrosion inhibition test
Test water: total hardness is 645mg/L, Ca
2+for 455mg/L, total alkalinity is 348mg/L, SO
4 2-for
140mg/L, Cl
-for 131mg/L.
Dosing: 25mg/L
Test method: adopt rotary hanging plate weight-loss method: carry out corrosion inhibition evaluation according to HG/T2159-91 method, test temperature: 50 DEG C, speed of rotation: 80r/min, test period: 72h, material is stainless steel, and it the results are shown in Table 1.
6, the compatible performance measurement with flocculation agent
With flocculant poly aluminum chloride (PAC) and anionic polyacrylamide, cationic polyacrylamide (PAM) compatibility test.
7, concrete outcome is as table 1
Table 1 performance measurement result
The above results shows, closed system special corrosion and scale inhibitor of the present invention has good scale inhibition and corrosion inhibition, and over-all properties is better, and cost performance is higher.
Claims (8)
1. a closed system special corrosion and scale inhibitor, is characterized in that, comprises the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 25 ~ 40%,
Graphene oxide aqueous dispersions 20 ~ 30%,
Maleic acid-acrylic acid copolymer 12 ~ 30%,
Sodium orthomolybdate 3 ~ 5%,
Cocoanut fatty acid diethanolamide 3 ~ 6%,
Zinc sulfate solution 15 ~ 40%.
2. closed system special corrosion and scale inhibitor according to claim 1, it is characterized in that: described graphene oxide aqueous dispersions, concentration is 1.5 ~ 2mg/ml, graphene oxide in graphene oxide aqueous dispersions is the modified graphene that carbon-coating surface has hydroxyl, carboxyl or carbonyl functional group, the number of plies is 15 ~ 20 layers, and particle diameter is 5 ~ 10nm.
3. closed system special corrosion and scale inhibitor according to claim 1, is characterized in that: described maleic acid-acrylic acid copolymer, solids content 45 ~ 55wt%, free monomer (in toxilic acid)≤9.0wt%.
4. closed system special corrosion and scale inhibitor according to claim 1, is characterized in that: described zinc sulfate solution massfraction is 10 ~ 15%.
5. closed system special corrosion and scale inhibitor according to claim 1, is characterized in that, comprises the component of following mass percentage:
Sulfonic acid methylamino poly-epoxy succinic acid 30%,
Graphene oxide aqueous dispersions 22%,
Maleic acid-acrylic acid copolymer 16%,
Sodium orthomolybdate 4%,
Cocoanut fatty acid diethanolamide 5%,
Zinc sulfate solution 23%.
6. the closed system special corrosion and scale inhibitor according to the arbitrary claim of 1-5, is characterized in that: working concentration is 10 ~ 150mg/L, and its pH value scope of application is 7 ~ 13, and temperature applicable range is 0 ~ 120 DEG C.
7. closed system special corrosion and scale inhibitor according to claim 6, is characterized in that: working concentration is 10 ~ 50mg/l, and its pH value scope of application is 7 ~ 11.5, and temperature applicable range is 20 ~ 80 DEG C.
8. the preparation method of closed system special corrosion and scale inhibitor described in the arbitrary claim of above-mentioned 1-5, it is characterized in that: by sulfonic acid methylamino poly-epoxy succinic acid, graphene oxide aqueous dispersions, maleic acid-acrylic acid copolymer and Sodium orthomolybdate are mixed in proportion, be heated to 65 ~ 95 DEG C, zinc sulfate solution is dripped in 1.5 ~ 2.0h, supersound process 15 ~ 20min, then 105 DEG C are warming up to, add cocoanut fatty acid diethanolamide, backflow 0.5 ~ 1h, again material is cooled to 75 ~ 85 DEG C, filtered while hot, filtrate is lowered the temperature, be closed system special corrosion and scale inhibitor of the present invention.
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| CN106277378A (en) * | 2016-08-30 | 2017-01-04 | 山东胜伟园林科技有限公司 | A kind of degradable antisludging agent and preparation method thereof |
| CN108017163A (en) * | 2016-10-31 | 2018-05-11 | 中国石油化工股份有限公司 | Non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and the processing method of recirculated cooling water |
| CN108017163B (en) * | 2016-10-31 | 2019-11-12 | 中国石油化工股份有限公司 | The processing method of non-Phosphorus composite anti incrustation eorrosion snhibiter and its application and recirculated cooling water |
| CN111377549A (en) * | 2020-03-13 | 2020-07-07 | 大唐绥化热电有限公司 | Special corrosion and scale inhibitor for recycling reclaimed water in power plant and preparation method thereof |
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