CN110746932B - Short-term antirust low-chlorine snow-melting agent and preparation method thereof - Google Patents
Short-term antirust low-chlorine snow-melting agent and preparation method thereof Download PDFInfo
- Publication number
- CN110746932B CN110746932B CN201911128602.4A CN201911128602A CN110746932B CN 110746932 B CN110746932 B CN 110746932B CN 201911128602 A CN201911128602 A CN 201911128602A CN 110746932 B CN110746932 B CN 110746932B
- Authority
- CN
- China
- Prior art keywords
- snow
- melting agent
- short
- melting
- potassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000002844 melting Methods 0.000 title claims abstract description 94
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 80
- 239000000460 chlorine Substances 0.000 title claims abstract description 46
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 54
- -1 oxalic acid imidazoline ester compounds Chemical class 0.000 claims abstract description 24
- 230000008018 melting Effects 0.000 claims abstract description 22
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 22
- BBKJIBJUWBIXIL-UHFFFAOYSA-N ethane-1,2-diamine;formic acid Chemical compound OC=O.NCCN BBKJIBJUWBIXIL-UHFFFAOYSA-N 0.000 claims abstract description 21
- HLCFGWHYROZGBI-JJKGCWMISA-M Potassium gluconate Chemical compound [K+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O HLCFGWHYROZGBI-JJKGCWMISA-M 0.000 claims abstract description 14
- 229960003189 potassium gluconate Drugs 0.000 claims abstract description 14
- 239000004224 potassium gluconate Substances 0.000 claims abstract description 14
- 235000013926 potassium gluconate Nutrition 0.000 claims abstract description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 12
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960003975 potassium Drugs 0.000 claims abstract description 12
- 239000011591 potassium Substances 0.000 claims abstract description 12
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 12
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 claims abstract description 12
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 13
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000007112 amidation reaction Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000004821 distillation Methods 0.000 claims description 3
- 238000005886 esterification reaction Methods 0.000 claims description 3
- 238000006386 neutralization reaction Methods 0.000 claims description 3
- 238000007363 ring formation reaction Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- 229940048086 sodium pyrophosphate Drugs 0.000 claims description 2
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims description 2
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 230000002401 inhibitory effect Effects 0.000 claims 1
- 239000005413 snowmelt Substances 0.000 claims 1
- 238000007710 freezing Methods 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 10
- 239000002184 metal Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 238000002161 passivation Methods 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract description 2
- 238000013329 compounding Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 23
- 239000000047 product Substances 0.000 description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 230000008014 freezing Effects 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 230000006378 damage Effects 0.000 description 6
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 5
- 230000002265 prevention Effects 0.000 description 5
- 235000002639 sodium chloride Nutrition 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 4
- 239000001110 calcium chloride Substances 0.000 description 4
- 229910001628 calcium chloride Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 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 3
- 150000001804 chlorine Chemical class 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 235000002906 tartaric acid Nutrition 0.000 description 3
- 239000011975 tartaric acid Substances 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 description 2
- 230000003449 preventive effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 235000019795 sodium metasilicate Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 229940095064 tartrate Drugs 0.000 description 2
- RTVSJIQVPCPNEQ-UHFFFAOYSA-N 2-(4,5-dihydroimidazol-1-yloxy)-2-oxoacetic acid Chemical compound C1CN(C=N1)OC(=O)C(=O)O RTVSJIQVPCPNEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 206010039203 Road traffic accident Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/18—Materials not provided for elsewhere for application to surfaces to minimize adherence of ice, mist or water thereto; Thawing or antifreeze materials for application to surfaces
- C09K3/185—Thawing materials
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
-
- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Combustion & Propulsion (AREA)
- Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
Abstract
The invention relates to a short-term rust-proof low-chlorine snow-melting agent and a preparation method thereof, belonging to the technical field of anti-freezing melting agents. The snow-melting agent is prepared by synthesizing and compounding water, oxalic acid imidazoline ester compounds, ethylenediamine formate, propiolic alcohol, anhydrous calcium chloride, potassium gluconate, potassium molybdate and potassium pyrophosphate. The oxalic acid imidazoline ester compound, the ethylenediamine formate and the propiolic alcohol are used as main components of the snow-melting agent, the snow-melting agent has an excellent antirust function, the ice point of the snow-melting agent can be greatly reduced by matching with anhydrous calcium chloride, the snow-melting and deicing capabilities of products are improved, and meanwhile, the adsorption and passivation functions on the metal surface are enhanced by using the potassium gluconate and the potassium molybdate, so that the deep antirust effect is achieved. The potassium pyrophosphate keeps the pH value of the snow-melting agent product at 8-9, and the antirust function can be better realized. The preparation method has the advantages of easily obtained raw materials, simple and convenient process operation and suitability for large-scale production, application and popularization.
Description
Technical Field
The invention relates to a snow-melting agent and a production method thereof, in particular to a short-term rust-proof low-chlorine snow-melting agent and a preparation method thereof, belonging to the technical field of anti-freezing melting agents.
Background
In winter snowfall weather, the road surface is wet and slippery due to the freezing of snow, traffic block or traffic accidents are easily caused, inconvenience is caused to traffic traveling, and snow removal is needed in time. The existing snow removing modes comprise mechanical snow removing, snow removing by spreading a snow melting agent, paving a snow melting road surface and the like. Spreading snow-melting agent is a snow removing method which is commonly adopted at present, and the snow-melting agent mainly comprises two types of chlorine-containing type and non-chlorine-containing type at present.
Most of the chlorine-containing snow-melting agent products in the prior art are mainly sodium chloride, calcium chloride or magnesium chloride, and the large amount of the chlorine-containing snow-melting agent products brings great harm to the environment, roads and vehicles and also brings great harm to the environment, roads and vehiclesThe soil is salinized and the plant growth is damaged, and the harm to the human health is caused. For example, the snow-melting agent disclosed in CN201810087493.5 uses calcium chloride and magnesium chloride in a mass ratio of 2:8 as raw materials, and the snow-melting agent disclosed in CN201811247855.9, which is easy to identify and reduces corrosion, uses industrial sodium chloride in a mass ratio of 85-90% as a main raw material, and Cl - The content is relatively high. Can corrode the reinforcing bar, cause the concrete expansion on surface to drop, inside the salt solution can invade the road, cause pitch adhesion to descend, the material drops to and reduce road surface performance, simultaneously, the salt solution can be along with snow rivers to road both sides pollute groundwater, cause that road border vegetation is dead, soil salinization, the destruction environment causes harm to health.
Although the snow-melting agent products aiming at the aspect are also improved, corrosion-reducing products such as sodium metasilicate, tartaric acid, salts thereof and the like are added. For example, CN200710016171.3 is prepared by adding 0.5-10% tartaric acid or tartrate into sodium chloride, mixing them uniformly, adhering the tartaric acid or tartrate onto the surface of sodium chloride particles to form coated particles, drying the coated particles at 140-160 deg.C until the water content is below 1%, sieving, and cooling. CN03130569.5 sodium metasilicate is added into the chlorine-containing snow-melting agent to reduce the corrosion of chlorine ions. Although the product can slightly reduce the corrosivity to metal facilities, the metal facilities can still be rusted and damaged in the service life of the snow-melting agent, the aim of real short-term rust prevention cannot be achieved, and the effect that the metal facilities on the road cannot be maintained for years cannot be really achieved. The non-chlorine snow-melting agent product does not contain chloride ions and has small corrosivity on metals, such as methanol, ethanol and the like, but has poor snow-melting and deicing capabilities, high cost, no antirust function and less application in the industry.
Aiming at the defects of snow-melting agent products in the prior art, the problems that chlorine salt snow-melting agents bring corrosion hazards to metal facilities and vehicles such as roads and the like, and non-chlorine snow-melting agents have poor snow-melting and deicing capabilities and the like, in order to combine the advantages of the two snow-melting agents and enable the snow-melting and deicing agents to have excellent snow-melting and deicing capabilities and antirust functions, a short-term antirust low-chlorine snow-melting agent and a preparation method thereof are in urgent need of development.
Disclosure of Invention
Aiming at the defects of the snow-melting agent product in the prior art, the snow-melting and deicing capabilities of the chlorine salt snow-melting agent are combined, the antirust function is added, and the functional use requirement of the snow-melting agent is met. The invention aims to provide a short-term rust-proof low-chlorine snow-melting agent and a preparation method thereof. The short-term rust prevention function is better realized while snow melting and ice melting are realized.
The specific technical scheme of the invention is as follows:
a short-term antirust low-chlorine snow-melting agent is synthesized and compounded by water, oxalic acid imidazoline ester compounds, ethylenediamine formate, propiolic alcohol, anhydrous calcium chloride, potassium gluconate, sodium molybdate and sodium pyrophosphate, and is characterized in that the short-term antirust low-chlorine snow-melting agent is prepared from the following raw materials in parts by mass:
a method for preparing the short-term antirust low-chlorine snow-melting agent comprises the following steps:
A. firstly, preparing an oxalic imidazoline ester compound and ethylenediamine formate according to requirements respectively for later use;
B. adding water, ethylenediamine formate and anhydrous calcium chloride according to the formula amount, heating to 50-70 ℃, stirring and dissolving for 0.5-1.5 h;
C. after the potassium gluconate, the potassium molybdate and the potassium pyrophosphate are completely dissolved into a transparent solution, adding the potassium gluconate, the potassium molybdate and the potassium pyrophosphate in the formula amount, and stirring for 0.5-1 h at the temperature of 60-70 ℃;
D. and after the mixture is completely dissolved into a transparent solution, adding the oxalic imidazoline ester compound and the propiolic alcohol according to the formula ratio, continuously stirring for 1-2 hours at the temperature of 60-70 ℃, cooling to room temperature after the mixture is completely dissolved uniformly, and discharging to obtain the short-term antirust low-chlorine snow-melting agent.
The preparation method of the oxalic imidazoline ester compound comprises the following steps: adding diethylenetriamine into oxalic acid, then adding tetrabutyl titanate serving as a catalyst, carrying out amidation reaction for 1-3h at 150-160 ℃ under the action of dimethylbenzene serving as a water-carrying agent, indicating that the amidation reaction is finished when the acid value of the system is reduced to 280-300 mgKOH/g, and then heating to 200 ℃ to carry out ring-closing reaction for 4-6 h to obtain an oxalic acid imidazoline compound with one end blocked; and then cooling to 60-70 ℃, adding ethanolamine to perform a neutralization esterification reaction with the carboxyl at the other end, keeping the temperature at 60-80 ℃, reacting for 1-2 h, and removing the xylene solvent by reduced pressure distillation to obtain the imidazoline oxalate ester compound which is a reddish brown viscous liquid.
Preferably, the molar ratio of the oxalic acid to the diethylenetriamine is 1: 1.05.
preferably, the addition amount of the catalyst tetrabutyl titanate is 2 per mill of the mass of the oxalic acid.
Preferably, the molar ratio of the oxalic acid to the ethanolamine is 1: 1.1.
the preparation method of the ethylenediamine formate comprises the following steps: firstly, adding ethylenediamine into an ice bath, keeping the temperature at 0-5 ℃, stirring, then dropwise and slowly adding formic acid, stirring for 1-2 hours after dropwise addition is finished, and stopping stirring to obtain the ethylenediamine formate.
Preferably, wherein the molar ratio of ethylene diamine to formic acid is 1: 2.
the invention has the beneficial effects that:
(1) the product of the invention can realize short-term rust prevention within 1 month, and basically can meet the time requirement of using the snow-melting agent in China.
(2) According to the invention, the oxalic acid imidazoline ester compound, the ethylenediamine formate and the propiolic alcohol are added, and meanwhile, the chloride raw material calcium chloride is matched, so that the freezing point of the snow melting agent can be greatly reduced, the freezing point of a final product reaches below-30 ℃, and the snow and ice melting effect is good.
(3) According to the invention, oxalic acid imidazoline ester compounds, ethylenediamine formate and propiolic alcohol are used for replacing traditional alcohols such as methanol, ethanol, ethylene glycol and the like as main components of the snow-melting agent, so that the snow-melting agent has an excellent antirust function besides the effect of lowering the freezing point, the functions of adsorption, passivation and the like on the metal surface are further enhanced by using potassium gluconate and potassium molybdate, the deep antirust effect is achieved, potassium pyrophosphate is used as a pH regulator, the pH value of a snow-melting agent product is kept in a range of 8-9, and the short-term antirust (1 month) function is better achieved while snow melting is achieved.
Detailed Description
In order to better understand the invention, the following examples further illustrate the content of the invention, but the content of the invention is not limited to the following examples, and the examples should not be construed as limiting the scope of the invention.
Example 1
A short-term antirust low-chlorine snow-melting agent and a preparation method thereof are characterized in that the short-term antirust low-chlorine snow-melting agent comprises the following raw materials in parts by mass:
the method for preparing the short-term rust-proof low-chlorine snow-melting agent comprises the following steps:
A. firstly, preparing an oxalic imidazoline ester compound and ethylenediamine formate according to requirements respectively for later use; the preparation method of the oxalic imidazoline ester compound comprises the following steps: firstly, adding 1 mol of oxalic acid, then adding 1.05 mol of diethylenetriamine, then adding tetrabutyl titanate with the mass of 2 per thousand of that of oxalic acid as a catalyst, carrying out amidation reaction for 1-3h at 150-160 ℃ under the action of dimethylbenzene as a water-carrying agent, when the acid value of a system is reduced to 280-300 mgKOH/g, indicating that the amidation reaction is finished, then heating to 200 ℃ to carry out ring-closure reaction for 4-6 h to obtain an oxalic acid imidazoline compound with one end blocked, then cooling to 60-70 ℃, adding 1.1 mol of ethanolamine to carry out neutralization esterification reaction with carboxyl at the other end, keeping 60-80 ℃ for reaction for 1-2 h, and carrying out reduced pressure distillation to remove a dimethylbenzene solvent to obtain the oxalic acid imidazoline ester compound which is red brown viscous liquid; the method of the short-term antirust low-chlorine snow-melting agent comprises the following steps: the preparation method of the ethylenediamine formate comprises the following steps: firstly, adding 1 mol of ethylenediamine into an ice bath, keeping the temperature at 0-5 ℃, stirring, then dropwise and slowly adding 2 mol of formic acid, stirring for 1-2 hours after dropwise addition, and stopping stirring to obtain ethylenediamine formate.
B. Adding water, ethylenediamine formate and anhydrous calcium chloride according to the formula amount, heating to 50-70 ℃, stirring and dissolving for 0.5-1.5 h.
C. After the potassium gluconate, the potassium molybdate and the potassium pyrophosphate are completely dissolved into a transparent solution, the potassium gluconate, the potassium molybdate and the potassium pyrophosphate are added according to the formula amount, and the mixture is stirred for 0.5 to 1 hour at the temperature of 60 to 70 ℃.
D. And after the mixture is completely dissolved into a transparent solution, adding the oxalic imidazoline ester compound and the propiolic alcohol according to the formula ratio, continuously stirring for 1-2 hours at the temperature of 60-70 ℃, cooling to room temperature after the mixture is completely dissolved uniformly, and discharging to obtain the short-term antirust low-chlorine snow-melting agent.
Example 2
A short-term antirust low-chlorine snow-melting agent and a preparation method thereof are characterized in that the short-term antirust low-chlorine snow-melting agent comprises the following raw materials in parts by mass:
the preparation method is the same as that of example 1.
Example 3
A short-term antirust low-chlorine snow-melting agent and a preparation method thereof are characterized in that the short-term antirust low-chlorine snow-melting agent comprises the following raw materials in parts by mass:
the preparation method is the same as that of example 1.
Example 4
A short-term antirust low-chlorine snow-melting agent and a preparation method thereof are characterized in that the short-term antirust low-chlorine snow-melting agent comprises the following raw materials in parts by mass:
the preparation method is the same as that of example 1.
Example 5
A short-term antirust low-chlorine snow-melting agent and a preparation method thereof are characterized in that the short-term antirust low-chlorine snow-melting agent comprises the following raw materials in parts by mass:
the preparation method is the same as that of example 1.
Comparative example 1:
the procedure is as in example 1 except that the imidazolinyl oxalate is not used.
Comparative example 2:
the procedure is as in example 1 except that ethylenediamine formate is used.
Comparative example 3:
the procedure is as in example 1 except that propiolic alcohol is not used.
Comparative example 4:
the procedure is as in example 1 except that anhydrous calcium chloride is not used.
Comparative example 5:
the procedure is as in example 1 except that potassium gluconate is not used.
Comparative example 6:
the procedure is as in example 1 except that potassium molybdate is not used.
Comparative example 7:
the procedure is as in example 1 except that potassium pyrophosphate is not used.
Comparative example 8:
the product of example 1 in CN201810087493.5 was used as comparative example 8.
Comparative example 9:
the product of example 1 in CN200710016171.3 was used as comparative example 9.
Comparative example 10:
the product of example 1 in CN03130569.5 was used as comparative example 10.
Comparative example 11:
30-35% methanol was used as comparative example 11.
And (4) comparing the results:
the performances of the snow melting agents prepared in the above examples 1 to 5 and comparative examples 1 to 10 and several main technical indexes are compared respectively, and the freezing point, snow melting and deicing capabilities, antirust performance and the like of different snow melting agents are compared in experiments.
The freezing point and the relative snow melting and deicing capacity are measured according to the national standard GB/T23851-2009 road ice melting and snow removing agent and the antirust performance experiment according to the national standard GB/T6144-2010 synthetic cutting fluid, wherein the antirust grade of the cast iron single sheet is as follows: a level: five drops are all free of rust; b, stage: four drops of the liquid are free of rust; c level: three drops of the liquid are free of rust; d stage: four to five drops of all rust.
EXAMPLES AND COMPARATIVE EXAMPLES preparation of snow-removing Agents Performance comparison
The detection result shows that: according to the short-term antirust low-chlorine snow-melting agent prepared by the invention, the oxalic acid imidazoline ester compound, the ethylenediamine formate, the propiolic alcohol and the calcium chloride are added in the examples 1-5, so that the freezing point of the snow-melting agent can be greatly reduced compared with the comparative examples 1-4, and the freezing point of a final product reaches below-30 ℃. Besides lowering the freezing point, the antirust paint also has excellent antirust function.
The components of comparative examples 1 to 3 have not only excellent freezing point and snow and ice melting ability, but also, importantly, they are the main components of the rust inhibitor and are matched with each other to obtain excellent rust prevention function; the lack of relevant components results in a significant drop in the freezing point, snow and ice melting ability and rust prevention of the product.
The comparative example 4 is that the chloride raw material anhydrous calcium chloride is matched to mainly improve the snow and ice melting capability and the freezing point of the product, and the shortage can cause the reduction of the freezing point and the snow and ice melting capability of the product.
According to the short-term rust-proof low-chlorine snow-melting agent prepared by the invention, potassium gluconate and potassium molybdate are added in the examples 1-5, and compared with the comparative examples 5-6, the functions of adsorption and passivation on the metal surface are further enhanced by using the potassium gluconate and the potassium molybdate, so that a deep rust-proof effect is achieved.
Comparative examples 8 to 10 are conventional chlorine salt snow-melting agents, have a freezing point lower than that of the product of the present example, and have high chloride ion content, no effective rust-proof component, remarkable corrosiveness and serious damage to metal facilities.
Comparative example 11 is methanol as a non-chlorine snow-melting agent, which has no remarkable rust preventive property because it has low viscosity, too fast volatilization, poor snow-melting and deicing ability, and is volatile on the metal surface, resulting in failure to effectively form a rust preventive layer, although its freezing point is low.
According to the short-term antirust low-chlorine snow-melting agent prepared by the invention, oxalic acid imidazoline ester compounds, ethylenediamine formate and propiolic alcohol are used for replacing traditional alcohols such as methanol, ethanol, ethylene glycol and the like as main components of the snow-melting agent, potassium pyrophosphate is used as a pH regulator, so that the pH of a snow-melting agent product is kept in a range of 8-9, and the short-term antirust function within 1 month is excellent while snow melting is realized.
In conclusion, the short-term antirust low-chlorine snow melting agent prepared by the invention has good snow melting performance and excellent short-term antirust function. The preparation method has the advantages of easily obtained raw materials, simple and convenient process operation and suitability for large-scale production, application and popularization.
Claims (7)
1. A short-term antirust low-chlorine snow-melting agent is synthesized and compounded by water, oxalic acid imidazoline ester compounds, ethylenediamine formate, propiolic alcohol, anhydrous calcium chloride, potassium gluconate, sodium molybdate and sodium pyrophosphate, and is characterized in that the short-term antirust low-chlorine snow-melting agent is prepared from the following raw materials in parts by mass:
the preparation method of the oxalic imidazoline ester compound comprises the following steps: adding diethylenetriamine into oxalic acid, adding tetrabutyl titanate serving as a catalyst, carrying out amidation reaction for 1-3h with water at 150-160 ℃ under the action of dimethylbenzene serving as a water-carrying agent, finishing the amidation reaction when the acid value of a system is reduced to 280-300 mgKOH/g, and then heating to 200 ℃ to carry out ring-closure reaction for 4-6 h to obtain an oxalic acid imidazoline compound with one end blocked; and then cooling to 60-70 ℃, adding ethanolamine to perform a neutralization esterification reaction with the carboxyl at the other end, keeping the temperature at 60-80 ℃, reacting for 1-2 h, and removing the xylene solvent by reduced pressure distillation to obtain the imidazoline oxalate ester compound.
2. A method for preparing the short-term rust inhibitive low chlorine snow melt agent according to claim 1, comprising the steps of:
A. firstly, preparing an oxalic imidazoline ester compound and ethylenediamine formate according to requirements respectively for later use;
B. adding water, ethylenediamine formate and anhydrous calcium chloride according to the formula amount, heating to 50-70 ℃, stirring and dissolving for 0.5-1.5 h;
C. after the potassium gluconate, the potassium molybdate and the potassium pyrophosphate are completely dissolved into a transparent solution, adding the potassium gluconate, the potassium molybdate and the potassium pyrophosphate according to the formula ratio, and stirring for 0.5-1 h at the temperature of 60-70 ℃;
D. after the mixture is completely dissolved into a transparent solution, adding the oxalic imidazoline ester compound and the propiolic alcohol according to the formula amount, continuously stirring for 1-2 hours at the temperature of 60-70 ℃, cooling to room temperature after the mixture is completely dissolved uniformly, and discharging to obtain the short-term antirust low-chlorine snow melting agent as claimed in claim 1.
3. The method for preparing a short-term rust-preventive low-chlorine snow-melting agent as claimed in claim 2, wherein: wherein the molar ratio of the oxalic acid to the diethylenetriamine is 1: 1.05.
4. a method for preparing a short-term rust-preventive low-chlorine snow-melting agent as claimed in claim 3, characterized in that: the addition amount of the catalyst tetrabutyl titanate is 2 per mill of the mass of the oxalic acid.
5. A method for preparing a short-term rust-preventive low-chlorine snow-melting agent as claimed in claim 3, characterized in that: wherein the mol ratio of the oxalic acid to the ethanolamine is 1: 1.1.
6. the method for preparing a short-term rust-preventive low-chlorine snow-melting agent as claimed in claim 2, wherein: the preparation method of the ethylenediamine formate in the step A comprises the following steps: firstly, adding ethylenediamine into an ice bath, keeping the temperature at 0-5 ℃, stirring, then dropwise and slowly adding formic acid, stirring for 1-2 hours after dropwise addition is finished, and stopping stirring to obtain the ethylenediamine formate.
7. The method for preparing a short-term rust-preventive low-chlorine snow-melting agent as claimed in claim 6, wherein: wherein the molar ratio of the ethylene diamine to the formic acid is 1: 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911128602.4A CN110746932B (en) | 2019-11-18 | 2019-11-18 | Short-term antirust low-chlorine snow-melting agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911128602.4A CN110746932B (en) | 2019-11-18 | 2019-11-18 | Short-term antirust low-chlorine snow-melting agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110746932A CN110746932A (en) | 2020-02-04 |
| CN110746932B true CN110746932B (en) | 2022-09-13 |
Family
ID=69283587
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911128602.4A Active CN110746932B (en) | 2019-11-18 | 2019-11-18 | Short-term antirust low-chlorine snow-melting agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110746932B (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820081A (en) * | 2014-02-28 | 2014-05-28 | 呼和浩特铁路局科研所 | Snow-melting agent |
| CN105754549A (en) * | 2016-03-25 | 2016-07-13 | 黄山九星环保科技有限公司 | Low-chloride snow-melting agent and preparation method and application thereof |
| CN105968052A (en) * | 2016-05-04 | 2016-09-28 | 辽宁科技学院 | Imidazoline corrosion inhibitor and preparation method thereof |
| CN106884171A (en) * | 2017-02-10 | 2017-06-23 | 南充市巨星化工有限责任公司 | A kind of preparation method of imidazoline inhibitor |
| CN109289696A (en) * | 2018-10-29 | 2019-02-01 | 天津先光化工有限公司 | A kind of preparation method of imidazoline amophoteric surface active agent |
| CN109385252A (en) * | 2018-12-03 | 2019-02-26 | 煤炭科学技术研究院有限公司 | A kind of composition of novel non-chlorine environmental-protecting type deicing salt and preparation |
-
2019
- 2019-11-18 CN CN201911128602.4A patent/CN110746932B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103820081A (en) * | 2014-02-28 | 2014-05-28 | 呼和浩特铁路局科研所 | Snow-melting agent |
| CN105754549A (en) * | 2016-03-25 | 2016-07-13 | 黄山九星环保科技有限公司 | Low-chloride snow-melting agent and preparation method and application thereof |
| CN105968052A (en) * | 2016-05-04 | 2016-09-28 | 辽宁科技学院 | Imidazoline corrosion inhibitor and preparation method thereof |
| CN106884171A (en) * | 2017-02-10 | 2017-06-23 | 南充市巨星化工有限责任公司 | A kind of preparation method of imidazoline inhibitor |
| CN109289696A (en) * | 2018-10-29 | 2019-02-01 | 天津先光化工有限公司 | A kind of preparation method of imidazoline amophoteric surface active agent |
| CN109385252A (en) * | 2018-12-03 | 2019-02-26 | 煤炭科学技术研究院有限公司 | A kind of composition of novel non-chlorine environmental-protecting type deicing salt and preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110746932A (en) | 2020-02-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5709813A (en) | Deicing composition and method | |
| US5919394A (en) | Deicing composition and method | |
| US7138071B2 (en) | Environmentally benign anti-icing or deicing fluids | |
| CN106190034B (en) | A kind of compound chloride-based type deicing salt of high-efficient corrosion inhibition type and preparation method thereof | |
| KR101361136B1 (en) | Method of manufacturing liquid type deicer | |
| US20090314983A1 (en) | Environmentally benign anti-icing or deicing fluids | |
| KR101426857B1 (en) | Eco friendly non-chloride deicer coposig mixture of salt of organic acid | |
| KR101471327B1 (en) | Eco snow remaval agent | |
| KR101028193B1 (en) | An eco-friendly composition for liquid type deicer | |
| KR100588820B1 (en) | Composition for liquid type snow-removing agent | |
| CN110746932B (en) | Short-term antirust low-chlorine snow-melting agent and preparation method thereof | |
| KR101021441B1 (en) | Eco-friendly liquid and solid type deicer composition, and producing apparatus of liquid type slaked lime used for the liquid type deicer composition | |
| KR101663165B1 (en) | Eco-friendly liquid type snow-removing agent using orginac acid and manufacturing apparatus thereof | |
| CN109415617B (en) | Aqueous deicing composition with inhibiting action | |
| US8440095B1 (en) | Anti-corrosive corn extracts | |
| US20100009073A1 (en) | Anticorrosion agents for halide brines | |
| KR100941376B1 (en) | Liquid type composition of deicing chemicals recycling wasted glacial acetic acid and manufacturing method thereof | |
| CN113201311A (en) | Organic environment-friendly snow removing agent and preparation method and application method thereof | |
| KR102483140B1 (en) | Snow removal composition with excellent eco-friendliness and anti-freeze performance | |
| KR20160034523A (en) | Eco-friendly deicer and preparing method of the same | |
| CN110819993B (en) | Long-acting corrosion inhibitor for solid chlorine salt snow-melting agent and preparation method thereof | |
| CN108795384B (en) | Salt-dust-free low-chlorine environment-friendly snow melting agent and preparation method thereof | |
| CN108467681B (en) | Environment-friendly anionic anti-freezing coating applied to surface of asphalt material and preparation method thereof | |
| CN112480878A (en) | Preparation method of efficient environment-friendly automobile antifreeze fluid | |
| CN113046196A (en) | Solid cleaning liquid concentrating agent and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240202 Address after: Room 801, 85 Kefeng Road, Huangpu District, Guangzhou City, Guangdong Province Patentee after: Guangzhou Dayu Chuangfu Technology Co.,Ltd. Country or region after: China Address before: 245041 No.39, Xihai Road, Tunxi District, Tunxi District, Mount Huangshan City, Anhui Province Patentee before: HUANGSHAN University Country or region before: China |
|
| TR01 | Transfer of patent right |