KR20170000825A - Manufacturing Method of Rapid Deicing Eco-Agent Using Dolomite Including Magnesium Minerals and its products - Google Patents

Abstract

The present invention relates to a method for producing an eco-friendly fast deicing agent using magnesium minerals such as dolomite, and to a product thereof. According to the present invention, it is possible to provide the eco-friendly fast deicing agent exhibiting fast melting functions. To this end, a chloride solution is purified so as to remove impurities, and an anticorrosive agent is added to reduce corrosiveness, in addition to an ionization accelerator.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a manufacturing method of an environment-friendly snow-removing agent using magnesium mineral such as dolomite,

Calcium chloride (CaCl ₂ ) has anhydrous, 1 water, 2 water, 4 water, 6 water and 8 water depending on the evaporation temperature of production. The solubility of 100 g water at 20 ℃ is strong in deliquescence and fever Solubility heat (The dissolving heat of 1mole of anhydrate is about 80 KJ (19.14cal), and it is used for dehydration, moisture absorption, icing, icing, confection, snow removal, , It accelerates the corrosion of the road surface, causes environmental damage to plants and human beings, and re-freezes molten water at a relatively low temperature, posing a safety problem.

The present invention is an eco-friendly quick-drying snow remover that alleviates or eliminates the above problems by using a magnesium-containing mineral such as dolomite, and is a field of fine chemical inorganic materials.

Magnesium chloride (MgCl ₂ ) has a solubility of 54.6 g in an aqueous solution of 100 g of water at 20 ° C and a high water solubility of 116.0 g in a water solution of 6, thus rapidly expressing the inhibitory action. Dolomite and other magnesium-containing minerals are dissolved in hydrochloric acid to purify the chloride solution to remove impurities and to prevent corrosion, thereby reducing corrosivity and promoting ionization, thereby producing an eco-friendly antiseptic agent capable of exhibiting a snow melting function.

 Langes Handbook of Chemistry: Editor John A. Dean  12695 chemical products Nippon Chemical Industry Co., Ltd.

In order to improve the long-term melting time which is the problem of the reduction of the calcium chloride, the re-icing at the lower temperature of the melting liquid, and the environmental damage due to the strong corrosiveness, dolomite which is a magnesium-calcium mixed minerals having high solubility as a Mg component [Ca.Mg _{(CO 3) 2), Huntite} [3Mg.Ca (CO 3) 4], gyeongso Baegun times with magnesium mono-component mineral _{Magnesite (MgCO 3), Brucite (} Mg (OH) by dissolving ₂₎ in hydrochloric acid MgCl _2. CaCl ₂ mixed solution or MgCl ₂ solution is prepared and the pH is adjusted with hydroxide such as calcium hydroxide to precipitate and remove metal impurities with hydroxide to accelerate ionization to shorten the melting time and to reduce the corrosion and reduce the corrosivity It is an object of the present invention to provide an anticorrosion-reducing eco-friendly property agent that improves safety that water does not re-freeze at -20 占 폚.

When the magnesium-containing raw mineral is crushed or pulverized and dissolved in a dilute hydrochloric acid solution, carbonic acid gas is discharged, resulting in a hydrochloric acid solution or a MgCl ₂ solution mixed with CaCl ₂ and MgCl ₂ .

Since the hydrochloric acid solution contains unreacted materials and impurities, the raw mineral is put into a solution with a yellowish brown solution and is left to stand to dissolve the unreacted material and mature.

When pH is adjusted to 3 to 5 by dropwise addition of hydroxide such as lime, magnesium hydroxide, caustic soda and caustic soda to the aging dissolving solution with stirring of hydrogen peroxide (H ₂ O ₂ ) as an oxidation promoter, Fe 2+ to 3+, Mn 2+, , Cr2 +, Pb2 +, and other metal ions are precipitated as solid hydroxides, which are separated by filtration to make a transparent ripening refining solution.

As the ionization accelerator, a solution of sodium metaphosphate in which strong metal ion blocking function and dispersing ability are expressed,

Gum Ghatti, PGA (propylene glycol alginate), Sucrose, and Alcohols Lignosulfonate were added to make a chloride solution that promotes dispersion and ionization.

_{Alcohol (Methyl CH 3 OH, Ethyl} C 2 H 5 OH) is a corrosion inhibiting function expression in order to remove the _{caustic, Urea [CO (NH 2)} 2], Sodium Nitrite (NaNO 2), Sodium Hexametaphosphate (NaPO 3) nP ₂ O ₅ was added and stirred to reduce the corrosiveness of the environmentally friendly snow-removing agent

to provide.

When spraying the environmentally friendly snow remover solution on ice, the snow removal and freeze-thawing action is carried out quickly, and the solution becomes safer because the re-icing starts at -20 ℃ 1 day later.

The eco-friendly snow-removing agent is dried and evaporated by a spray dryer to obtain an eco-friendly snow-drier having powdered magnesium chloride, magnesium chloride and calcium chloride mixed.

In order to prevent moisture absorption of the above-mentioned powder property removers and to facilitate storage and handling, at least one of agar, starch, fatty acid, resin acid, and stearic acid is selected and dry-coated so that it is moisture- Thereby providing an environmentally friendly property of the coated powder to be expressed.

The present invention provides an eco-friendly snow-removing agent, such as corrosion resistance, environmental impact, safety of re-sintering, long time of snow removal, shortening of snowing time, reduction of corrosiveness, safety by re- Which is a large amount of mineral in Korea, such as dolomite.

In order to measure the amount of ice melt of conventional snow removers and inventions under the same conditions, weights of unmelted ice were weighed and expressed as Graphs by time of immersion of ice blocks in the same concentration of snow remover solution, .

The present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following experimental examples.

(Experimental Example 1) Magnesite-containing minerals, dolomite hydrochloric acid dissolution

Specific experiments are carried out with a solution obtained by dissolving dolomite containing Mg component as a base material of the present invention in hydrochloric acid.

    Dissolved Minerals: Dolomite

    Dolomite Quantity: Oresite 20 ~ 30mmφ 2000g

    Amount of hydrochloric acid used: concentration 35% 4000g

               Dolomite hydrochloric acid dissolution experiment        Hydrochloric acid dissolution          Solution / dissolution rate  Remarks dolomite Amount of hydrochloric acid Sum solution Zeolite Sum Dissolution% 2.000 gr 1,000gr 3,000 gr 1,114 gr 1,688gr 2,802 gr 15.60% 1,688gr 1,000gr 2,688gr 1,298gr 1,212gr 2,510 gr 28.20% 1,212gr 1,000gr 2,212gr 1,266gr  754gr 2,020gr 37.79% 754gr 1,000gr 1,754 gr 1,268 gr 312gr 1,580gr 58.62% 2,000 gr 4,000 gr 6,000 gr 4,946gr 312gr 5,258 gr 84.40%

 Dissolution considerations: The faster the dissolution rate and the faster the dissolution at PH 1.7

            Immersed in hydrochloric acid for a long time to dissolve in PH4.15.

   Dolomite is well soluble in hydrochloric acid and slowly dissolves at pH below 1.7,

   Due to the termination of the dissolution, the continuous PH-controlled dissolution method is recommended and the sealing process

   Toxicity of chlorine gas should be blocked.

   The chemical equation of dissolution is as follows (dolomite amount 2,000 g / 184.31 = 10.851 mole)

     Reaction formula CaMg (CO 3) 2 + 4HCl + HCl water → CaCl 2 + MgCl 2 + 2CO 2 ↑ + 2H 2 O +

     Molecular weight 184.31 + 145.80 + Hydrochloric acid water → 110.90 + 95.21 + 88 + 36 + Hydrochloric acid water

     Reaction Dolomite Ore + Hydrochloric Conc + Hydrochloric Acid → CaCl2 + MgCl2 + 2CO2 ↑ + 2H2O + Hydrochloric Acid

     Reaction amount 2,000 g + 1,582 g + 2,418 g - 1,203 g + 1,033 g + 955 g + 391 g + 2,418 g

  Theoretical concentration of hydrochloric acid solution: (1,203 + 1,033) ÷ (1203 + 1033 + 391 + 2418) = 0.4432 = 44.32%

  Concentration of dissolved solution: 44,42% (Measuring instrument KETT Infrared moisture meter FD-720)

(Experimental Example-2) Purification test of dolomite hydrochloric acid solution

2000 g of the hydrochloric acid solution was dispensed into two 1,000 CC Beakers of 1,000 g, and the impurities were purified as follows.

                          next

1. Add 5 drops of 35% H ₂ O ₂ as an oxidizing agent to the solution while stirring,

     2. A 22% strength lime oil was added dropwise to adjust the pH to 4.0, and the mixture was allowed to stand for 12 hours to separate the supernatant liquid. The precipitate was filtered to prepare dolomite hydrochloric acid dissolved refined liquid.

 (Experimental Example-3) Ice melting comparative experiment

   1) Preparation of experiment: 1. 100cc beaker was poured into 5 bottles of 100CC beverages and frozen for 3 hours in a cold room.

               2. Each of the 500CC Beaker was filled with 300g (solid content: 74.70g) of 24.90% concentration of snow remover and cooled to 3 ° C in a refrigerated room as follows. 3. The contents of Beaker are;

                  #One. Waterworks 300g

                  #2. 168.17g of dolomite solution was added and 131.83g of water was diluted to dilute 300g of diluted dolomite solution with solid content of 24.90%

                  # 3. Liquid Calcium Chloride Solution Concentration 24.90% 300g

                  #4. # 2 In the same solution as the dolomite solution, oxygen solution of meta-phosphorus as an ionization promoter and 2% of each of Sucrose solution,

                  # 5. To the same solution as the # 3 liquid calcium chloride solution, add 2 g of each of Sucrose and Meta phosphorus as an ionization promoter,

               4. Refrigerating chamber Beaker with 5 spaces and 1 / 1000g air gap and Stop Watch

   2) Laboratory hours: 1. Charge each beaker of ice mass (100 g same weight and same shape) of experiment preparation # 1

               2. The ice weight was divided into 5 minutes / 10 minute intervals

               3. Ice weight measurement result table is as follows.

      Results Data sheet Time: minutes / weight: gram time Control group    Raw material sample   Ionization treatment sample        Raw material sample Melting agent   water Dol salt Salt solution Dol salt Salt solution   water Dol salt Salt solution Ice  100g  100g  100g  100g  100g   50g   50g  50g  05 minutes 94.632 79.141 83.272 81.519 86.473 42.007 38.436 39.797   10 91.516 74.186 77.341 72.925 79.715 39.504 33.758 35.402   15 90.509 70.062 74.147 66.794 73.483 37.144 30.165 31.557   20 89.220 66.984 70.884 60.808 67.790 35.007 26.915 29.062   25 87.914 62.828 67.894 55.707 61.836 33.116 23.025 24.242   30 87.247 59.880 66.111 51.118 56.790 31.413 19.789 20.859   35 86.027 55.600 61.758 46.486 52.126 30.184 16.135 17.834   40 85.308 52.015 59.730 43.411 49.190 28.722 13.113 14.447   45 84.567 49.795 57.422 40.649 46.220 27.412 10.623 12.321   50 83.483 47.504 55.317 37.798 44.090 25.942  7.213 10.595   55 82.592 44.498 53.112 35.891 41.504 24.563  5.285  8.590   60 81.541 42.654 51.153 33.833 40.498 23.348  3.613  6.788   65 80.912 40.536 47.724 31.209 37.893 21.990  2.168  5.363   70 80.266 37.901 47.064 29.373 36.552 20.792  0.986  4.178   75 79.306 35.242 45.077 27.947 35.160 19.680  0.460  3.171   80 78.456 33.321 44.208 26.162 33.654 18.560  -0-  2.300   85 77.677 31.245 41.731 23.759 31.446 17.088  1.474   90 76.933 28.922 40.191 22.147 28.115 15.865  0.930  100 75.384 25.104 36.579 15.915 23.413 14.915  0.560  110 74.963 22.150 34.383 12.463 20.677 14.015  0.242  120 73.915 19.464 31.916  9.093 18.018 13.172  0.125  -0-  130 72.599 17.074 29.684  7.325 16.444 11.628  140 71.186 14.477 26.912  4.876 13.827  150 70.482 12.665 24.862  3.546  160 68.864 10.843 22.263  2.345  170 68.035  8.736 19.784  1.396  9.491  180 65.988  7.033 17.495  0.273  6.810  185  -0-  190 65.249  5.396 15.688  200 64.121  3.913 13.634  210 62.944  2.923 12.269  220 62.288  1.850 10.341  230 61.149  0.520  8.118  240 59.960  -0-  6.565  2.799  250 59.161  5.115  0.580  260 57.853  4.057  -0-  270 56.173  3.074  280 55.293  2.244  290 53.849  1.394  300 52.884  0.730  310 51.520  0.332  320 49.671  -0-

 4). Test result Melting time

   1 dolomite hydrochloric acid Melting point of dissolution solution End point: 4 hours 00 minutes (240 minutes) 75%

   2 Liquid calcium chloride solution Melting point: 5 hours 20 minutes (320 minutes) 100%

   3 Ionized dolomite Solubility liquid Melting point: 3 hours 05 minutes (185 minutes) 58%

   4 Ionized calcium chloride solution Melting point: 4 hours and 20 minutes (260 minutes) 81%

 5) Freezing temperature of melting solution

    The ice-melting solution subjected to the melting test in Experimental Example-3 was placed in a -20 ° C freezer for 30 hours

    The observed icing conditions are as follows (see attached photo)

    1 ionized dolomite hydrochloric acid solution - partially soft ice in solution at 20 ℃

    2 ionization Conventional calcium chloride - freezing at 9.0 ° C

 6) Test results

    1. Liquid calcium chloride ice 100g Melting time 320 minutes

    2. Melting time of dolomite hydrochloric acid solution 240 minutes

    3. The melting time of dolomite hydrochloric acid solution was 185 minutes,

   4. Ionized Conventional Calcium Chloride Melting Time Reduced by 60 minutes to 260 minutes

 7) Conclusion of the examination

   1. The dolomitic hydrochloric acid solution has a cooling time of 240 minutes and a shortening of 80 minutes (25%) compared to the liquid calcium chloride

   2. Dolomite hydrochloric acid solution with addition of ionization accelerator decreased the melting time 185 minutes (42%)

   3. When dolomitic hydrochloric acid solution is accelerated to ionization, the re-icing temperature of the solution for cooling ice is -20 ℃

     Calcium chloride - more safety than 9 ℃.

   4. Ionization accelerating treatment of conventional snow removers such as calcium chloride and salt shortens the melting time by 19%.

   5. Melting curve of snow removing part Graph attached to drawing file

 (Experimental Example-4) Metal corrosion test by solution

  1) Preparation of experiment: 1. 300cc Beaker Weigh 200g of test solution as follows.

                    # 1 Water Water 200g

                    # 2 Liquid calcium chloride solution concentration 24.90% 200g

                    # 3 Dolomitic hydrochloric acid dissolution Purified liquid concentration adjusted to 24.90% to 200 g

                    To the same solution as # 4 # 3, 3% of sodium metabisulfite and 2% of anhydrous acetic acid were added and stirred

                2. 8 pieces of Washer with 5cm of iron piece

   2) Test execution: 1. Two pieces of steel pieces are charged to # 1 ~ # 4 beaker

                 2. Red color of liquid due to rust of iron. Visual observation of sediment and photos

                   Corrosion Test Summary Table  Contents    Water supply   Calcium chloride solution   invention   Imported snow remover Liquid quantity    300ml   300ml    300ml   300ml Solid concentration    - 0 -   20%    20%    25% Refining process      -   process    process    process Ion treatment      -     -    process    process Corrosion treatment      -     -    process    process Number of metals    2   2    2    2 One-day politics   Brown   Brown river   Clear liquid    Clear liquid   30 hours Corrosion Corrosion   Clear liquid No clear liquid / rust Two-day politics Reddish brown turbid rust Reddish brown turbid rust   Clear liquid Translucent syringes Red

     Actual photo: see photo in drawing file

Claims (1)

Dolomite and other magnesium-containing minerals in hydrochloric acid to prepare a mixed solution of magnesium chloride and calcium chloride and a hydrochloric acid solution as a magnesium chloride solution;

Adding the mineral to the hydrochloric acid solution to further dissolve the undissolved product, further dissolving the mineral, and aging the solution to prepare an aged chloride solution;

The magnesium component-containing mineral may be at least one selected from the group consisting of Magnesite, Brucite, dolomite, Huntite, light white lime, white lime unhydrate and magnesium chloride

[Claim 2]
Hydrogen peroxide (H ₂ O ₂ ) is added to the aged chloride solution or magnesium chloride as an oxidizing agent, and hydroxide is added to adjust pH of the solution to 4 ± 1. The impurities such as metal ions are precipitated as hydroxide, filtered and purified Preparing a refined salt solution;

The hydroxide is _{Ca (OH) 2, NaOH,} KOH, NaClO, NH 4 OH, NH 4 Cl, HClO, Na 2 O 2, Selecting one or more of NaClO;

[Claim 3]
A step of adding a corrosion inhibitor and an ionization promoter to the chloride solution of each step and conventional snow removers such as calcium chloride to reduce the corrosiveness and to produce a highly reactive liquid snow removing agent;

Drying the liquid property-imparting agent by an air stream type dryer or reduced-pressure evaporation;

The corrosion inhibitor may be selected from alcohols (CH ₃ OH / C ₂ H ₅ OH), sodium nitrite (NaNO ₂ ), Urea {CO (NH ₂ ) ₂ }, sodium hexametaphosphate (NaPO ₃ ) nP ₂ O _5, etc .;

The ionization accelerator may be selected from one or more of sodium metaphosphate, gum arabic, soy polysaccharide, Sucrose, Xantan Gum, Gellan Gum, Gum Ghatti, Lignosulfonate, Alcohols and PGA (alginic acid propylene glycol ester).

The addition ratio of the corrosion inhibitor and the ionization promoter is added in the range of 0.5 to 5.0 parts based on the solid content of the chlorinated solution so that the functions are uniformly expressed.

[Claim 4]
A step of selectively coating at least one of agar, fatty acid, resin acid and stearic acid in order to impart a moisture-proof function to the powdery property-

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