JPS62273280A - Ice preventing method and composition for surface of road - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

Detailed Description of the Invention 3. Detailed Description of the Invention Background of the Invention [Field of Industrial Application] The present invention relates to waterproofing or dustproofing agents and their use. More specifically, the invention relates to the conversion of old sulfide solutions (spe.
nt 1iQIJOr).

Corrosion damage caused by roadway waterproofing or dustproofing is reduced by the present invention.

[Conventional Technique'#i] Commercial, industrial and public needs generally require that traffic be secured with reasonable safety even on snow or ice! recognized. However, relying solely on snow or ice removal by mechanical means is insufficient to ensure safe and efficient operation of traffic. Currently, the only possible means by which "bare pavement" maintenance can be carried out is through the use of waterproofing salts.

Rock salt or sodium chloride is the main agent used primarily for waterproofing because it is cheap, easy to transport, and can be made into easily dispersible forms.

The price of waterproofing salt is for metal guard rails, bridge supports,
Metal concrete reinforcing rods and r for automobiles
It does not include the costs arising from the G4 eclipse, which is an excessively low estimate. In the US alone, the cost of pruning defective bridge repairs reaches $500 (Chemical Ha
Marketing Reporter, August issue, 27
．． (1984).

Formamide spray with urea and calcium formate instead of alkali metal or alkaline earth metal chlorides,
Calcium magnesium acetate, metal sulfates, phosphates,
Other agents have been used, such as mixtures with nitrates, amides, alcohols, long chain amines and sodium dichromate. All of these drugs have not achieved widespread use due to their high cost, low efficacy, and/or high toxicity.

Some studies utilized lignosulfonates as a component of waterproofing or dustproofing agents to reduce the corrosivity of alkaline earth metal chloride salts added to road surfaces. Special Public Service 1977
-12310 specification.

The use of a ternary mixture of calcium chloride, low-volume calcium lignosulfonate and calcium hydroxide as a dust or antifreeze agent is disclosed. 1-3% (dry weight) mixture of lignosulfonate calcium? No. 13 (lignosulfonate:calcium chloride ratio of 1:35 or less) was tested and found essentially no corrosion inhibition. Some anticorrosion activity was observed when calcium hydroxide was combined with calcium chloride. However, when both calcium lignosulfonate and calcium hydroxide are heated together with calcium chloride, a greater rust-preventive effect is observed, so the specification of the above-mentioned Japanese Patent Publication No. Sho specifically states that calcium lignosulfonate and calcium hydroxide are mixed together with calcium chloride. Concerning formulations containing in combination. The formulations disclosed in the above patent each contain 1 to 5% calcium sulfonate and at least the same amount of calcium hydroxide. Tests showed that the pH of these solutions was about 10 or higher.

[Problems to be Solved by the Invention] Old sulfide solutions have been used for a long time as dustproofing agents that are added directly to dusty or gravel roads.

It is known that alkali metal and alkaline earth metal chloride salts are used for dust control. Due to transportation costs, sulfide or chloride salts may be limited to use in certain areas.

Conventional waterproofing or dustproofing agents such as sodium chloride, calcium chloride, magnesium chloride or rock salt ultimately cost the consumer much more corrosion damage than would be expected from the original material. Therefore, compositions that alleviate corrosion problems would be a highly desirable development in the art of waterproofing or dustproofing for road surfaces.

SUMMARY OF THE INVENTION It is an object of the present invention to provide an inexpensive additive to waterproofing salts to reduce corrosion.

Another object of the invention is to provide a waterproofing or dustproofing agent that has less tendency to corrode steel or aluminum road supports, bars, beams or motor vehicles.

Yet another object of the invention is to produce a waterproofing agent with anti-slip properties.

[Means for Solving the Problems] According to the above and other objects, the present invention provides, in one aspect, a method for applying a nalphite waste solution to a road surface selected from the group consisting of an alkali metal and an alkaline earth metal chloride. The ratio of the lignosulfonate content to the metal chloride salt of the old sulfide solution (dry weight)
A method for waterproofing and dustproofing road metals that is less corrosive, characterized in that the mixture is added in an amount such that the pH of the mixture is approximately 1:25 to approximately 15:1 and the pH of the mixture is approximately 4.5 to approximately 8.5. I will provide a.

In another aspect, the present invention provides a mixture of an old sulfide liquor and a metal chloride salt selected from the group consisting of an alkali metal and an alkaline earth metal chloride, wherein the lignosulfonate content of the old sulfide liquor is reduced by the metal chloride. The ratio (dry weight) to salt is about 25 to about 15:1,
There is provided a waterproof and dustproof composition comprising an amount of the mixture having a Dll of about 4.5 to about 8.5. In another embodiment, an anti-slip agent may be mixed with the sulfide heavy liquor-chloride salt mixture prepared above.

DETAILED DESCRIPTION According to the invention, the use of alkali metal or alkaline earth metal chloride salts as waterproofing or dustproofing agents is suitable for use in metal road barriers, bridges, concrete reinforcing bars and It has been found that the corrosivity to automobiles can be significantly reduced by adding old sulfide liquid. Since the mixtures of the invention have a substantially neutral pH, corrosion due to low or high pH is avoided. For example, aluminum can undergo corrosion at relatively high alkaline pH.

The effectiveness of metal chloride salts in promoting road waterproofing is due in part to their low price, ability to penetrate frozen surfaces and break sheets of ice to allow normal traffic to pass through and remove them from roads. Depending on the ease and uniformity with which it is applied over the surface. Several J'As are currently used such as sodium chloride, calcium chloride, magnesium chloride, potassium chloride or mixtures thereof. These are sometimes used in mineral form, such as rock salt. Any of these can be considered for use in the present invention. Sodium chloride and magnesium chloride are most frequently used in roads and are the preferred materials for the practice of this invention.

Old rulphite solution is a viable additive in that it is readily available, effective in reducing corrosion, relatively inexpensive, and generally non-toxic. Old sulfide liquor is a by-product of sulfide valve mills that process wood or other plant material to separate cellulose or valves from the liquor. Such methods are, of course, well known. The main component of old sulfide liquid produced in mills is sulfonate, which is generally dried after drying.
It has been found that about 40% to about 70% or more of the liter is present, with the remainder consisting of hydrocarbons and their constituents and interpoint compounds. In addition to old sulfide liquors, such as those obtained from the sulfide valve manufacturing process (with substantially no solids removed), a fermentation process may be used to convert at least a portion of the carbohydrates into alcohol or protein by-products ([sulfide] Sulfide old liquid converted to old liquid or vanalin (vanalin) after alkali oxidation
Old sulfide liquors that have been produced (raffinate) are also contemplated for use in the present invention and are included within the scope of the term "old sulfide liquors" as used herein.

Old sulfide liquors contain lignosulfonates as salts, such as magnesium, calcium, sodium, potassium or ammonium salts, and the weight ratios used herein are with respect to this salt.

It has been found that at the lower effective limit of the ratio (dry weight) of old sulfide solution to metal chloride salt, the ratio (dry weight) of lignosulfonate to metal chloride salt is about 1:25. Once the ratio exceeds an upper limit of about 15:1, one begins to lose the benefits obtained by using the blend of ingredients. A ratio of about 1:25 to about 15=1 can be used for waterproofing or dustproofing, but when used for ice,
A range of about 1:15 to about 2:1 is preferred, and a range of about 1=2 is particularly preferred. Approximately 1:4 when used for dustproofing
A range of ˜about 2=1 may be preferred to provide best results. In each case, the ratio represents the ratio of the dry weight of the sulfonate salt in the old sulfide solution to the dry weight of the metal chloride salt.

The mixtures of the invention have approximately neutral pH. p of the mixture
++ is about 4.5 to about 8.5, and mixtures with a pH of about 5 to about 8 are particularly preferred. Although the mixture itself may provide the desired pH, the pH may be adjusted if desired.

When it is desired to avoid increasing the pH, the following bases can also be used. Since the pH of many old sulfite solutions tends to be slightly acidic, it is not often necessary to lower the pH, but this can be easily done using a mineral acid. pl+ herein is the DI measured when the mixture of the invention is dissolved in water to provide a solution with a total solids concentration of 10% by weight.

In operation, either liquid or dry aged sulfide liquor is mixed with solids or solutions of metal chloride salts (followed by drying if appropriate) to provide the liquid or solid mixture contemplated by the present invention. It's okay. In one aspect of the invention, although the invention contemplates applying a mixture of the above components to a surface, the invention contemplates applying each component separately to a road surface, whether in liquid or solid form. It is also intended to.

Since these components are essentially physical mixtures, the following suitable mixing devices may be used.

Additionally, other ingredients such as anti-slip agents may be added during mixing. Common anti-slip materials include sand, limestone, cinder grid, etc. Old sulfide solutions may consist essentially of chloride salts plus non-corrosive additives.

When used on roads and dry areas for dust control, methods in which the components are administered with a liquid are commonly used. Multiple components can be administered in liquid form, one can be administered as a solid and the other can be administered as a liquid;
Alternatively, each component can be administered in solid form and then the surface moistened.

Since ice provides moisture, the application of the mixture to icy roads or paths at risk of icing can be carried out either in liquid or solid form.

Salt mixtures are often applied as solids in freezing conditions. However, such implementation does not preclude the option of dispensing either or both of the components in liquid form.

The amount of substance applied to the road surface varies widely depending on the purpose (e.g. dust proofing or waterproofing) and the severity of the conditions. Salt solutions tend to be more corrosive and therefore the total amount of sulfide heavy liquid in solution on the road is a factor in minimizing corrosion. (or during snowfall), a proportion of the component having a relatively large amount of sulfide heavy liquid and/or a high application rate is desirable. However, the ratio and/or darkness applied is easily within the skill of the art.

When an anti-slip agent such as sand, limestone, cinder grid, etc. is present, the mixture is mixed to provide an aqueous suspension of the anti-slip agent. Sulfite 1 ~ Prepare a dry mixture of old liquor and anti-slip agent, and metal chloride? +Can also be stored with salt until needed. The dry mixture can be prepared by simply mixing the dry solids or by sprinkling a solution of llllite waste solution onto the anti-slip agent and then drying the mixture. Alternatively, the dry mixture can be applied to the surface separately or mixed with the metal chloride salt, and the components can be applied in any desired combination in liquid and solid form.

EXAMPLES The invention is further illustrated by the following specific examples. These examples are illustrative and are not intended to limit the scope of the invention. In these examples, the pH was adjusted using the oxide or hydroxide of the intermetallic ion corresponding to the metal of the metal chloride to ensure that the pH from run to run of each example was substantially the same and for comparison. provided the base.

Example 1 A solution of magnesium chloride was prepared with the following concentrations of aged calcium sulfide liquid (CaSSL) and magnesium chloride. Saccharom the original Ca5SL
Yces cerevisiae was used to produce alcohol by WJB, and the fermented Ca5SL was about 75%
Calcium lignosulfonate (on a dry solids basis)
Included. The fall was adjusted to approximately neutral using MQO. Corrosion rate 1966 Hagma company '111
Measurements were made using a Model 70 C0rrater (registered trademark) corrosion rate measuring device with a soft metal probe and then with an aluminum ^11oy5454 probe.

Total solution weight percentage Corrosion rate 5
0 7.4 1.4 5.75 5
6.8 0.8 3.05 10
6.6 0.85 15
6.8 0.8 2.410 0
B, 5 2.0 8. '110 5
7.1 0.5 2.110 10
6.8 0.5 1.710 15
6.6 0.40 5 7.
5 0.5 2.9 Example 2 Mild steel washers were immersed in the same solution used in Example 1 and hIi-treated for 25 days at ambient temperature.

The weight loss of the washer was measured.

5 0 7, 4 8.05
5 6, 8 4.45 10
6.6 4.05 15 G,
8 6.610 0 6, 5
6.010 5 7.1 4.
410 10 6.8 4.810
15 G, 6 4.40
5 7, 5 5.7 Example 3 Prepared M0CI2 solution and prepared 1966 Hagma Company 11
The samples were allowed to stand overnight before being tested on a Model 170 Corrater®-F using a mild steel probe. Explain the effect of dilution on the corrosivity of a solution.

10 4 5.7 1.35
2 6.3 2゜02.5
1 6.7 3.41.25 0.
5 G, 9 7.4Q, 625 0.
25 7. Q 12.9 NaCl solution was prepared and the pH was adjusted to that of the above MOCI□ solution.

As these data show, the more dilute the solution, the more corrosion occurs.

1045.72.5 5 2 6, 3 3.02.5
1 6.7 6.01.25
0.5 6.9 10.00.625
A 0.25 7.0 14.6 CaC12 solution was prepared and I) II was adjusted to pl+ in the above example.

10 4 5.7 1.55
2 6.3 1.52.5
1 6.7 3.61.25 0.
5 7.0 6.00.625 0.2
5 7. Q 7.4 Example 4 A solution of 2.9% MOCI2 was prepared. pl+ rare Mo
Adjusted with O slurry. After allowing the sample to equilibrate overnight, it was placed in a Magma '141170 corrator (
Tested using a registered trademark. Next, mild steel washer V-
was placed in solution for 30 days, and ff1fa loss was measured.

Total solution weight M percentage Corrosion rate of mild steel 2.9
0 7.3 6.6 12.62.
9 0.5 6.9 5.9 4.92
．． 9 1. Q 7.1 2.9 3.
02.9 1.5 7.4 2.05
2.92.9 5.0 7゜4 2.1
2.4 Example 5 A sodium chloride solution was prepared and N
a Adjusted with OH and stored overnight.

5 0 7.0 10.55
2 6.3 3.01007゜06,9 10 4 5.7 2.520
0 7.0 2.5 Example 6 The corrosion rate of mild steel of a MgCl2 solution consisting of fermented cassL or unfermented sodium sulfide old solution (N a S S L ) was measured to investigate the corrosivity. Not yet 8 years old
NMNaSSL contained approximately 65% sodium lignosulfonate.

5 10 0 6.6 0.8 4
．． 15 0 10 7.0 0.5
4.0 Example 7 A calcium chloride solution containing fermented Ca5SL was
Corrosion properties were measured in a 1-day test.

5 0 6.1 B, E) 5
5 5, 8 4.7 Example 8 Please refer to Example 4 for conditions.

Percentage of total solution weight 8.6 0.0 7.5 3.6
6.58.6 0.5
7.4 0.6 2.58.6
1.0 7.3 0.6
2.08.6 1.5 7.1
0.6 2.0 Example 9 After adjusting the pH of a calcium chloride solution containing fermented Ca5SL with CaO, the corrosivity was measured.

5.0 0.25 6゜32.55.0
1.0 7.1 2.45.0 2
．． 0 8.1 1.50.625 0.
25 7.0 7.40.625 2.0
7.0 1.8 Example 10 After adjusting the pl+ of a solution of sodium chloride and 1111)7L, Ca5SL with dilute sodium hydroxide, the corrosivity was measured.

5.0 0.0 7.0 10.55.
0 0.25 8.1 4.75.0
1.0 7.1 3.75.0 2
．． 0 6.3. 3.02.5 1.0
6.6 6.02, 5 2.0
7.0 2.50.625 0.25 7
．． m 14.60.625 2.0 7.
0 2.1 The data summarized above show that the addition of heavy sulfide solution significantly reduces the corrosivity. In Example 4, a 2.9% MqC12 solution The ratio to MoCl3 is 1
/6 shows a 60% reduction in weight loss due to corrosion compared to the same salt solution without sulfide heavy liquor. Corrosion will further decrease if more sulfide heavy liquid is suspended.

Example 8 shows that an 8.6% MgCl2 solution with a ratio of MoCl3 to sulfide heavy liquid of 1/17 reduces weight loss due to corrosion by 60% compared to the same test mixture containing no sulfide heavy liquid. ing. Example 10 shows that in a 5% NaCl solution, when the ratio of calcium 4-norphite old solution to NaCl was about 1/20, the effective corrosive effect was 5.8 mil/year compared to the same test mixture that did not contain sulfide heavy solution. (corrosion rate reduced by more than half). Examples 1 and 2 also show that the fermented calcium sulfide heavy liquor itself produces somewhat more corrosion than many of the sulfide heavy liquor-metal chloride mixtures.

Since modifications of the invention will become apparent to those skilled in the art, the invention is limited only by the scope of the claims.

Claims (16)

[Claims] (1) A waterproofing method for road surfaces that causes less corrosion of road metals, the ratio of lignosulfonate to metal chloride (
dry weight) is about 1:15 to about 2:1, and the pH is about 4.
．． adding to the snow or ice covered road surface an effective amount of a composition consisting essentially of a mixture of a lignosulfonate and a metal chloride, wherein the metal salt is an alkali metal and alkaline earth metal salts. (2) The method according to claim 1, wherein the lignosulfonate and the salt are added in a dry state. (3) The method according to claim 1, wherein the lignosulfonate comprises an old sulfide liquor, and the old sulfide liquor and the salt are added as a solution to the road surface. 4. The method of claim 1, wherein an anti-slip agent is also present in the mixture. 5. The method of claim 1, wherein the ratio is from about 1:8 to about 3:2. (6) The method of claim 1, wherein the pH of the mixture is about 5 to about 8. (7) The method according to claim 1, wherein the metal chloride is sodium chloride. (8) The method according to claim 1, wherein the metal chloride is magnesium chloride. (9) The method according to claim 1, which comprises an old calcium sulfide solution in which lignosulfonate is fermented. (10) The method of claim 1, wherein the lignosulfonate consists of old sodium sulfide liquor, such as obtained from the sulfide process. (11) consisting essentially of a mixture of lignosulfonate and alkali metal chloride, wherein the ratio of lignosulfonate to alkali metal chloride (dry weight) is about 1:25 to about 15:1, and the pH of the mixture is about 4.5 to about 8.
5. An anti-icing composition that is less corrosive to road metals. (12) the alkali metal salt is sodium chloride,
12. The waterproofing composition of claim 11, wherein the ratio of lignosulfonate to sodium chloride (dry weight) is from about 1:15 to about 2:1. (13) consisting essentially of a blend of a lignosulfonate and a mixture of an alkali metal chloride and an alkaline earth metal chloride, the ratio of lignosulfonate to the mixture (dry weight) being from about 1:25 to about 15:1; A waterproofing composition that is less corrosive to road metals, wherein the formulation of lignosulfonate and a salt mixture of an alkali metal chloride and an alkaline earth metal chloride has a pH of about 4.5 to about 8.5.
A waterproof composition characterized in that: (14) The alkali metal chloride is sodium chloride, the alkaline earth metal chloride is magnesium chloride, and the ratio of the lignosulfonate to the salt mixture of sodium chloride and magnesium chloride is about 1:15 to
14. The waterproofing composition of claim 13, wherein the ratio is about 2:1. (15) The waterproof composition according to claim 12, wherein the ratio is about 1:8 to about 3:2. (16) The waterproof composite according to claim 14, wherein the ratio is about 1:8 to about 3:2.