HU206225B - Melting mixture for removing snow and ice from surfaces, particularly for ensuring winter traffic on public roads - Google Patents

Abstract

Antifreeze and snow and ice removing agent contains 20-90 (wt.)% waste concentrate (I) from the alcohol industry, with a dry substance content of 200-750 g/kg, 10-80% water and opt. additives (II). (I) is pref. based on molasses. (II) may be (a) NaCl, CaCl2, KCl, MgCl2 and/or urea; (b) sand, river gravel, slag and/or sawdust; and/or (c) a surfactant with an HLB value of 6-12, pref. 8-10. For removing snow and ice, the agent is strewn from a mobile vehicle in an amt. of 0.05-0.4 l/m2 road surface.

Description

FIELD OF THE INVENTION The present invention relates to a melting mixture for de-icing surfaces, especially for winter traffic on public roads, which optionally comprises a salt-salt mixture and other additive (s) for reducing the freezing point of water.

Road transport is developing dynamically from year to year. As the development progresses, the cross-section of the road network is getting narrower, which is even more pronounced in the winter, resulting in ever-increasing traffic jams and the risk of accidents. As a result, winter road cleaning requires, in addition to mechanical heat removal, chemical de-icing. Chemicals used for chemical road cleaning are predominantly chemicals containing various chloride ions, such as sodium chloride, magnesium chloride, calcium chloride, which are either applied singly in solid or liquid form or mixed with sand and / or other particulate matter. . The very disadvantage of using such materials is their environmental impact.

Thus, due to their harmful effects on the soil, the physical properties of the soil can be greatly impaired and alkalinised.

High salt concentrations also cause significant damage to surface waters.

Last but not least, damage to vegetation is also significant, since salinity is absorbed through plant parts and through the root system, resulting in partial or complete extinction of grass and tree species along the roads.

We also need to mention the corrosion effect of known melting compounds, which can be applied to vehicles, concrete coverings, reinforced concrete structures, metal objects in the ground - eg. through corrosion of gas pipelines - causing millions of damage not only in our country but worldwide.

The above problem is covered in very extensive literature. Most of these, however, deal primarily with mechanical solutions for mechanical snow removal and chemical de-icing, or parts thereof, and provide related equipment. Chemicals used for de-icing and de-icing are generally well-known and have been used for decades, such as CaCl ₂ , MgClH ₂ and NaCl. so e.g. in the Federal Republic of Germany 1 million tons of industrial salt is used annually, while in Budapest 15-17 000 m ^{3 of} industrial salt and 5 000 m ^{3 of} 36% industrial corrosive MgCl ₂ solution are used annually.

Of course, attempts have also been made to replace the above-mentioned salts, e.g. with ammonium sulfate, ammonium nitrate, ammonium chloride. However, experience has shown that the environmental impact could not be eliminated in this way and that, furthermore, the high cost of using salts is disadvantageous.

There are also known solutions in which de-icing is performed by mixing the known salts - chlorides, nitrates - optionally with NaOH in the road building material itself. Continuous wear on the road surface always results in new and new de-icing particles coming into contact with snow or ice adhering to the road surface. Such solutions are disclosed in HU 169,601, US 4,094,649 and US 4,152,473.

This way of designing the road surface can reduce the environmental impact of the chemicals used in de-icing, but it does not solve the problem of de-icing itself, as the number of road surfaces created by this technology is limited and by conventional technology . In this case, de-icing can only be achieved using known melting mixtures.

The use of ureas, alkylene glycols, alcohols or mixtures thereof has been replaced by water soluble salts to reduce environmental damage.

HU 162 461 U.S. Patent No. 4,123,198 discloses a melting agent containing urea as the main component and small amounts of phosphates to reduce the corrosion effect of urea.

A similar melting mixture is disclosed in U.S. Patent No. 3,928,221. Patent Specification, 23-25% by weight of urea,

It is a mixture of 11-15% ethylene glycol and 35-40% methanol and the pH is adjusted to 8.1-8.4 to reduce corrosion.

CH 611 333 discloses a de-icing mixture containing 30-40% by volume of C 2 -C 6 alylene glycol, dissolved in water, and a dye that shows the melting of the melt mixture.

The known melting mixtures described above have proven to be most advantageous from both a practical and an environmental point of view, but the following disadvantages prevent their widespread application:

- Urea is a metal corrosive compound which, although corrosive, can be reduced but not completely eliminated, and has a significant soil-damaging effect.

- Glycols, which are petroleum-based compounds, are expensive and also harmful to the environment, especially to plants.

It is noted that GB 1 463 401 is incorporated herein by reference. In particular, the US Patent No. 4,123,125 proposes an antifreeze salt salt instead of ethylene glycol for internal combustion engines because of the high price and limited availability of ethylene glycol. However, this salt mixture also contains components that are harmful to the environment and toxic and are therefore not suitable for de-icing free surfaces such as public areas.

- Methanol is toxic and flammable, so handling and storing it has many disadvantages and is also toxic.

- Likewise, the other short-chain glycols used in the melting mixture known hitherto are flammable and expensive.

Melting mixtures containing polyvinyl acetate and polyvinyl alcohol are also known. These

However, materials are also expensive and harmful to the environment.

Thus, materials used to date for chemical snow and ice removal are disadvantageous in many respects. However, there are very high requirements for the materials 5 to overcome these disadvantages.

One such requirement is e.g. water solubility, availability in large quantities, minimizing environmental and corrosion effects, low cost and applicability in conventional equipment.

It is an object of the present invention to provide a melting mixture which eliminates the disadvantages of the materials used so far and satisfies the requirements thereof: namely, water-soluble, inexpensive, available in large quantities, non-commissive and environmentally friendly, that is, spreadable. 20

The invention is based on the discovery that large-scale fermentation of the world-wide fermentation from various raw materials produces a substantial amount of the so-called spirit distillate which can be produced by proper distillation of a very good quality antifreeze agent. This waste concentrate is a completely neutral concentrate which, due to the chemical composition of the autolysed yeast cells contained in it, is anticorrosive due to the high protein content, reduces the corrosion effect of the solid salt or solid salt-sand mixture that may be used with it. . With this, 35 previously unknown properties of the alcoholic waste used for agricultural purposes have been explored and exploited. Alcoholic concentrates or other similar substances have not yet been used for de-icing surfaces.

The object of the present invention is achieved by a melting composition comprising from 20 to 90% by weight of a protein concentrate containing 200-750 g / kg of dry solids and up to 60% by weight of water, optionally containing salt mixtures and additives known per se. . Experimental experience has shown that it is advantageous for the melt mixture to contain 60-90% by weight of waste concentrate and 10-40% by weight of water.

In a preferred embodiment of the melting mixture according to the invention, the waste concentrate comprises molasses-based alcoholic waste 50 or sugar-cane-based alcoholic waste or carbohydrate-containing base and waste material for sugaring and fermentation.

Another preferred embodiment of the melting mixture according to the invention is 700 g / kg dry matter, 600 g / kg organic matter, 100 g / kg ash, 10 g / kg Ca, 20 g / kg Na, g / kg K, 2 g / kg. kg S, 300 mg / kg Fe, 1 g / kg P, 30 mg / kg

Contains molasses-based waste concentrate containing Mn and 20 mg / kg Zn.

In a further preferred embodiment of the melting mixture according to the invention, besides 23% by weight of the alcoholic waste concentrate and 9% by weight of water, 34% by weight of rock salt and 34% by weight of additive - river sand.

A preferred embodiment of the melting mixture according to the invention comprises NaCl, CaCl ₂ , KCl, MgCl ₂ or urea and / or mixtures thereof as salt or salt mixtures.

Another preferred embodiment of the melting mixture according to the invention is as an additive a sand, river gravel and / or sawdust particles having a grain size of 0.2 to 5 mm, preferably 0.5 to 2 mm, or hydrofxl-lipophilic groups having a HLB value of 6-12, preferably 8-10. containing from 0.1 to 26%, preferably from 0.5 to 1% by weight, of a solution containing.

The melting mixture according to the invention will now be described in more detail with reference to some embodiments.

During the distillation of alcohol, usually sugar and alcohol-free cca remains at 80100 ° C during fermentation of various carbohydrate-containing substances and distillation to obtain alcohol. 10-15% dry matter - so-called. is a slurry which is concentrated under vacuum to a dry matter content of 40-70% in order to reduce transport costs.

Its composition varies between Table I values:

/. spreadsheet

Solids 400-700 g / kg Organic material 400-600 g / kg Crude protein 100-250 g / kg Ash 100-250 g / kg ca 8- 15 g / kg So 15-30 g / kg K 60-80 g / kg mg 1-3 g / kg Cu, P, S, Fe, Mn, Zn 5 g / kg The melting mixture shown in the embodiment is a

contains as industrial waste concentrate a molasses-based waste concentrate the composition of which is shown in Annex II. See Table 1.

Table IL

Solids 700 g / kg Organic material 600 g / kg Ash 100 g / kg ca 10 g / kg So 20 g / kg K 80 g / kg S 3 g / kg Fe 300 mg / kg P 1 g / kg Mn 30 mg / kg Zn 20 mg / kg

The use of the waste concentrate used in the melting mixture according to the invention is illustrated by the following examples:

HU 206 225 Β v '

Example 1

On the UNICAR 2/2 base machine with a UN 15 wet salt grinder with standard adhesive salt blasting technology to replace the CaCl ₂ used to date

1.5 t 5 mm sieve (34% w / w) and sieve

1.5 t prescreened through river sand (34 wt%) mixture, and the blasting machine tanks filled with 1 t 70% solids concentrate (23 wt%) and 0.5 m ³ of water (9 weight percent) of 8 m of variation in width of 10 g / m ² de-icing was carried out with the addition of salt. The light brown color of the concentrate made the concentrate evenly distributed.

The experiment has proved that the substance is capable of replacing the previously used but environmentally polluting and corrosive CaCl ₂ .

Example 2

We also performed a routine experiment to replace CaCl ₂ and prevent decay with the Dutch NIDO spreader and sprayer, where

Sprayed with 0.05-0.4 1 / m ⁴ of 7.5 g / m ² undiluted concentrate with 70% dry matter and 15 g / m ² rock salt (1: 2 concentrate: salt mixing ratio).

After watering, the road surface regained its original black color, proving that the melting mixture is completely suitable for replacing the CaCl ₂ used previously.

Example 3

The purpose of the experiment was to completely replace the rock salt, which proved the use of various dilution waste concentrates alone.

The test was performed on a fallen snow layer 9 cm thick at an external temperature of -10 ° C. The 70% dry matter concentrate was diluted with water to 60% and 50% dry matter on 20,378 m ² road surface. No additive was used and thus the melting effect was investigated.

Compared with the industrial salt-sand mixture used hitherto, it was found that the melting effect of 50% dry matter concentrate was the same in time and activity, while the 60% dry matter concentrate had a melting effect of 1.5 hours shorter than the known and wide salt-sand mixture.

Furthermore, while the effect of the melting mixture used to date is completely slowed down at -7 ° C, the 60% concentrate has a melting effect at -13.6 ° C.

Under various weather conditions, mixed with different amounts of water, the waste concentrate was found to melt the snow faster than conventional melting mixtures, and ice, for example. the waste concentrate diluted with water at 65% by weight at 0 ° C and diluted with water at 54% by weight at -5 ° C.

A cost analysis was also carried out in this field experiment and it was found that at 50 and 60% dry solids, the cost was 0.078 Ft / m ² , compared to the conventional salt mixture, which was 0.16 Ft / m ² .

Example 4

For a series of experiments in a climate chamber at -5 ° C, the melting of water frozen on a bitumen surface was investigated with the following compositions of melting mixtures:

a) case

50% by weight of wastes with a dry matter content of 70% by weight

20% by weight of water containing 0.5% SOLASTAT (laurin10 acid polyglycol ester, HLB 10.2), 10% by weight of wood flour of 1 mm grain size for hydrophobization, 20% by weight of sand of 1 mm grain size

b) case

40% by weight of solid waste 70% by weight dry weight 20% by weight sand 20% urea.

As a result of the treatment, the ice layer on the bitumen surface melted very rapidly.

Example 5

The corrosion effect was investigated on iron plates immersed in a 20% NaCl solution containing 25 and 50% solids. The plates soaked in the waste concentrate did not show any change over 14 months as compared to the plates soaked in NaCl solution, which rusted completely within 3 days.

The same test was performed in a salt chamber to determine weight loss. The result of this study was a weight loss of 14% in the presence of NaCl and 10% in the presence of CaCl ₂ over a 3x24 hour period, and no weight loss in the presence of 50% dry waste 35% concentrate.

The amount of rust converted to surface is summarized in the following table:

Material used Quantity of rust in g / m ² 1% NaCl solution 60 1% solution of MgCl ₂ 50 1% CaCl ₂ solution 40 hulladéksűrítmény 0

Example 6

The melting mixture containing the 50% solid waste concentrate was sprayed onto a concrete surface frozen at -10 ° C with a 3 mm thick ice layer, in the form of a fine spray. The melting mixture sprayed on the concrete surface caused the ice surface to break down and set the temperature of the eutectic to -60 ° C, resulting in ice cracking and liquefaction.

Example 7

A series of experiments was performed on a -5 ° C climate chamber4

EN 206 225 Β of steel to investigate the anti-adherence effect of the carbon blend of the present invention, carbon powder having a grain size of 5 to 10 mm.

10% by weight sawdust (particle size: 1 mm) and a weight% hydrophobising surfactant (HLB value: 0.2) were added to the diluted waste concentrate to spray the wall of the container. 3 g / kg of the same mixture is added to the coal powder. It was found that the mixture prevented the carbon powder from sticking together without reducing the calorific value of the carbon powder.

The advantages of the melting mixture according to the invention with respect to the known mixture are shown below:

As a result of the complex effects described above, e.g. the risk of drifting of solid matter deposited prior to freezing due to wind or vehicle airflow, as the material captures individual particles on the surface of the pavement, eliminates anything on the roadside and is therefore more economical due to its lower weight / surface ratio.

The current freezing resistance of NaCl at 29% saturation solution is about -20 ° C, while the waste concentrate used in the melting mixture according to the invention is mixed with an equal volume of water at a concentration of 39-40 refractometers and can be transported at pump .

Further advantages are that the waste concentrate, including any mixture, which can be accurately metered without difficulty at any temperature and in any weather situation, immediately enters the frozen snow and ice layer when sprayed, resulting in a melting process throughout the sprayed surface, and Thus, the distribution on the surface of the casing is considerably smoother.

Due to the advantageous property of the waste concentrate content, the melting mixture according to the invention gradually melts the ice from the surface downwards, the surface of the casing cools slowly and evenly, and the temperature differences in the vertical and horizontal directions are smaller. The latter prevents the sudden cooling of the liquid capillary water in the capillaries of the unfrozen layer of concrete and thus the "peeling" or deterioration of the road surface, which is very common with the chemicals used today, and which is mainly the point-like heat principle.

_fc This is mainly the case with thicker ice armor or the melting of automotive ice sheets.

A further advantage of using the melt mixture according to the invention in solution is to provide a complete environment and corrosion protection. The sprayer is capable of defrosting a longer section in one pass, the vehicle speed is significantly higher at spraying - up to 50 km / h - and the solution can be stored in virtually any container available.

We would also like to point out that the liquor concentrate has been used so far for animal feed and fertilizer by injection, so its harmful effects are not to be expected.

The melting mixture according to the invention, as evidenced by the examples, is not only for public roads, but also for bulk goods, e.g. can also be used for de-icing coal, coal dust.

Claims (9)

PATENT CLAIMS Melting mixture for removing snow and ice from surfaces, in particular for winter circulation, containing chemical agent (s), optionally salt and salt mixture and other additive (s), reducing the wood boiling point of water, characterized in that It contains from 200 to 750 g / kg of dry matter, protein concentrate of spirit industry and up to 60% by weight of water. Melting mixture according to Claim 1, characterized in that the waste concentrate comprises molasses-based alcoholic waste. The melting mixture according to claim 1, characterized in that the waste concentrate comprises zucchini-based alcoholic waste. Melting mixture according to claim 1, characterized in that it contains waste material from the saccharification and fermentation of carbohydrate-containing base and waste material. The melting mixture according to claim 1, characterized in that 700 g / kg dry matter, 600 g / kg organic matter 100 g / kg ash, 10 g / kg Ca, 20 g / kg Na, 80 g / kg K, 3 g / kg S, 300 mg / kg Fe, 1 g / kg P, 30 mg / kg Contains molasses based waste concentrate containing 35 Mn and 20 mg / kg Zn. 6. Melting mixture according to any one of claims 1 to 3, characterized in that 23% by weight of the liquor concentrate and 34% by weight with 9% by weight of water It also contains 40 salts - rock salt - and 34% by weight of additives - river sand. 7. Melting mixture according to any one of claims 1 to 3, characterized in that NaCl, CaCl ₂ , KCl, MgCl ₂ or urea are used as salt or salt mixtures. 45 and / or a mixture thereof. 8. Melting mixture according to any one of claims 1 to 3, characterized in that the additive comprises glaze with a grain size of 0.25 mm, preferably 0.5-2 mm, sand, river gravel and / or sawdust. Melting mixture according to any one of Claims 1 to 7, characterized in that the additives containing hydrophilic lipophilic groups having a HLB of 6-12, preferably 8-10 HLB, are present in an amount of 0.1-2%, preferably 0.5-11%. aqueous solution.