NZ623854B2 - Deicing composition comprising molasses and lignin derivative - Google Patents
Deicing composition comprising molasses and lignin derivative Download PDFInfo
- Publication number
- NZ623854B2 NZ623854B2 NZ623854A NZ62385412A NZ623854B2 NZ 623854 B2 NZ623854 B2 NZ 623854B2 NZ 623854 A NZ623854 A NZ 623854A NZ 62385412 A NZ62385412 A NZ 62385412A NZ 623854 B2 NZ623854 B2 NZ 623854B2
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- NZ
- New Zealand
- Prior art keywords
- molasses
- deicing
- chloride
- ppm
- sodium
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 94
- 235000013379 molasses Nutrition 0.000 title claims abstract description 88
- 229920005610 lignin Polymers 0.000 title claims abstract description 52
- FAPWRFPIFSIZLT-UHFFFAOYSA-M sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 66
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 52
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 43
- 239000011780 sodium chloride Substances 0.000 claims abstract description 38
- SCVFZCLFOSHCOH-UHFFFAOYSA-M Potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims abstract description 31
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L MgCl2 Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000001103 potassium chloride Substances 0.000 claims abstract description 20
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 20
- 229920001732 Lignosulfonate Polymers 0.000 claims abstract description 19
- 239000004117 Lignosulphonate Substances 0.000 claims abstract description 19
- HLBBKKJFGFRGMU-UHFFFAOYSA-M Sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000004280 Sodium formate Substances 0.000 claims abstract description 19
- 235000019357 lignosulphonate Nutrition 0.000 claims abstract description 19
- VMHLLURERBWHNL-UHFFFAOYSA-M sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000001632 sodium acetate Substances 0.000 claims abstract description 19
- 235000017281 sodium acetate Nutrition 0.000 claims abstract description 19
- 235000019254 sodium formate Nutrition 0.000 claims abstract description 19
- ZORPJCONVDWMSP-UHFFFAOYSA-J calcium;magnesium;tetraacetate Chemical compound [Mg+2].[Ca+2].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O ZORPJCONVDWMSP-UHFFFAOYSA-J 0.000 claims abstract description 18
- UXVMQQNJUSDDNG-UHFFFAOYSA-L cacl2 Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 17
- 239000001110 calcium chloride Substances 0.000 claims abstract description 17
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 17
- 235000011056 potassium acetate Nutrition 0.000 claims abstract description 17
- WFIZEGIEIOHZCP-UHFFFAOYSA-M Potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims abstract description 16
- 229910001629 magnesium chloride Inorganic materials 0.000 claims abstract description 15
- 235000011147 magnesium chloride Nutrition 0.000 claims abstract description 15
- 235000011148 calcium chloride Nutrition 0.000 claims abstract description 12
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 claims abstract description 8
- 241000209149 Zea Species 0.000 claims abstract description 8
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims abstract description 8
- 235000005822 corn Nutrition 0.000 claims abstract description 8
- 235000005824 corn Nutrition 0.000 claims abstract description 8
- 240000000111 Saccharum officinarum Species 0.000 claims abstract description 7
- 235000007201 Saccharum officinarum Nutrition 0.000 claims abstract description 7
- 239000006188 syrup Substances 0.000 claims abstract description 7
- 235000020357 syrup Nutrition 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- 239000007787 solid Substances 0.000 claims description 46
- 239000010426 asphalt Substances 0.000 claims description 23
- 238000003892 spreading Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 5
- 241000219094 Vitaceae Species 0.000 claims description 4
- 239000011449 brick Substances 0.000 claims description 4
- 239000004567 concrete Substances 0.000 claims description 4
- 235000021021 grapes Nutrition 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 235000007686 potassium Nutrition 0.000 claims description 4
- 229940035295 Ting Drugs 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 2
- 235000015424 sodium Nutrition 0.000 claims 2
- 238000005507 spraying Methods 0.000 claims 1
- 230000002829 reduced Effects 0.000 abstract description 6
- 235000004284 Vitis rupestris Nutrition 0.000 abstract 2
- 239000012267 brine Substances 0.000 description 16
- 239000011550 stock solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000007710 freezing Methods 0.000 description 7
- 239000000654 additive Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 241000196324 Embryophyta Species 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002023 wood Substances 0.000 description 4
- 241000195493 Cryptophyta Species 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-L Sulphite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 235000000346 sugar Nutrition 0.000 description 3
- 150000008163 sugars Chemical class 0.000 description 3
- 238000010257 thawing Methods 0.000 description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N D-sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N Hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- LZFOPEXOUVTGJS-ONEGZZNKSA-N Sinapyl alcohol Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O LZFOPEXOUVTGJS-ONEGZZNKSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011384 asphalt concrete Substances 0.000 description 2
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 description 2
- -1 calcium magnesium Chemical compound 0.000 description 2
- DTYCRHCCLVCUDT-UHFFFAOYSA-J calcium;magnesium;tetrachloride Chemical compound [Mg+2].[Cl-].[Cl-].[Cl-].[Cl-].[Ca+2] DTYCRHCCLVCUDT-UHFFFAOYSA-J 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 235000016068 Berberis vulgaris Nutrition 0.000 description 1
- 241000335053 Beta vulgaris Species 0.000 description 1
- 210000002421 Cell Wall Anatomy 0.000 description 1
- 241000282619 Hylobates lar Species 0.000 description 1
- 241000229754 Iva xanthiifolia Species 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L Magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 229910003202 NH4 Inorganic materials 0.000 description 1
- PTNLHDGQWUGONS-OWOJBTEDSA-N Paracoumaryl alcohol Chemical compound OC\C=C\C1=CC=C(O)C=C1 PTNLHDGQWUGONS-OWOJBTEDSA-N 0.000 description 1
- 229960004793 Sucrose Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating Effects 0.000 description 1
- 230000000996 additive Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004061 bleaching Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000003841 chloride salts Chemical group 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000875 corresponding Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 239000011121 hardwood Substances 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 230000003301 hydrolyzing Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000670 limiting Effects 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M methanoate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 230000000813 microbial Effects 0.000 description 1
- 125000002293 monolignol group Chemical group 0.000 description 1
- 229930014251 monolignols Natural products 0.000 description 1
- 230000001264 neutralization Effects 0.000 description 1
- PVNIIMVLHYAWGP-UHFFFAOYSA-N nicotinic acid Chemical group OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained Effects 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229920005552 sodium lignosulfonate Polymers 0.000 description 1
- 239000011122 softwood Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N sulfonic acid Chemical group OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 230000000007 visual effect Effects 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
Abstract
Disclosed is a deicing composition comprising (i) a deicing agent selected from the group consisting of sodium chloride, calcium magnesium acetate, calcium chloride, magnesium chloride, potassium chloride, potassium acetate, sodium acetate, sodium formate, potassium formate, (ii) a lignin derivative, and (iii) molasses. The deicing composition remains effective over a longer period of time, so that the deicing agent can be applied less frequently and the damage to especially highly porous road surfaces will be reduced. Also disclosed is a process for preparing the deicing composition and to a process for deicing a surface using the deicing composition. In certain embodiments the lignin derivative is lignosulphonate. In certain embodiments the molasses is selected from the group consisting of molasses derived from corn (syrup), sugar beet, sugar cane, and grapes. , and (iii) molasses. The deicing composition remains effective over a longer period of time, so that the deicing agent can be applied less frequently and the damage to especially highly porous road surfaces will be reduced. Also disclosed is a process for preparing the deicing composition and to a process for deicing a surface using the deicing composition. In certain embodiments the lignin derivative is lignosulphonate. In certain embodiments the molasses is selected from the group consisting of molasses derived from corn (syrup), sugar beet, sugar cane, and grapes.
Description
DEICING ITION COMPRISING MOLASSES AND LIGNIN
DERIVATIVE
The present ion relates to a deicing composition and to a process for the
ation of said deicing composition. It furthermore relates to a process for
g a surface and to a kit of parts for use in said process. Finally, it relates to
the use of a combination of a lignin derivative and es for improving the
efficiency of a deicing composition.
Wintry conditions provide inconveniences for roads and traffic in the form of snow
or black ice. Obviously, eliminating snow, frost, and ice on roads and highways
has enormous safety benefits. Sodium chloride (NaCl) is commonly used to
control snow and ice formation on roadways, highways, and sidewalks. The
sodium chloride works as a deicing agent by dissolving into precipitation on
roadways and lowering the freezing point, thereby melting ice and snow. Other
salts that can be used as deicers include for example calcium chloride and
magnesium chloride. These compounds depress the freezing point of water to an
even lower temperature than sodium chloride. Also potassium chloride is
sometimes used as a deicer. r, commonly known alternative to road salt is
calcium magnesium acetate. Other, less known deicer salts include potassium
acetate, sodium acetate, sodium formate, and potassium e.
The wintry conditions also cause damage to asphalt, bituminous, and te
surfaces. These surfaces have porous structures. Asphalt in particular comprises
a number of subsurface channels. When the air/ground ature becomes
sufficiently low, an aqueous on which is present in the channels of the
asphalt will expand upon freezing, thus creating mechanical stress in the asphalt.
Especially after repeated freezing and thawing, the asphalt will break, resulting in
es. Not only do large sums of money have to be spent each year to repair
3O d roadways and highways, potholes can also result in dangerous
situations fortraffic. Furthermore, the additional maintenance required will result in
additional traffic jams.
The problem of damage to roadways and highways because of the expansion and
ction of water or water-based solutions during freezing and thawing cycles
has become an even bigger issue since the introduction of a new type of asphalt,
the so—called highly porous asphalt, in the nineties. This highly porous asphalt
concrete may comprise up to 20% of hollow space. This has the advantage that
rain and melt water will flow away quickly from the t surface through the
subsurface channels into the soil. The asphalt road surface itself retains practically
no moisture, and hence, is not slick and slippery even in case of heavy rainfall.
While the use of this type of asphalt has an enormous beneficial effect on safety
under rainy conditions, a disadvantage is that under wintry conditions more of the
deicing agent is needed in order to keep the roads free of snow and ice during the
winter, as the deicing agent will also flow away from the road surface with the melt
water.
It is an object of the present invention to e a deicing composition which has
improved g properties, or at least provides the public with a useful choice.
More particularly, it is an object of the present invention to e a deicing
composition which remains effective over a longer period of time, so that the
deicing agent can be applied less frequently and the damage to ally highly
porous road surfaces will be reduced.
Surprisingly, the objective has been met by adding a combination of two types of
ves, viz. a lignin derivative and molasses, to a deicing agent. In more detail,
the present invention relates to a deicing composition comprising (i) a deicing
agent selected from the group consisting of sodium chloride, calcium magnesium
e, calcium chloride, magnesium chloride, potassium chloride, potassium
acetate, sodium acetate, sodium formate, and potassium formate, (ii) a lignin
derivative, and (iii) molasses.
[followed by page 2a]
In one aspect, there is ed a deicing composition comprising
(i) a deicing agent selected from the group consisting of sodium
chloride, m magnesium acetate, calcium chloride, ium
chloride, potassium chloride, potassium acetate, sodium acetate,
sodium formate, and potassium formate,
(ii) between 10 ppm and 10,000 ppm of a lignin derivative, and
(iii) between 10 ppm and 50,000 ppm of molasses.
In a further aspect, there is provided a use of a combination of a lignin derivative
and molasses for improving the efficiency of a deicing composition comprising a
g agent selected from the group consisting of sodium chloride, calcium
magnesium acetate, m de, magnesium chloride, potassium chloride,
potassium acetate, sodium acetate, sodium formate, and potassium formate in the
deicing of surfaces.
[followed by page 3]
WO 68299
It was found that the g composition according to the present invention has
an ed performance. It was found that by using the specific ation of
molasses and a lignin derivative, the deicing agent will remain active over a longer
period of time.
In addition, it was found that the use of the deicing composition according to the
present invention reduces damage to road surfaces after repeated freezing and
thawing.
The g composition according to the present invention was found to be less
ive than conventional deicing compositions.
Due to better adhesion properties of the deicing composition compared to use of
the deicing agent alone, less deicing agent is likely to be blown away and the
deicing agent will be retained on the road for a longer period of time.
The deicing agent present in the deicing composition according to the present
invention is selected from the group consisting of sodium de, calcium
magnesium acetate, calcium chloride, magnesium chloride, potassium chloride,
potassium acetate, sodium acetate, sodium formate, and potassium formate.
Preferably, however, the deicing agent is a chloride salt, is. it is preferably
selected from the group consisting of sodium chloride, calcium chloride,
magnesium chloride, and potassium de. More preferably, m chloride is
used as the deicing agent in the compositions according to the present invention.
Most preferably, sodium chloride is used as the deicing agent in the compositions
ing to the t invention, as it is cheap and available in large quantities.
The deicing composition according to the present invention can be in aqueous
form, solid form or in the form of a slurry.
if the deicing composition is an aqueous composition, the deicing agent is
preferably present in an amount of at least 5% by weight, more ably at least
% by weight, and most preferably at least 20% by weight (based on the total
weight of the deicing composition). Preferably, such aqueous deicing composition
comprises at most the saturation concentration of the deicing agent.
The deicing composition ing to the present invention can also be in the
form of a slurry, ning deicing agent at concentrations higher than the
tion concentration.
if the deicing composition is in the form of a solid, it may comprise as little as 5%
by weight of deicing agent (based on the total weight of the deicing composition) if
it is, for e, mixed with gritting material like sand. ably, however, the
solid deicing composition according to the present invention comprises at least
50% by weight of the deicing agent, yet more preferably at least 70% by weight,
and most preferably at least 96% by weight of the deicing agent (based on the
1O total weight of the g composition).
The biopoiymer lignin present in the deicing composition is an amorphous polymer
related to cellulose that provides rigidity and together with cellulose forms the
woody cell walls of plants and the cementing material between them. it generally
has an average molecular weight of at least 10,000 Da. Lignin is most commonly
found in wood, but can also be found in plants and algae. it consists of the
monolignols paracoumaryl alcohol, coniferyi alcohol, and sinapyl alcohol. These
monomers are incorporated in varying amounts.
Lignin can be rendered water—soluble by exposing it to acidic or alkaline conditions
or bleaching it (treatment with e.g. H202 or hypochlorite), thus increasing the
number of aliphatic and aromatic hydroxyl and carboxylic acid functionalities or
hydrolyzing it to lower molecuiar fragments. Under neutral conditions, lignin can
be hydrophilized by sulphite pulping while introducing sulphonate or sulphonic
acid functionality.
The term “lignin derivative” as used hout the specification is meant to
denote all compounds (including salts) derived from lignin using at least one of the
just-described procedures and which have a solubility of at least 10 g per iitre in
water at 25°C. Other al functionalities may be present as long as they do
not compromise the overall water-solubility. ably, the lignin derivative
according to the present ion has a lar weight of at least 5 kDa, more
preferably at least 10 kDa. More preferably, the lignin derivative carries carboxylic
acid onality, while most preferably, it carries sulphonate or nic acid
groups (i.e. it is a ulphonate).
A lignosulphonate, ing to the present invention, is a sulphonated Iignin
derived from the biopolymer lignin. During the pulping process of wood in the
presence of sulphite, the lignosulphonate is produced as a by—product. The
product can be (chemically) ed and spray-dried, though r of these steps
is required for a good efficacy in accordance with the present invention.
Lignosulphonates have very broad ranges of molecular mass (they are very
polydisperse). For example, a range of from LOGO—140,000 Da has been
reported for softwood. ulphonates with lower values have been reported
for hardwoods.
The lignin derivative suitable for use in the composition according to the present
invention is preferably a lignin derivative derived from wood, plants or algae. It is
also possible to use a mixture of lignin derivatives originating from different
sources. Most preferable is the use of a Iignin tive derived from wood. All
types of lignin derivatives can be used in the composition according to the present
invention, i.e. including the Na, K, Ca, Mg, or NH4 salts.
The lignin derivative is typically present in the deicing composition according to
the present invention in an amount of at least 10 ppm, more ably at least
100 ppm, and most preferably at least 500 ppm. It is preferably present in an
amount of less than 10,000 ppm, more preferably in an amount of less than 8,000
ppm, and most preferably in an amount of less than 5,000 ppm.
The lignin derivative concentrations are expressed in ppm, herewith defined as
mg lignin derivative per kg of the total deicing composition.
The molasses to be present in the g composition according to the present
invention can be any molasses conventionally used for deicing purposes. it is
noted that it is possible to use molasses which have been subjected to one or
more purification steps, such as the removal of sulphites, sulphur dioxide, ash,
microbial life forms or other insolubles, as removal of these contaminants does
not have an adverse effect on mance in the deicing composition. It is
furthermore noted that it is possible to use chemically, biologically, physically or
otherwise treated molasses, such as, but not exclusively, desugared beet
molasses, acid/base treated molasses, carboxylated molasses (wherein sugars
present in molasses have been carboxylated with conventional techniques), and
molasses containing one or more additives. Preferably, the molasses is ed
from the group consisting of molasses derived from corn ), molasses
derived from sugar beet, molasses derived from sugar cane, and molasses
derived from .
The term “molasses” includes all the above types of treated or untreated
molasses.
Preferably, the molasses is beet or cane sugar molasses containing n 20%
and 80% by weight of sugars, yet more preferably containing between 40% and
60% by weight of , most preferably between 45% and 55% by weight of
sugars.
The molasses is typically present in the deicing composition according to the
present invention in an amount of at least 10 ppm, more preferably at least 100
ppm, and most preferably at least 500 ppm. it is preferably t in an amount
of less than 50,000 ppm, more preferably in an amount of less than 10,000 ppm,
and most preferably in an amount of less than 5,000 ppm.
The molasses concentrations are expressed in ppm, herewith defined as mg
molasses per kg of the total deicing composition.
The t ion furthermore relates to a process for preparing the deicing
composition according to the present invention. Said process consists of ng
an aqueous treatment solution comprising a lignin derivative and molasses onto a
deicing agent selected from the group ting of sodium chloride, calcium
magnesium acetate, calcium chloride, magnesium chloride, potassium chloride,
potassium acetate, sodium acetate, sodium formate, and potassium formate.
ably, the aqueous treatment solution is d onto the deicing agent in an
amount so that the resulting deicing composition will comprise at least 10 ppm,
more preferably at least 100 ppm, and most ably at least 500 ppm of the
lignin derivative and at least 10 ppm, more preferably at least 100 ppm, and most
preferably at least 500 ppm of the molasses. Preferably, the resulting deicing
composition comprises no more than 10,000 ppm, more preferably no more than
8,000 ppm, and most preferably no more than 5,000 ppm of the lignin derivative.
1O Preferably, the ing deicing composition comprises no more than 50,000
ppm, more preferably no more than 10,000 ppm, and most preferably no more
than 5,000 ppm of the molasses.
As described above, the lignin derivative is preferably derived from plants or
algae. it can also be a mixture of lignin derivatives ating from ent
sources. The molasses is preferably ed from the group consisting of
molasses derived from corn (syrup), molasses derived from sugar beet, and
molasses derived from grapes.
The present invention furthermore relates to a process for deicing a e. Said
surface can be deiced in various ways.
in one embodiment the deicing composition according to the t invention is
spread onto said surface.
In another embodiment, the process for deicing a surface comprises the steps of
mixing a solid deicing agent selected from the group consisting of sodium chloride,
calcium magnesium acetate, calcium chloride, magnesium chloride, potassium
chloride, potassium e, sodium acetate, sodium formate, and potassium
formate with an aqueous treatment on comprising a lignin derivative and
molasses, and spreading the thus obtained mixture onto said surface. This
method is a preferred embodiment, since the risk of the deicing composition being
blown away is greatly reduced. Furthermore, a better adhesion of the deicing
ition to the road surface is attained.
In yet another embodiment, the process for deicing a surface comprises the steps
of preparing an aqueous solution sing n 5% by weight and the
saturation concentration of a solid deicing agent selected from the group
consisting of sodium de, calcium magnesium acetate, calcium chloride,
magnesium chloride, potassium chloride, potassium acetate, sodium acetate,
sodium formate, and potassium formate, a lignin derivative, and molasses and
applying said mixture onto said surface, e.g. by ng. This method is also a
1O preferred embodiment, since the risk of the deicing ition being blown away
is also greatly reduced in this method. Furthermore, a better adhesion of the
deicing composition to the road surface is attained.
In yet another embodiment of the present invention, the process for deicing a
surface comprises the steps of spreading a deicing agent selected from the group
ting of sodium chloride, calcium magnesium acetate, calcium chloride,
magnesium de, potassium chloride, ium acetate, sodium acetate,
sodium formate, and potassium formate in solid or s form onto said
surface and separately spreading a lignin derivative and molasses in solid or
aqueous form onto said surface.
The surface to be deiced is. preferably a surface selected from the group
consisting of non-porous asphalt road, asphalt road, porous t road,
concrete road, bituminous road, brick road, graveled path, cobbled road, unpaved
road, and pavement.
Preferably, at least 1 g of deicing agent, at least 0.01 mg of a lignin derivative, and
at least 0.01 mg of molasses is introduced per m2 of said surface. Preferably, no
more than 50 g of deicing agent is introduced per m2 of surface to be deiced.
Preferably, no more than 500 mg of a lignin derivative and no more than 2500 mg
of molasses are introduced per m2 of surface to be deiced.
WO 68299 2012/071678
In yet another aspect of the present invention, it relates to a kit of parts for use in
the process for deicing a surface. The kit of parts comprises an anti-icing
composition comprising a deicing agent ed from the group consisting of
sodium de, calcium magnesium acetate, calcium chloride, magnesium
chloride, potassium chloride, potassium acetate, sodium acetate, sodium formate,
and potassium formate as a component (a) and an aqueous on comprising
between 0% and its saturation concentration of the g agent, between 10
ppm and its saturation concentration of lignin derivative, and between 10 ppm and
1O its saturation concentration of molasses as a component (b). Preferably,
component (a) forms between 60 and 99.99% by weight of the kit of parts and
component (b) forms between 0.01% and 40% by weight of the kit of parts (with
component (a) and (b) adding up to 100%). Component (a) can be in the form of
an aqueous solution, a slurry, or a solid (vfde .
Component (b) can also be a solid mixture of lignin derivative and molasses.
ingly, the present invention also relates to a kit of parts for use in the
process for deicing a surface according to the present invention comprising an
anti-icing ition comprising a deicing agent selected from the group
consisting of sodium chloride, calcium magnesium acetate, calcium chloride,
magnesium chloride, potassium chloride, potassium acetate, sodium acetate,
sodium formate, and potassium formate as a component (a) and a solid
component comprising a lignin derivative and molasses as a component (b).
ably, component (3) forms between 90 and 99.9% by weight of the kit of
parts and component (b) forms between 0.1% and 10% by weight of the kit of
parts (with component (a) and (b) adding up to 100%). Component (a) can be in
the form of an aqueous solution, a slurry, or a solid (vide supra). Preferably, it is in
the form of a solid.
Finally, the present invention relates to the use of a combination of a lignin
derivative and molasses for improving the efficiency of a g composition
2012/071678
sing a deicing agent selected from the group consisting of sodium chloride,
calcium magnesium acetate, m chloride, magnesium chloride, potassium
chloride, potassium acetate, sodium acetate, sodium formate, and ium
formate, in the deicing of a surface. As said, said surface is preferably selected
from the group consisting of non—porous asphalt road, asphalt road, porous
asphalt road, concrete road, nous road, brick road, graveled path, cobbled
road, unpaved road, and pavement.
The present invention is further illustrated by the following non-limiting
Examples and Comparative Examples.
EXAMPLES
Example 1: ng tests
Materials:
Abbreviation Material Origin
H20 Water Tap water
NaCl NaCl, Sanal P grade AkzoNobel, Mariager,
Denmark
RM Raw Molasses Suiker Unie,
Netherlands
Ll Lignosulphonate Na 244, Borregaard,
spray dried Karlsruhe Germany
2012/071678
Machines
Machine Origin Settings
Refrigerator -29 deg Celsius
Sample ation
in all ations below, 22% by weight of NaCl brine is referred to as “brine”.
Possible impurities in the products are not accounted for in the calculation of the
final compound concentration; this concentration is defined as the ratio of
weighed amount of compound and total mass of the sample.
Compound concentrations are expressed in ppm, herewith defined as mg
compound / kg total sample mass.
Stock solutions
All preparations were d out batchwise. The mentioned amounts represent
the typical batch size at which all samples were prepared.
/ Brine was prepared by the dissolution of 220 9 NaCl into 780 g water.
J The lignosulphonate solutions were prepared by the slow addition of
sodium lignosulphonate powder to vigorously stirred brine. The brine was
stirred by means of a magnetic stirrer. Lignosulphonate stock solutions
contained either 30,000 or 3,000 or 300 ppm lignosulphonate.
f The RM solutions were prepared by careful on to vigorously stirred
brine. The brine was stirred by means of a magnetic stirrer. The stock
ons contained either 3,000 ppm or 30,000 ppm of RM.
Final solutions
The final sample solutions were obtained by mixing lignosulphonate and/or
molasses stock solutions and the addition of brine. Three examples:
/ Brine containing 1,000 ppm LI and 1,000 ppm RM: mixing
0 10 grams of 3,000 ppm LI stock solution
0 10 grams of 3,000 ppm RM stock solution
0 10 grams of brine
/ Brine containing 1,000 ppm LI and 10 ppm RM: mixing
0 10 grams of 3,000 ppm Ll stock solution
0 0.1 grams of 3,000 ppm RM stock solution
0 19.9 grams of brine
/ Brine containing 10,000 ppm Li and 1,000 ppm RM: mixing
0 10 grams of 30,000 ppm LI stock solution
0 10 grams of 3,000 ppm RM stock solution
0 10 grams of brine
All samples were prepared following the above-exemplified principle.
All s had the exact total weight of 30 grams, contained in a Greiner tube
(PP, 50 mL, Greiner ).
Experimental conditions
These Greiner tubes were stored in the fridge for a maximum of 2 days until the
start of the experiment. Upon starting the experiment, the tubes were stored in
the r at -29°C and evaluated by eye for their solids content, with an
cy of 5-10% per sample. The evaluation of solids t was done by
eye, implying the estimation of solids content with respect to the total volume of
the sample. All samples were prepared in three-fold and the presented solid
contents are calculated as the average of all three samples.
Results
Table 1 is a matrix representation of all combinations of lignosulphonate and
molasses tested at ent concentrations. Lignosulphonate is arranged
horizontally, with the leftmost column showing the samples without
lignosulphonate. The raw es is arranged vertically, with the uppermost
row showing the s without molasses. in the grey bars, the concentrations
of the corresponding additives are given in ppm (mg/kg). All numbers in the
white area represent the solids content after 24 hours.
The reference samples containing either lignosulphonate or molasses always
show high solids content, although not always 100% solids. However, after
longer time all these reference samples without exception completely solidified.
All other samples comprising both lignosulphonate and molasses do not solidify
completely, if at all. In all cases the solid content is much lower than that of their
respective references. From this table it can be derived that there is synergy
n ulphonate and molasses.
Table 1:
Lignosulphonate
In Table 2, detailed results of the experiments summarized in Table 1 are
shown. For each entry it is mentioned which ves were present and the
volume% of solids present in the sample after a certain time (in hours).
Table 2:
Composition
no additives Time (h) 0
Solids 87 100
Time (h)
Solids 93 100
100 ppm Ll
II80 93 100 100
1,000 ppm Ll Time (h)
Solids % OOOOOOOOO 753 ---87 87 98
,000 ppm Ll Time(h) 6 ---
Solids (%) 93
ppm RM Time (h) CO ..L 4 12100
*4;—Solids % 7
100 ppm RM Time (h) 4 31 1:00 .-100
Solids (%) OOOOOOOOOOOOOOOOOOOO 10 100 12030 II100
1,000 ppm RM Time (h) 4 5 23
Solids (0/2) \lO 98 100 100
,000 ppm RM Time (h) 21 23
Solids (%) .A. 83
ppm Ll + Time (h) 75
1,000 ppm RM Solids (%) 0
100 ppm LI + Time (h) 75
1,000 ppm RM Solids (%) 0
1000 ppm LI + Time (h) 6
1,000 ppm RM Solids % 0
,000 ppm LI + Time (h) 75
1,000 ppm RM Solids (%) 0
1,000 ppm Ll + Time (h) 75
ppm RM Solids % 0
1,000 ppm U + Time (h)
100 ppm RM Solids % N
1,000 ppm LI + '
,000 ppm RM Solids
WO 68299
Figures 1-2 have been added for further illustration. The results of Comparative
Examples A, B, C, D, E, H and Examples 1, 2, 3, and 4 (see
Table 2) can be found in Figure 1, with
A ->l<- representing no additives
| representing 10 ppm Li
J -A- representing 100 ppm LI
K -:1- representing 1,000 ppm LI
L -¢~- representing 10,000 ppm Li
D -+- representing 1,000 ppm RM
1 representing 10 ppm LI + 1,000 ppm RM
2 -A- representing 100 ppm Li + 1,000 ppm RM
3 -I- representing 1,000 ppm Li + 1,000 ppm RM
4 representing 10,000 ppm LI + 1,000 ppm RM
The results of ative Examples A, F, G, H, I, D and Examples 4, 5, 6, and
7 can be found in Figure 2 with
A ~>i<~ representing no additives
representing 10 ppm RM
C -A- enting 100 ppm RM
D -:1- representing 1,000 ppm RM
E -O- representing 10,000 ppm RM
K -+- representing 1,000 ppm LI
representing 10 ppm RM+ 1,000 ppm Li
6 -A- representing 100 ppm RM+ 1,000 ppm LI
3 -l- representing 1,000 ppm RM+ 1,000 ppm Li
7 representing 10,000 ppm RM+ 1,000 ppm Li
Both Figures show the synergy between lignosulphonate and molasses. All grey
dashed lines (samples containing only one ent) go up quickly to 100%
solid content, whereas all black solid lines (samples containing a mixture of
ulphonate and molasses) stay well below all grey dashed lines.
The fact that the compositions according to the present invention do not become
solid at a temperature as low as ~29°C has the age that damage to road
surfaces due to wintry conditions is reduced. After all, as explained in the
description, said damage is caused by repeated freezing and g of aqueous
compositions inside the roads porous structure, as the mechanical stress thus
d results in potholes.
Example 2: Measurement of frost damage to asphalt
A y was selected with two lanes in each direction. Both directions had very
comparable asphalt quality and c density and identical weather conditions.
Both directions were physically separated and de-iced by the abovementioned
method. In this way, the reference and g compositions were independently
applied and analyzed. On both sides the development of damage was quantified:
cracks were ed in meters and raveling was expressed as an areal
percentage. This analysis was done for each 100 m section. The development of
raveling and cracks during the winter is reported in Tables 3 and 4.
Item Details
Composition Spreading: 50% by weight solid NaCl + 50% by weight
brine (22% by weight NaCl + 0.3% by weight Ll + 0.3% by
weight RM). The additive content is expressed in dry mass.
Reference Spreading: 50% by weight solid NaCl + 50% by weight
brine (22% by weight NaCl)
Duration One winter season (December —- March)
Location Denmark, highway, two lanes in both directions.
Asphalt Dense asphalt concrete, ten years old with some existing
raveling and cracks.
Deicing 86 deicing actions were carried out throughout the winter
2012/071678
Weather Temperatures mostly between -5 and +5 °C, some wintry
precipitation.
Sections 51 reference sections and 49 sections where the preferred
deicing composition was applied. Each measuring 100 m
in length.
Analysis Raveling and cracks analyzed according to the Dutch
CROW standard by means of detailed visual inspections:
CROW publication 146a, 2005).
ing Raveling is quantified in areal ons and in the
categories (zero (0), light (L), medium (M), and severe (8)).
These categories are part of the above-mentioned CROW
standard.
Table 3: Development of raveling
Reference 0.12% (2) 1.39% (13) 0.04% (1)
{ Deicing composition 0.34% (1) 0.00% (48) l 0.00% (48)
Table 3 gives the fraction of road surface area that underwent deterioration in
terms of raveling. The occurring s were unraveled g into lightly
raveled (indicated as 0 —- L, column 1), lightly raveled turning into medium d
(indicated as L -— M, column 2), and unraveled turning into medium raveled
(indicated as 0 — M, column 3). The number of occurrences (number of 100 m-
sections) is given in parentheses. In total, 15 reference sections of 100 m suffered
from increased raveling, whereas only 1 100m section d with the deicing
ition showed increased raveling. The totals mentioned in Table 3 show
that the deicing composition reduces the development of raveling approximately
by a factor of 4.
Table 4: Development of cracks
l ‘ Before After
winter I Gain.
winter
[ Reference | 62.2 (10) 97.2 (11) l 35(5)
lDeicing composition l 126 (20) 147 (20) 1 21 (2)
Table 4 gives the total crack length in . in parentheses the number of
sections with cracks is given. Despite the larger number of initial cracks and the
higher total crack length, the cracks developed approximately 3 times less if the
deicing composition was used.
The above results show that the deicing composition according to the invention
effectively reduces frost damage (raveling and cracks) ed to the reference
deicing method.
Claims (1)
- Claims A deicing composition comprising (i) a deicing agent selected from the group consisting of sodium chloride, calcium magnesium acetate, calcium de, magnesium chloride, potassium chloride, potassium acetate, sodium acetate, sodium e, and potassium formate, (ii) between 10 ppm and 10,000 ppm of a lignin tive, and (iii) between 10 ppm and 50,000 ppm of molasses. Deicing composition according to claim 1 wherein the molasses is ed from the group consisting of molasses derived from corn (syrup), es derived from sugar beet, molasses derived from sugar cane, and es derived from grapes. Deicing composition according to claim 1 or 2 wherein the deicing composition is - an aqueous deicing composition comprising at least 5% by weight, based on the total weight of the deicing composition, of deicing agent, 20 - a solid deicing composition comprising at least 50% by weight, based on the total weight of the deicing composition, of deicing agent, - a deicing composition in slurry form, comprising deicing agent in an amount higher than its saturation concentration. g composition according to any one of claims 1-3 wherein the molasses is selected from the group ting of molasses derived from corn (syrup), molasses derived from sugar beet, molasses d from sugar cane, and molasses derived from grapes. Deicing composition according to any one of claims 1-4 wherein the deicing agent is sodium chloride. Deicing composition according to any one of claims 1-5 wherein the lignin tive is lignosulphonate. A process for preparing a deicing composition according to any one of claims 1—6 comprising the step of spraying an aqueous treatment solution comprising a lignin derivative and molasses onto a deicing agent selected from the group consisting of sodium chloride, calcium magnesium acetate, calcium chloride, magnesium chloride, potassium chloride, potassium acetate, sodium acetate, sodium formate, and potassium formate, wherein 1O the lignin tive is present in the ing deicing composition in an amount of between 10 ppm and 10,000 ppm and the molasses is present in the resulting deicing composition in an amount of between 10 ppm and 50,000 ppm. 15 A process according to claim 7 wherein the deicing agent is sodium chloride. A process ing to any one of claims 7-8 wherein the molasses is selected from the group consisting of molasses d from corn (syrup), 20 molasses derived from sugar beet, molasses derived from sugar cane, and molasses derived from grapes. 10. A process for deicing a surface, said process comprising (i) the step of spreading a deicing composition according to any one of 25 claims 1-6 onto said surface; or (ii) the steps of mixing a solid deicing agent selected from the group consisting of sodium chloride, calcium magnesium acetate, calcium chloride, magnesium de, potassium chloride, ium acetate, sodium acetate, sodium formate, and potassium formats 30 with an s treatment on comprising a lignin derivative and molasses, and spreading the thus obtained mixture onto said surface, or (iii) the steps of preparing an s solution comprising between 5% by weight and the saturation concentration of a solid deicing agent selected from the group consisting of sodium chloride, calcium magnesium acetate, calcium chloride, magnesium chloride, potassium chloride, potassium acetate, sodium acetate, sodium formate, and potassium formate, lignin derivative, and molasses, and applying said mixture onto said surface, or (iv) the steps of spreading a deicing agent selected from the group consisting of sodium chloride, calcium magnesium acetate, calcium 1O chloride, ium chloride, potassium chloride, potassium acetate, sodium acetate, sodium formate, and potassium formats in solid or s form onto said surface, and separately spreading lignin tive and molasses in solid or aqueous form onto said surface. 11. s according to claim 10 wherein the g agent is sodium chloride. 12. Process according to claim 10 or 11 wherein the molasses is selected from 20 the group consisting of molasses derived from corn (SyrUp). molasses derived from sugar beet, molasses derived from sugar cane, and molasses derived from . 13. Process according to any one of claims 10-12 wherein the surface is 25 selected from the group consisting of non—porous asphalt road, asphalt road, porous asphalt road, concrete road, bituminous road, brick road, graveled path, cobbled road, unpaved road, and pavement. 14. Process according to any one of claims 10-13 n between 1 and 50 g 30 of g agent, n 0.01 and 500 mg of lignin derivative, and between 0.01 and 2,500 mg of molasses is introduced per m2 of said surface. 15. A kit of parts for use in the process according to any one of steps (ii) to (iv) of claim 10 or any one of claims 11 to 14 r as these claims depend from any one of steps (ii) to (iv) of claim 10, the kit of parts comprising - an anti-icing composition comprising a deicing agent selected from the group consisting of sodium chloride, calcium magnesium acetate, calcium chloride, magnesium chloride, potassium chloride, potassium acetate, sodium acetate, sodium formate, and potassium formate as a component (a), and 10 — as a component (b) either (i) an aqueous solution comprising between 0% and its saturation concentration of the deicing agent, between 10 ppm and its saturation concentration of lignosulphonate, and between 10 ppm and its saturation tration of molasses or (ii) a solid component comprising lignin derivative and molasses. 16. Kit of parts ing to claim 15 with component (b) being an aqueous solution comprising between 0% and its saturation concentration of the deicing agent, n 10 ppm and saturation concentration of the lignin derivative, and between 10 ppm and its saturation tration of the 20 molasses, and wherein component (a) forms between 60 and 99.99% by weight of the kit of parts and component (b) forms between 0.01% and 40% by weight of the kit of parts. 17. Use of a ation of a lignin derivative and molasses for improving the 25 efficiency of a deicing composition comprising a deicing agent ed from the group consisting of sodium chloride, calcium magnesium acetate, calcium chloride, magnesium chloride, potassium chloride, potassium acetate, sodium e, sodium formate, and potassium formate in the deicing of surfaces. 18. Use ing to claim 17, wherein the surfaces are ed from the group consisting of non-porous asphalt road, asphalt road, porous asphalt road, concrete road, bituminous road, brick road, graveled path, cobbled road, unpaved road, and pavement. 19. Deicing composition according to any one of claims 1 to 6, substantially as 5 herein bed with reference to any one of the Examples and/or
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP11188481 | 2011-11-09 | ||
EP11188481.3 | 2011-11-09 | ||
PCT/EP2012/071678 WO2013068299A1 (en) | 2011-11-09 | 2012-11-02 | Deicing composition |
Publications (2)
Publication Number | Publication Date |
---|---|
NZ623854A NZ623854A (en) | 2016-08-26 |
NZ623854B2 true NZ623854B2 (en) | 2016-11-29 |
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