U.S. patent application number 15/450062 was filed with the patent office on 2017-06-22 for methods for reducing odors in asphalt.
The applicant listed for this patent is Owens Corning Intellectual Capital, LLC. Invention is credited to Robert Edwin Quinn.
Application Number | 20170174887 15/450062 |
Document ID | / |
Family ID | 48570527 |
Filed Date | 2017-06-22 |
United States Patent
Application |
20170174887 |
Kind Code |
A1 |
Quinn; Robert Edwin |
June 22, 2017 |
METHODS FOR REDUCING ODORS IN ASPHALT
Abstract
Compositions and methods for reducing the foul odors of a
hydrocarbonaceous material such as asphalt comprise the addition of
an odor reducing amount of a reducing carbohydrate and/or a soluble
zinc compound. The reducing carbohydrate may be a monosaccharide,
oligosaccharide or polysaccharide, including a starch; and it may
be used as a sole odor reducing agent or in combination with
soluble zinc compounds and/or other odor reducing compounds.
Inventors: |
Quinn; Robert Edwin; (New
Albany, OH) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Owens Corning Intellectual Capital, LLC |
Toledo |
OH |
US |
|
|
Family ID: |
48570527 |
Appl. No.: |
15/450062 |
Filed: |
March 6, 2017 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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13706980 |
Dec 6, 2012 |
9631093 |
|
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15450062 |
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61567673 |
Dec 7, 2011 |
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 2555/60 20130101;
C08L 2555/82 20130101; C08K 5/098 20130101; C08K 5/1545 20130101;
C08L 95/00 20130101; C08K 3/10 20130101; C08L 95/00 20130101; C08L
95/00 20130101; C08K 3/10 20130101; C08L 95/00 20130101; C08L 3/00
20130101; C08L 95/00 20130101; C08L 5/00 20130101; C08L 95/00
20130101; C08K 5/1545 20130101; C08L 2555/62 20130101; C08K 5/07
20130101; C08L 1/00 20130101 |
International
Class: |
C08L 95/00 20060101
C08L095/00; C08K 5/07 20060101 C08K005/07; C08K 5/098 20060101
C08K005/098; C08K 5/1545 20060101 C08K005/1545 |
Claims
1. A method for reducing the undesirable odors of a
hydrocarbonaceous material, comprising adding to the
hydrocarbonaceous material a composition containing an odor
mitigating amount of at least one reducing carbohydrate.
2. The method of claim 1 wherein the reducing carbohydrate is a
monosaccharide.
3. The method of claim 2 wherein the monosaccharide is glucose.
4. The method of claim 1 wherein the reducing carbohydrate is a
polysaccharide.
5. The method of claim 4 wherein the polysaccharide has a DE from
about 2 to about 70.
6. The method of claim 1 wherein the reducing carbohydrate is an
oligosaccharide.
7. The method of claim 1 wherein the hydrocarbonaceous material is
an asphalt.
8. The method of claim 1 wherein the odor mitigating amount is from
about 0.001% w/v to about 5.0% w/v.
9. The method of claim 1, further comprising adding to the
hydrocarbonaceous material at least one additional odor mitigating
compound.
10. The method of claim 9 wherein the at least one additional odor
mitigating compound is selected from a soluble zinc compound or a
carbonyl compound having a molecular weight greater than about 100
Daltons and a boiling point greater than about 375.degree. F.
11. A method for reducing the undesirable odors of a
hydrocarbonaceous material, comprising adding to the
hydrocarbonaceous material a concentrate containing an odor
mitigating amount of at least one soluble zinc compound.
12. The method of claim 11 wherein the soluble zinc compound is a
salt of a C8-C20 fatty acid.
13. The method of claim 12 wherein the soluble zinc compound is
selected from salts of lauric acid, myristic acid, myristoleic,
palmitic acid, palmitoleic acid, stearic acid, oleic acid,
linioleic acid, and linolenic acid.
14. The method of claim 11 wherein the soluble zinc compound is a
salt of a C12-C18 fatty acid.
15. The method of claim 11 further comprising adding to the
hydrocarbonaceous material at least one additional odor mitigating
compound.
16. The method of claim 12 wherein the at least one additional odor
reducing compound is selected from a reducing carbohydrate or a
carbonyl compound having a molecular weight greater than about 100
Daltons and a boiling point greater than about 375.degree. F.
17. The method of claim 11 wherein the hydrocarbonaceous material
is an asphalt.
18. The method of claim 11 wherein the odor mitigating amount is
from about 0.001% w/v to about 5.0% w/v.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a divisional of U.S. patent application
Ser. No. 13/706,980, filed on Dec. 26, 2012, which claims priority
to U.S. Provisional Application Ser. No. 61/567,673, filed Dec. 7,
2011, and is related to but does not claim priority from prior
filed U.S. patent application Ser. No. 12/343,664, filed Dec. 24,
2008, the entire contents of which are incorporated herein by
reference.
BACKGROUND
[0002] The present invention relates generally to hydrocarbonaceous
compositions, such as asphalts and bitumens. More particularly the
present invention generally relates to compositions for reducing
the foul, undesirable or unpleasant odors emitted from such
hydrocarbonaceous compositions.
[0003] Two primary uses of asphalt include road paving and roofing
coatings. Asphalt-based roofing materials, such as roofing
shingles, roll roofing, and built-up roofing, are installed on the
roofs of buildings and residential dwellings to provide protection
from the elements. When asphalt is used in roofing applications,
the asphalt is first heated in a vessel, such as a gas-fired
roofing kettle. As the temperature of the asphalt rises, volatile
materials, such as hydrocarbons, sulfides, and mercaptans, are
emitted that can have strong, unpleasant, foul odors. The odors
emitted are not only unpleasant to smell, but they may also be an
irritant to workers and/or other individuals in the vicinity of the
vessel or to those who come within close range of the hot asphalt.
For instance, the odorous fumes from the asphalt may cause
headaches and/or irritation to the eyes and mucus membranes of the
nose and throat, which can result in a deterioration of worker
productivity and/or in increase in the number of sick days taken by
workers.
[0004] Although the properties of asphalts used in paving generally
differ from those used in roofing coatings, the problem of heating
and release of volatile and malodorous compounds is common to both
roofing and paving asphalts.
[0005] Many attempts to reduce undesirable odors emitted from
odor-causing compounds are known in the art. Non-limiting examples
of some of these approaches and odor-masking additives are set
forth below.
[0006] In a first approach, exemplified by U.S. Pat. No. 6,488,988
to Trumbore, et al. and U.S. Pat. Nos. 5,989,662 and 6,107,373 to
Janicki, et al. a physical barrier is formed on the surface of the
asphalt to reduce fuming. Trumbore teaches that a substantially
insoluble blanket material is added to the liquid asphalt to form a
skin on the surface of the asphalt and reduce the fuming. Examples
of blanket materials include polyurethane, polyethylene
terephthalate, ground soda bottles, starch, and cellulosic
materials. Janicki, et al. disclose methods of reducing fumes
produced from a kettle of molten asphalt that includes adding about
0.25 to about 6.0% by weight of a polymer (e.g., polypropylene) to
the asphalt. The polymer material preferably forms a skin across
substantially the entire upper surface of the asphalt. Janicki
teaches that at least a 25% reduction of the visual opacity of the
fumes, at least a 20% reduction of the hydrocarbon emissions of the
fumes, and at least a 15% reduction of suspended particulate
emissions of the fumes is obtained.
[0007] In other approaches, essential oils are added as
odor-masking compounds. For example, U.S. Pat. No. 5,271,767 to
Light, Sr., et al. discloses a composition that consists
essentially of (1) liquid asphalt, hot-mix asphalt, hot-mix, or
cold lay asphalt with added latex and (2) an additive that contains
a citrus terpene (4-isopropyl 1-methylcyclohexene) D-limonene mixed
with a vegetable oil such as cottonseed oil, soya oil, rapeseed
(canola) oil, peanut oil, etc. and a silicone oil dispersant. It is
taught that when 0.5-1.0 parts of the composition are mixed with
99.0-99.5 parts liquid asphalt, the resulting liquid asphalt
composition is substantially free of objectionable odors. Also,
U.S. Pat. No. 7,037,955 to Timcik and U.S. Patent Publication No.
2006/0155003 to Timcik, et al. disclose methods for reducing odor
in an oil based medium such as asphalt by adding an essential oil
to the oil-based medium in an odor reducing amount. The essential
oil may be one or more essential oils or essential oil components,
and includes natural extracts of various products of aromatic
plants and trees. Essential oils for use in the invention include
ajowan, angelica root, angelica seed, aniseed china star, carrot
seed, and fir needle, among many others. Examples of essential oil
components include terpenes, alcohols, aldehydes, aromatics,
phenolics, esters, terpene derivatives, non-terpene essential oil
components, and terpene derivatives.
[0008] In yet another approach, U.S. Pat. Nos. 6,461,421 and
6,987,207 to Ronyak discloses compositions that include an
odor-suppressing amount of an aldehyde or a ketone along with a
carboxylic acid ester; and, in the latter case, also including a
soy methyl ester. It is asserted that the composition significantly
reduces the odor given off by a hydrocarbonaceous material such as
asphalt.
[0009] Further, U.S. Patent Publication No. 2009/0314184 to Quinn,
et al. discloses the use of certain aldehyde-containing
compositions, with or without ketones but without esters, for
reducing the malodors of asphalts. The disclosed aldehydes include
2-chlorobenzaldehyde, 4-chlorobenzaldehyde,
alpha-methylcinnamaldehyde, 4-anisaldehyde, epsilon-cinnamaldehyde,
vertraldehyde, 4-ethoxy-3-methoxybenzaldehyde,
3-ethoxy-4-hydroxybenzaldehyde, 3-nitrobenzaldehyde, vanillin, and
cinnamaldehyde. In exemplary embodiments the composition consists
solely of vanillin.
[0010] US patent Publication No. 2008/0146477 to Mentink, et al.
discloses certain compositions and methods for treating asphalts
and bitumens, the compositions containing certain specific esters
of glutaric, succinic and adipic acids, or ethers or esters of a
product derived from the internal dehydration of a sugar. The
purpose of Mentinck's compositions appears to be a renewable source
of additives to replace the current use of vegetable, mineral or
fossil oils in the making of adjuvants for fluxes and binders for
asphalts. The criteria set forth for these adjuvants do not mention
odor-reduction.
[0011] US Patent publication 2009-0145330 to Draper, et al,
discloses the use of certain inorganic zinc compounds like zinc
oxide, zinc sulfonate or zinc carbonate, typically in nanoparticle
formats, for reducing the evolution of hydrogen sulfide from
asphalts.
[0012] U.S. Pat. No. 4,147,212 to Tisdale discloses the use of
water soluble zinc ammonium carbonate salts for reduction of
sulfides in drilling and working with oil and gas. US Patent
Publication 2009/0012214 to Butler, et al. describes the use of
heavy metal, water insoluble soaps (e.g. zinc stearate) to alter
the viscosity and/or rheological properties of asphalts.
[0013] Thus there remains a need in the art for odor reduction
using effective though low-cost compositions capable of reducing
odors in hydrocarbonaceous materials such as asphalt.
SUMMARY
[0014] In one aspect, the invention relates to a hydrocarbonaceous
material having reduced foul odors. The hydrocarbonaceous material
includes one or more asphalts and an odor mitigating concentrate
containing an odor mitigating compound in an odor mitigating
amount. The foul odors may be reduced relative to the asphalt in
the absence of the odor mitigating concentrate. The odor mitigating
compound may be selected from at least one reducing carbohydrate,
at least one soluble zinc compound, and a combination of both a
reducing carbohydrate and a soluble zinc compound.
[0015] In another aspect, the present invention relates to methods
for reducing foul odors in hydrocarbonaceous materials like
asphalts. In a first variation of the method, the undesirable odors
of a hydrocarbonaceous material may be reduced by adding to the
hydrocarbonaceous material a concentrate containing an odor
mitigating amount of at least one reducing carbohydrate. In a
second variation of the method, the undesirable odors of a
hydrocarbonaceous material may be reduced by adding to the
hydrocarbonaceous material a concentrate containing an odor
mitigating amount of at least one soluble zinc compound. In a third
variation, at least one reducing carbohydrate and at least one
soluble zinc compound are both used to mitigate odors.
Additionally, other known odor reducing compounds may be
present.
[0016] In some exemplary embodiments, the odor mitigating reducing
carbohydrate may be mono- oligo- or poly-saccharide. The soluble
zinc compounds may include salts of C8-C20 fatty acids; for example
salts of C12-C18 fatty acids.
[0017] One exemplary feature of the present invention is the
reduction of volatile offensive gasses given off by asphalts,
especially including hydrogen sulfides and mercaptans (thiols).
[0018] Other advantages and features are evident from the following
detailed description.
DETAILED DESCRIPTION
[0019] Unless defined otherwise, all technical and scientific terms
used herein have the same meaning as commonly understood by one of
ordinary skill in the art to which the invention belongs. Although
any methods and materials similar or equivalent to those described
herein can be used in the practice or testing of the present
invention, the preferred methods and materials are described
herein. All references cited herein, including books, journal
articles, published U.S. or foreign patent applications, issued
U.S. or foreign patents, and any other references, are each
incorporated by reference in their entireties, including all data,
tables, figures, and text presented in the cited references.
[0020] Unless otherwise indicated, all numbers expressing ranges of
magnitudes, such as quantities of ingredients, properties such as
molecular weight, reaction conditions, dimensions and so forth as
used in the specification and claims are to be understood as being
modified in all instances by the term "about." Accordingly, unless
otherwise indicated, the numerical properties set forth in the
specification and claims are approximations that may vary depending
on the desired properties sought to be obtained in embodiments of
the present invention. Notwithstanding that the numerical ranges
and parameters setting forth the broad scope of the invention are
approximations, the numerical values set forth in the specific
examples are reported as precisely as possible. Any numerical
values, however, inherently contain certain errors necessarily
resulting from error found in their respective measurements. All
numerical ranges are understood to include all possible incremental
sub-ranges within the outer boundaries of the range. Thus, a range
of 30 to 90 degrees discloses, for example, 35 to 50 degrees, 45 to
85 degrees, and 40 to 80 degrees, etc.
Hydrocarbonaceous Materials and Bad Odors
[0021] The odor-emitting hydrocarbonaceous material may be any
hydrocarbonaceous material that emits at ambient temperatures or
elevated temperatures undesirable or objectionable odors. These
hydrocarbonaceous materials may be based on one or more natural
oils, synthetic oils, or a combination thereof.
[0022] The mineral oils such as liquid petroleum oils and solvent
treated or acid-treated mineral oils of the paraffinic, naphthenic
or mixed paraffinic-naphthenic types often contain sulfur
compounds. Oils derived from coal or shale are also included.
Synthetic oils may include hydrocarbon oils such as, for example,
polymerized olefins, alkylbenzenes, polyphenyls, alkylated diphenyl
ethers, alkylated diphenyl sulfides, alkylene oxide polymers,
esters of dicarboxylic acids, silicon-based oils, and the like.
[0023] Unrefined, refined and re-refined oils, either natural or
synthetic (as well as mixtures of two or more of any of these) of
the type disclosed herein may be included. Unrefined oils are those
obtained directly from a natural or synthetic source without
further purification treatment. For example, a shale oil obtained
directly from retorting operations, a petroleum oil obtained
directly from primary distillation or ester oil obtained directly
from an esterification process and used without further treatment
would be an unrefined oil. Refined oils are similar to the
unrefined oils except they have been further treated in one or more
purification steps to improve one or more properties. Many such
purification techniques are known to those skilled in the art such
as solvent extraction, secondary distillation, acid or base
extraction, filtration, percolation, etc. Re-refined oils may be
obtained by processes similar to those used to obtain refined oils
applied to refined oils which have been already used in service.
Such re-refined oils are also known as recycled, reclaimed or
reprocessed oils and often are additionally processed by techniques
directed to the removal of spent additives and oil breakdown
products.
[0024] The terms "asphalt" and "bitumen" are often used
interchangeably, and refer to any of a variety of hydrocarbonaceous
pitch materials that are solid or semi-solid brown or black masses
at room temperature that gradually liquefy when heated. They occur
naturally in some regions of the world, and can be obtained as the
residue of fractional distillation of petroleum. Asphalt is further
described by Kirk-Othmer, Encyclopedia of Chemical Technology, Vol.
3, Third Ed. (1978) pp. 284-327, John Wiley & Sons, New York.
An additional discussion appears in the publication entitled "A
Brief Introduction to Asphalt and some of its Uses", Manual Series
No. 5 (MS-5), The Asphalt Institute, 7th Ed., September, 1974. Both
of these references are incorporated herein by reference.
[0025] In accordance with some exemplary embodiments, the asphalts
may include natural asphalts and petroleum-refined asphalts which
are generally known for roofing and paving applications. The
natural asphalts may include, for example, asphaltite such as
gilsonite, grahamite and glance pitch; lake asphalt such as
trinidad asphalt; and rock asphalt. The petroleum-refined asphalts
may include (i) "straight" asphalt obtained by distillation of a
crude oil (unblown and substantially unoxidized), (ii) "blown" or
"oxidized" asphalt produced by blowing an oxygen-containing gas
into a straight asphalt in the presence or absence of a catalyst,
(iii) solvent-extracted asphalt obtained when asphaltic material is
separated from the petroleum fraction containing it by the use of
propane or other solvents, and (iv) cut-back asphalt which is a
mixture of straight asphalt and a light petroleum solvent. In some
exemplary embodiments, the asphalts include petroleum tar and
asphalt cement. The petroleum tars include oil gas tar obtained as
a by-product when gases are produced from petroleum fractions, such
tar in refined form, cut-back tar obtained by mixing a light
petroleum fraction with such tar, and tar-pitch obtained as a
residue by removing the volatile fraction from such tar. Any of
these kinds of asphalt may be used singly or jointly. Straight
asphalt is useful for paving applications, and oxidized and blown
asphalts are useful for roofing applications.
[0026] Such hydrocarbonaceous materials may contain one or more
volatile (at ambient or elevated temperatures) organic compounds
(VOCs) such as aliphatic or aromatic hydrocarbons (e.g., methane,
ethane, propane, one or more butanes, pentanes, hexanes, benzene,
and the like). In the case of asphalts specifically, these and
other VOC hydrocarbons, sulfides, and mercaptans may each
contribute to the bad odor attributed to asphalt. The terms "foul",
"bad", "malodorous", "unpleasant", and "undesirable" are all used
interchangeably to characterize the objectionable odor associated
with asphalt. Such odors may be caused by many of the
above-mentioned compounds, but mercaptans (R--SH) and hydrogen
sulfide (H.sub.2S), even in small concentrations, contribute
significantly to the bad odor; the odor of "rotten eggs" is
sometimes used to describe the foul smell.
[0027] The presence of these volatile compounds can be determined
using known analytical techniques such as sensory electrodes and
gas chromatography. The Honeywell Lumidor Micromax Plus is one
sensory electrode instrument. It measures certain malodorous
headspace gases such as H.sub.2S, as well as some odorless gasses
and others. One measurement, LEL, measures the Lower Explosive
Limit of combustible gases, such as methane, ethane, propane,
butane, and others. Some of these are thought to contribute to the
foul odors of heated asphalt as well. Other specific undesirable
VOCs are disclosed in Tables 1-24 of U.S. Patent Publication No.
2009/0314184 to Quinn, et al., already incorporated herein in its
entirety, and include, for example, hydrogen sulfide, butane thiol,
thiopene, 2-methyl thiopene, ethyl thiopene, pentane thiol, hexane
thiol, dimethyl disulfide, dibenzothiophene, butyl
dibenzothiophene, benzene thiol, methylbenzenethiol, o-cresol,
p-cresol, phenol, dibenzofuran, quinoline, and decene.
[0028] In accordance with the present invention, an "odor
mitigating amount" of an odor mitigating composition is that
quantity of the odor mitigating composition that reduces at least
some of the offensive volatile constituents of the foul odors
emitted from asphalt or other hydrocarbonaceous materials. A useful
measure of reduction is the fraction of VOCs remaining after
treatment, compared to an equivalent untreated control sample.
Another measure is the related "percent reduction" from the
baseline untreated sample. Either of these measures may be applied
to specific individual VOCs or as an average reduction over
multiple VOCs, as shown in U.S. Patent Publication No.
2009/0314184. Thus, in some exemplary embodiments, an "odor
mitigating amount" shows an average reduction of at least 10%, at
least 20%, at least 25%, at least 30%, at least 40%, at least 50%
or at least 60%. In some exemplary embodiments, the average
reduction may be from about 20 to 95%, from about 30 to 90% or from
about 40 to 80%.
[0029] In accordance with various exemplary embodiments, odor
mitigating compounds added to the hydrocarbonaceous material in an
odor mitigating amount to reduce the unpleasant or objectionable
odors. In some exemplary embodiments, the odor mitigating compounds
may be added in small increments up to 5% (weight/volume or "w/v")
of the hydrocarbonaceous material; e.g. from about 0.001% to about
5.0% w/v, or from 0.05% to about 1.0% w/v. In some exemplary
embodiments, odor mitigating compounds are added in small
increments up to 1% w/v.
[0030] While the concentrations above are given for the ultimate
dilution of the odor mitigating compounds in the hydrocarbonaceous
material, it is often preferable to prepare concentrated
dispersions (or "concentrates") of odor mitigating compounds in a
carrier vehicle, and to add the liquid concentrates to the
hydrocarbonaceous material. Inventive odor mitigating concentrates
employing a carrier vehicle may comprise about 1-50% by volume of
odor mitigating compounds and about 50-99% by volume of carrier.
Dilution with a carrier vehicle may be particularly useful where
only a very small amount of compound is required to reduce odor,
thereby facilitating handling of the additive. It is also easier to
measure and add concentrated liquids to asphalt, than solids or
powders. Dilution with a carrier may also help dissolve the
compound in the hydrocarbonaceous material. In such cases, an
inventive concentrate contains one or more odor mitigating
compounds dispersed in a relatively concentrated dispersion in a
carrier vehicle.
[0031] In some exemplary embodiments, the carrier vehicle is a
liquid that is relatively unreactive with the odor mitigating
compounds. It should not contribute malodorous compounds itself,
but may even contribute to odor mitigation. The odor mitigating
compounds may soluble or dispersible in the vehicle, and the
vehicle may be miscible with the hydrocarbonaceous material. In
some exemplary embodiments, the carrier vehicles include certain
oils and certain polyethers. The carrier oils may include, for
example, mineral oil, vegetable oil, fatty acid alkyl esters, or
mixtures thereof. Exemplary carriers include fatty acid alkyl
esters or mixtures of fatty acid alkyl esters. The fatty component
of the fatty acid ester may be linear or branched C8-C20 alkyl.
Exemplary carriers may include fatty acid methyl ester(s) and fatty
acid ethyl esters; and also methyl and ethyl esters of palm,
coconut, canola, peanut, sunflower, and safflower oils. Suitable
polyethers may include polyethylene glycols (PEG). In some
exemplary embodiments, the PEG contains substituents that are
nonionic and contain phenyl groups and/or hydrocarbon chains.
Specific examples include octylphenol ethoxylates and nonylphenol
ethoxylates sold under tradenames TRITON X.TM. and TERGITOL.TM.
(available from Dow Chemical, Midland, Mich.). Tergitol NP-4 is one
suitable carrier.
Reducing Carbohydrates
[0032] The invention generally relates to the use of reducing
carbohydrates as odor mitigating compounds to reduce or mitigate
bad odors emitted from hydrocarbonaceous materials. In accordance
with the present invention, "reducing carbohydrate" or "reducing
sugar" means any carbohydrate/sugar that either has an aldehyde
functional group or is capable of forming one in solution through
isomerisation. In some exemplary embodiments, this functional group
allows the carbohydrate/sugar to act as a reducing agent to reduce
certain chemicals. For example, in Benedict's reagent and Fehling's
solution, both of which are used to test for the presence of a
reducing sugar, the reducing sugar reduces copper (II) ions to
copper (I), which then forms a brick red copper (I) oxide
precipitate.
[0033] Many sugars with ketone groups in their open chain form are
capable of isomerizing via a series of tautomeric shifts to produce
an aldehyde group. Such isomermization may result from dissolution
and/or thermal decomposition. Therefore, ketone-bearing sugars like
fructose may be considered reducing sugars. However, in some
exemplary embodiments, it is the isomer containing an aldehyde
group which is, since ketones cannot be oxidized without
decomposition of the sugar. This type of isomerization may
catalyzed by the base present in solutions which test for the
presence of aldehydes. Monosaccharides which contain an aldehyde
group are known as aldoses, and those with a ketone group are known
as ketoses.
[0034] Simple monosaccharides exist in solution in ring form as a
hemiacetal or hemiketal which gives rise to an additional chiral
carbon, and to alpha and beta forms of each sugar. This additional
asymmetric carbon is the carbonyl carbon, and is also called the
"anomeric" carbon since two "anomers" (i.e. alpha and beta forms)
are formed depending on which side of the flat carbonyl bond is
attacked by the hydroxyl nucleophile. However, these closed rings
may produce reducing sugars when the hemiacetal or hemiketal form
isomerizes to the open or straight chain form, which contains the
aldehyde or ketone functional group, respectively. Heat is a
condition known to promote this isomerization.
[0035] However, the present invention is not limited to
monosacharides. Disaccharides, oligosaccharides, polysaccharides,
maltodextrins, dextrins and even starches may all have reducing
capability and are within the definition of reducing
carbohydrate/sugar if they have, or can isomerize to have, an
aldehyde group. While simple glucose has been found to be adequate,
there may be advantages to longer polymers of reducing sugars, by
virtue of the additional molecular weight. In some exemplary
embodiments, glucose polymers such as starch and starch-derivatives
like glucose syrup, maltodextrin and dextrin, the macromolecule
begins with a reducing sugar, a free aldehyde. More hydrolysed
starch contains more reducing sugars. The percentage of reducing
sugars present in these starch derivatives (relative to dextrose)
is called the "dextrose equivalent" (DE). In some exemplary
embodiments, polymeric carbohydrates may (with or without
hydrolysis) have a DE in the range of about 2 to about 70 for
polymeric saccharides, and between about 70-100 for monomeric and
oligomeric sacccharides.
[0036] Other reducing monosaccharides may include glucose,
fructose, glyceraldehyde and galactose. Many disaccharides, such as
lactose and maltose, also have a reducing form, as one of the two
units may have an open-chain form with an aldehyde group. Sugars
having (full) acetal or ketal linkages are not reducing sugars, as
they do not have free aldehyde chains. They therefore may not react
with any of the reducing-sugar test solutions. Thus, sucrose and
trehalose, in which the anomeric carbons of the two units are
linked together forming an acetal, are non-reducing disaccharides
since neither of the rings is capable of opening.
[0037] The present inventive concepts may include any isomeric and
stereochemical forms of these saccharides. Furthermore, derivatives
of saccharides may also be suitable, provided they retain their
reducing nature after derivatization or can regain reducing
capability under the rigorous heat conditions of asphalt
processing. Thus, the saccharide may include O-glycosides,
N-glycosides, O-alkyl (e.g. methyl, ethyl), O-acylated sugars,
amino sugars, sugar alcohols (like sorbitol, xylitol, erythritol,
etc.) and the like.
[0038] In some exemplary embodiments, the reducing carbohydrates
have a molecular weight greater than about 100 Daltons. In this
context, the term "molecular weight" is meant to denote a weight
average molecular weight (in Daltons). In some exemplary
embodiments, the reducing carbohydrates have a molecular weight
from about 100 to about 1,000,000, from about 120 to about 100,000,
and from about 120 to about 10,000.
[0039] A single type of reducing carbohydrate may be used alone in
an odor mitigating amount; or it may be used in combination with
other types of reducing carbohydrates in an odor mitigating
composition or concentrate, the odor mitigating composition in
total being used in an odor mitigating amount. Additionally, a
single type of reducing carbohydrate or a combination of reducing
carbohydrates in an odor mitigating amount may be used in
combination with other odor-mitigating compounds such as, for
example, the vanillin-type carbonyl compounds and/or terpene-type
essential oil compounds known in the literature, or the soluble
zinc compounds described herein.
[0040] While not intending to be limited to any particular theory
of operation, it is believed that the reducing carbohydrates react
with H.sub.2S and/or mercaptan (thiol) compounds having the general
formula R.sup.3--SH, and complex or sequester them, reducing their
volatility. In some exemplary embodiments, the reaction may involve
the formation of hemithioacetals or thioacetals (when the
carbohydrate has an aldehyde) or hemithioketals or thioketals (when
the carbohydrate has a ketone. The following reaction scheme
illustrates a proposed reaction mechanism, but this is not proven
and not essential to the invention.
##STR00001##
[0041] Structure I represents the reducing sugar, having an
aldehyde functional group when R=H and a ketone functional group
when R.sup.1=a carbon chain. R.sup.2 represents the remainder
portion of the sugar, which may cyclize with R.sup.1 to form the
carbon chain of a ketone. Structure II represents malodorous
mercaptans (thiols) where R.sup.3 is an aliphatic or aromatic
chain, or hydrogen sulfide if R.sup.3=H. Structure III represents a
hemi(thio)acetal or hemi(thio)ketal, depending if structure I is an
aldehyde or a ketone, respectively. This reaction is analogous to
the acetalation reaction with alcohols, except that thiols are more
reactive than alcohols in this regard. In the presence of an excess
of thiol compounds II, the reaction may proceed to structure IV,
which is the full thioacetal or thioketal. Depending on the size
and molecular weight of the sugar remainder R.sup.2, and the
mercaptan chains R.sup.3, a fairly large structure III or IV may be
created, thus reducing the volatility of such compounds.
Soluble Zinc Odor Mitigating Compounds
[0042] In some exemplary embodiments, the odor mitigating compounds
include soluble zinc compounds. "Soluble" as used herein does not
refer to water solubility; but rather solubility in
hydrocarbonaceous materials like asphalts. ASTM procedure D2042-09
Standard Test Method for Solubility of Asphalt Materials in
Trichloroethylene is a useful test for solubility of and in
asphalts. As applied to roofing asphalts, the standard requires a
minimum of 99% solubility, such that less than 1% (by weight) of
content of the asphalt is captured by the filter paper; 99% or more
is dissolved by the trichloroethylene. A comparable standard may be
used to define solubility in hydrocarbonaceaous materials; i.e. a
compound is "soluble" as defined herein if at least 99% of added
compound is dissolved in the trichloroethylene. Certain inorganic
zinc compounds like zinc oxide, zinc sulfonate or zinc carbonate
are not "soluble" as the term is used herein and are not within the
odor mitigating soluble zinc compounds of the invention.
[0043] Illustrative soluble zinc compounds include, for example,
the salts of a C8-C20 fatty acid, for example salts of lauric acid
(zinc laurate), myristic acid (zinc myristate), myristoleic (zinc
myristolate), palmitic acid (zinc palmitate), palmitoleic acid
(zinc palmitolate), stearic acid (zinc stearate), oleic acid (zinc
oleate), linoleic acid (zinc linolate), and linolenic acid (zinc
linolenate). Other zinc salts include the salts of neodecanoic acid
(zinc neodecanoate), 2,4-dimethyl-2-isopropylpentanoic acid,
2,5-dimethyl-2-ethylhexanoic acid, 2,2-dimethyloctanoic acid, and
2,2-diethylhexanoic acid and naphthenic acid, which is a mixture of
cyclopentyl and cyclohexyl substituted carboxylic acids, and
2-ethylhexanoic acid.
[0044] In some exemplary embodiments, the soluble zinc compound is
a salt of a C12-C18 acid. In some exemplary embodiments, the
even-numbered fatty acids are more prevalent naturally and less
expensive, so it may be advantageous to utilize salts of even
numbered fatty acids in the C8-C20 range or the C12-C18, such as
laurate, myristate, myristolate, palmitate, palmitolate, stearate,
oleate, linolate, and linolenate.
[0045] Other illustrative zinc compounds may include salts of
modified fatty acids having from about 4 to about 20 carbons, the
modifications including (1) branching of the hydrocarbon chains,
and (2) possessing substituents of hydroxyl, amino and carboxyl
groups in the hydrocarbon chain, or (3) both (1) and (2). Notably,
modified acids having amino substituents may include the natural or
synthetic amino acids and modified fatty acids having carboxyl
substituents include dicarboxylic acids that may form ionic
polymers with divalent zinc. When such zinc salts of modified fatty
acids are also "soluble", they are included within the
invention.
[0046] In some exemplary embodiments, the odor mitigating soluble
zinc compounds are added to the hydrocarbonaceous material in an
odor mitigating amount to reduce the unpleasant or objectionable
odors. In exemplary embodiments, the soluble zinc odor mitigating
compounds may be added in small increments up to 5% (weight/volume
or "w/v") of the hydrocarbonaceous material; e.g. from about 0.001%
to about 5.0% w/v, or from 0.05% to about 1.0% w/v. In some
exemplary embodiments, odor mitigating compounds are added in small
increments up to 1% w/v.
Additional Odor Mitigating Compounds
[0047] In some exemplary embodiments, the odor mitigating compounds
include aldehydes and ketones, such as, for example, those
described in U.S. patent Publication 2009/0314184 to Quinn, et al.,
incorporated herein by reference. These compounds collectively are
referred to herein as "carbonyl compounds" and have a molecular
weight greater than about 100 Daltons and a boiling point greater
than about 375.degree. F., or greater than about 400.degree. F.
and, in some embodiments, at least about 450.degree. F. Specific
examples of such aldehyde-containing carbonyl compounds include
2-chlorobenzaldehyde, 4-chlorobenzaldehyde,
alpha-methylcinnamaldehyde, 4-anisaldehyde, epsilon-cinnamaldehyde,
vertraldehyde, 4-ethoxy-3-methoxybenzaldehyde,
3-ethoxy-4-hydroxybenzaldehyde, 3-nitrobenzaldehyde, vanillin, and
cinnamaldehyde. In exemplary embodiments the composition consists
solely of vanillin. Specific examples of such ketone-containing
carbonyl compounds include, but are not limited to, camphor,
isophorone, isobutyrophenone, propiophenone, 4-methylacetophenone,
carvone, 4-chloroacetophenone, 2-benzoylbenzoic acid,
2'-acetonaphthone, benzophenone, fluorenone, 4'-ethoxyacetophenone,
4'-chlorobenzophenone, 4-acetylbenzonitrile, and
4'-hydroxyacetophenone.
[0048] These additional "carbonyl compounds" may be used in
combination with reducing carbohydrate compounds and/or soluble
zinc compounds described herein.
Process of Use
[0049] Odor mitigating concentrates and compositions useful in the
invention can be made by routine methods using the odor mitigating
compounds. Carrier vehicles may be used if desired and are
described above.
[0050] The compounds or concentrates may be added to the
hydrocarbonaceous material in various ways. In some exemplary
embodiments, odor mitigating compounds or concentrates may be added
to hydrocarbonaceous materials in hot-storage tanks. In other
exemplary embodiments, the odor mitigating compounds or
concentrates may be added to hydrocarbonaceous materials that are
mixed with thermoplastic resins. In some exemplary embodiments,
pellets of odor-reduced asphalt and resin are formed for dilution
into other thermoplastics in molding operations. In this way the
asphalt pellets are diluted as filler to extend the resins and
provide it with unique properties as is known in the art. In still
other exemplary embodiments, the odor mitigating compounds or
concentrates may be added "on site" to kettles or drums of hot
asphalt. For example, in built up roofing (BURA), asphalt is heated
to about 350-450 F and many layers are formed as a composite
roofing material. Paving asphalts are heated to about 250-350 F.
The high temperature at which these products are typically used
contributes to the volatility, as is known, although it also
enhances the chemical reactions between the malodorous VOCs and the
odor mitigating compounds, so as to enhance their elimination from
volatile emissions.
EXAMPLES
[0051] The following examples serve to as illustrative embodiments
and in no way limit the present invention.
Example 1
Preparation of Asphalt Samples
[0052] Three samples of asphalts were obtained from different
sources and identified as Tanks, #9, #17 and #43. The respective
composition of these samples is set forth in Table 1 below.
TABLE-US-00001 TABLE 1 Sample Asphalt Compositions Tank #9 Tank #17
Tank #43 Composition 100% MAP Detroit 100% Exxon-Mobil Oxidized
Roofing Coating: of Asphalt Flux Joliet PG 64-22, 45% Country Mark
Sample lightly oxidized to 35.1% MooseJaw Type I with Softening 10%
Exxon-Mobil Joliet PG 64-22 Point of 145-150 F. 4.5% Conoco
Phillips PG 52-28 4.5% Conoco Phillips Flux 0.125% Phosphoric Acid
Initial Levels of: O.sub.2 (wt %) 20.6 20.7 20.5 LEL* (%) 3 2 19
H.sub.2S (ppm) 37 82 104 *LEL refers to Lower Explosive Limit, as
explained herein.
Example 2
Testing of Carbohydrate Odor Reducers in Asphalt Samples
[0053] Carbohydrate compounds (samples F, G and H) were tested for
odor reduction in each of the three asphalt samples from Example 1.
Controls included no additive (sample A), and two levels of
vanillin additives as taught per US 2009/0314184 (samples B and C).
The control and experimental sample compositions are set forth in
Table 2, below. Note, omitted compositions D and E tested odor
control zinc compounds as described in Example 3 below.
TABLE-US-00002 TABLE 2 Experimental odor reducing samples
containing carbohydrates A B C F G H Asphalt composition from 300
300 300 300 300 300 Tank, 9, 17 or 43 (g) vanillin 0 0.1 0.1 0 0 0
(g) polypropylene pellets (g) 0 0 3.6 0 0 0 Glucose (anhydrous) (g)
0 0 0 3 7.5 15
[0054] The 18 samples are thus designated by one of three tank
numbers (#9, #17 or #43) and one of six composition letters (A-C,
F-H). In the experiments, each of the 18 samples was mixed in a
pint container until uniform, and was then stored in an oven at
about 380 F (193 C) overnight. The samples were transferred to a
quart container with a 1/4 inch hole in the lid to allow for
headspace gas analysis of hydrogen sulfide (H.sub.2S), carbon
monoxide (CO) and lowest explosive limit (LEL) gases using a
Honeywell Lumidor MicroMax Plus monitor. Since CO is odorless, its
values were not felt relevant and not recorded here. An initial
reading was observed for t=0, and the containers were stored in the
oven again at 380 F (193 C). The headspace gases were measured
again at t=24 hours and t=10 days. The Lumidor was observed for
peak measurements, and also at a consistent 2 minutes from opening
each container. The Lumidor data, as well as some subjective
observations are provided in Tables 3, 4 and 5, below, in which
tr=trace, sl=slight, N/A=not available.
[0055] It should be noted that headspace gases provide a reasonable
measure of the odors emanating from asphalt when volatile
components in the sample liquid reach equilibrium with the
headspace air. There are two instances where this equilibrium is
potentially not reached: (1) on the initial reading, where
equilibration may not yet be reached; and (2) when a skin forms on
the top of the liquid sample preventing the escape of volatile
components. The data in the Tables below is interpreted in light of
these caveats. For example, the 24 hour measure is a better initial
comparison than t=0, and samples where a skin formed must be
interpreted cautiously.
TABLE-US-00003 TABLE 3 Tank #9 Samples A B C F G H Initial H.sub.2S
(ppm) 2 4 3 2 2 4 Initial LEL (%) 0 0 0 1 2 1 Initial Observations
sharp H2S tr. H2S, tr. H2S, sl. burnt sl. burnt sl. burnt vanillin
vanillin sugar sugar, gas sugar, gas bubbles bubbles 24-hour
H.sub.2S-peak 128 95 70 45 42 23 (ppm) 24-hour LEL-peak (%) 6 6 6 6
6 5 24-hour H.sub.2S-2 min 61 27 33 25 22 12 (ppm) 24-hour LEL-2
min (%) 4 4 4 4 4 4 24 hr Observations sharp H2S tr. H2S, tr. H2S,
sl. burnt sl. burnt sl. burnt vanillin vanillin sugar sugar, gas
sugar, gas bubbles bubbles 10 day H.sub.2S-peak (ppm) 513 275 333
235 182 220 10 day LEL-peak (%) 6 4 5 5 4 4 10 day H.sub.2S-2 min
(ppm) 191 130 148 113 93 109 10 day LEL-2 min (%) 4 3 4 4 3 3 10 d
Observations no skin, no no no solids tr. Solids tr. Solids H2S
odor vanillin vanillin odor odor, pellets at edge
TABLE-US-00004 TABLE 4 Tank #17 Samples A B C F G H Initial
H.sub.2S (ppm) 43 44 41 22 10 4 Initial LEL (%) 2 2 2 2 1 1 Initial
Observations strong strong strong sl. burnt sl. burnt sl. burnt
odor odor odor sugar; tr sugar, gas sugar, gas vanillin vanillin
solids bubbles, bubbles, solids solids 24-hour H.sub.2S-peak 29* 42
35 50 25 30 (ppm) 24-hour LEL-peak (%) 3* 4 4 7 5 5 24-hour
H.sub.2S-2 min 11* 14 12 20 11 18 (ppm) 24-hour LEL-2 min (%) 2* 2
2 4 4 4 24 hr Observations (all strong strong strong sl. burnt sl.
burnt sl. burnt samples have some skin odor odor odor sugar; tr
sugar, gas sugar, gas over surface) vanillin vanillin solids
bubbles, bubbles, solids solids 10 day H.sub.2S-peak (ppm) 3 24 5
18 17 17 10 day LEL-peak (%) 1 1 0 1 1 1 10 day H.sub.2S-2 min
(ppm) 0 9 3 9 9 5 10 day LEL-2 min (%) 0 0 0 0 0 0 10 d
Observations (all no skin, non- non- tr. Solids, tr. Solids,
skinned over) H2S odor vanillin, vanillin, burnt burnt sour smell
sour smell smell smell *a pump problem caused some delay in testing
sample A after opening the container
TABLE-US-00005 TABLE 5 Tank #43 Samples A B C F G H Initial
H.sub.2S 4 4 2 2 1 1 (ppm) Initial LEL (%) 0 0 0 0 0 0 Initial sl.
odor sl. odor sl. odor sl. burnt sl. burnt sl. burnt Observations
vanillin vanillin sugar sugar, sugar, solids solids 24-hour 9 7 10
4 5 122* H.sub.2S-peak (ppm) 24-hour 1 1 2 1 1 8* LEL-peak (%)
24-hour 4 2 6 1 1 1* H.sub.2S-2 min (ppm) 24-hour 1 0 1 0 0 6*
LEL-2 min (%) 24 hr vanillin vanillin sugar sugar sugar
Observations (all samples viscous with skin) 10 day 8 9 6 5 4 60*
H.sub.2S-peak (ppm) 10 day 6 5 4 4 2 18* LEL-peak (%) 10 day 4 5 4
2 2 N/A* H.sub.2S-2 min (ppm) 10 day 3 2 2 2 1 N/A* LEL-2 min (%)
24 hr Observations (all samples viscous with skin) *absence of 1/4
inch hole in this container lid during storage likely skewed these
results; N/A due to high moisture flow clogging of pump
[0056] It can be observed that the measures of offensive headspace
gasses in samples containing carbohydrate compounds (F, G and H)
were generally equivalent or lower than control samples at initial
times and, while most samples worsened over time, the effect of
this was typically less pronounced in samples F, G and H.
Example 3
Testing of Soluble Zinc Odor Reducers in Asphalt Samples
[0057] Soluble zinc compounds (samples D and E) were tested for
odor reduction in each of the three asphalt samples from Example 1.
Controls included no additive (sample A), and two levels of
vanillin additives as taught per US 2009/0314184 (samples B and C).
The control and experimental sample compositions are set forth in
Table 6, below.
TABLE-US-00006 TABLE 6 Experimental odor reducing samples
containing zinc compounds A B C D E Asphalt composition from 300
300 300 300 300 Tank, 9, 17 or 43 (g) vanillin 0 0.1 0.1 0 0 (g)
polypropylene pellets (g) 0 0 3.6 0 0 zinc stearate (g) 1.5 6
[0058] The 15 samples are thus designated by one of three tank
numbers (#9, #17 or #43) and one of five composition letters (A-E).
In the experiments, each of the 15 samples was mixed in a pint
container and tested using a Honeywell Lumidor MicroMax Plus
monitor, as in Example 2. The Lumidor data, as well as some
subjective observations are provided in Tables 7, 8 and 9, below,
in which tr=trace, sl=slight, N/A=not available. The equilibrium
caveats mentioned in Example 2 apply here as well.
TABLE-US-00007 TABLE 7 Tank #9 Samples A B C D E Initial H.sub.2S
(ppm) 2 4 3 1 1 Initial LEL (%) 0 0 0 0 0 Initial Observations
sharp H2S tr. H2S, tr. H2S, mild oil mild oil vanillin vanillin
odor odor 24-hour H.sub.2S-peak 128 95 70 3 1 (ppm) 24-hour
LEL-peak 6 6 6 11 8 (%) 24-hour H.sub.2S-2 min 61 27 33 1 0 (ppm)
24-hour LEL-2 min 4 4 4 7 6 (%) 24 hr Observations sharp H2S tr.
H2S, tr. H2S, mild oil mild oil vanillin vanillin odor odor 10 day
H.sub.2S-peak 513 275 333 179 10 (ppm) 10 day LEL-peak 6 4 5 6 6
(%) 10 day H.sub.2S-2 min 191 130 148 87 9 (ppm) 10 day LEL-2 min 4
3 4 522 522 (%) 10 d Observations no skin, no no no odor no odor
H2S odor vanillin vanillin odor odor, pellets at edge
TABLE-US-00008 TABLE 8 Tank #17 Samples A B C D E Initial H.sub.2S
43 44 41 2 2 (ppm) Initial LEL 2 2 2 0 2 (%) Initial strong strong
strong mild odor mild odor Observations odor odor odor vanillin
vanillin 24-hour 29* 42 35 7 2 H.sub.2S-peak (ppm) 24-hour 3* 4 4 5
7 LEL-peak (%) 24-hour 11* 14 12 2 1 H.sub.2S-2 min (ppm) 24-hour
2* 2 2 3 4 LEL-2 min (%) 24 hr strong strong strong mild odor mild
odor Observations (all samples odor odor odor have some skin over
surface) vanillin vanillin 10 day 3 24 5 8 4 H.sub.2S-peak (ppm) 10
day 1 1 0 1 1 LEL-peak (%) 10 day 0 9 3 4 1 H.sub.2S-2 min (ppm) 10
day 0 0 0 0 0 LEL-2 min (%) 10 d no skin, non- non- Observations
H2S odor vanillin, vanillin, (all skinned sour smell sour smell
over) *a pump problem caused some delay in testing sample A after
opening the container
TABLE-US-00009 TABLE 9 Tank #43 Samples A B C D E Initial H.sub.2S
(ppm) 4 4 2 2 1 Initial LEL (%) 0 0 0 0 0 Initial Observations sl.
odor sl. odor sl. odor tr odor tr odor vanillin vanillin 24-hour
H.sub.2S-peak 9 7 10 5 4 (ppm) 24-hour LEL-peak (%) 1 1 2 2 1
24-hour H.sub.2S-2 min 4 2 6 4 0 (ppm) 24-hour LEL-2 min (%) 1 0 1
1 1 24 hr Observations (all vanillin vanillin samples viscous with
skin) 10 day H.sub.2S-peak (ppm) 8 9 6 2 2 10 day LEL-peak (%) 6 5
4 3 6 10 day H.sub.2S-2 min (ppm) 4 5 4 1 1 10 day LEL-2 min (%) 3
2 2 2 4 24 hr Observations (all samples viscous with skin)
[0059] It can be observed that the measures of offensive headspace
gasses (especially H.sub.2S) in samples containing soluble zinc
compounds (D and E) were initially lower than control samples and,
while most samples worsened over time, the effect of this was
typically less pronounced in samples D and E.
[0060] The foregoing description of the various aspects and
embodiments of the present invention has been presented for
purposes of illustration and description. It is not intended to be
exhaustive or all embodiments or to limit the invention to the
specific aspects disclosed. Obvious modifications or variations are
possible in light of the above teachings and such modifications and
variations may well fall within the scope of the invention as
determined by the appended claims when interpreted in accordance
with the breadth to which they are fairly, legally and equitably
entitled.
* * * * *