U.S. patent number 3,650,711 [Application Number 04/807,418] was granted by the patent office on 1972-03-21 for fuel composition.
This patent grant is currently assigned to Ethyl Corporation. Invention is credited to Richard G. Abowd, Jr., Alvin J. Unick.
United States Patent |
3,650,711 |
Unick , et al. |
March 21, 1972 |
FUEL COMPOSITION
Abstract
Disclosed herein are compositions of matter having valuable
combustion properties. The compositions are particularly desirable
in combinations having enhanced ignition and continued combustion
properties in forms based on natural source and manmade
(reconstituted) firewood and briquettes for heating, cooking and
the like. The compositions involved contain mixtures of straight
chain and branched chain olefins and paraffins of selected
molecular weight with preference for the co-presence of higher
alcohols, the latter being particularly effective components for
purposes of enhancing the fabrication and burning characteristics
of some of the compositions.
Inventors: |
Unick; Alvin J. (Baton Rouge,
LA), Abowd, Jr.; Richard G. (Farmington, MI) |
Assignee: |
Ethyl Corporation (New York,
NY)
|
Family
ID: |
25196331 |
Appl.
No.: |
04/807,418 |
Filed: |
March 14, 1969 |
Current U.S.
Class: |
44/545; 44/589;
44/603; 44/590 |
Current CPC
Class: |
C10L
5/44 (20130101); C10L 5/00 (20130101); C10L
11/04 (20130101); Y02E 50/10 (20130101); Y02E
50/30 (20130101) |
Current International
Class: |
C10L
5/40 (20060101); C10L 5/44 (20060101); C10L
5/00 (20060101); C10L 11/04 (20060101); C10L
11/00 (20060101); C10l 009/00 (); C10l
011/00 () |
Field of
Search: |
;44/1,6,15,24,41 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Dees; C. F.
Claims
We claim:
1. In combination, a compact porous combustible carbonaceous body
selected from the group consisting of cellulose and carbon and,
additionally,
from about 5 to about 25 percent by weight of pore-contained
organic combustible contained with the pores of the carbonaceous
body consisting essentially of aliphatic hydrocarbons and aliphatic
alcohols,
the aliphatic hydrocarbons containing only carbon and hydrogen and
being a mixture of olefins and paraffins having predominantly from
about eight to about 24 carbon atoms per molecule and having an
olefin/paraffin weight ratio from about 1:1 to about 10:1,
the alcohols consisting essentially of molecules having from about
four to about 30 carbon atoms and having only one hydroxyl group
per molecule, said group being primary,
the weight ratio of aliphatic hydrocarbons to alcohol being from
about 1:0 to about 1:1.
2. The combination of claim 1 wherein the compact porous
carbonaceous body consists essentially of compacted particles of
cellulose.
3. The combination of claim 2 wherein the compacted particles
consist essentially of subdivided wood.
4. The combination of claim 2 wherein the compacted particles
consist essentially of wood sawdust.
5. The combination of claim 2 wherein the compacted particles are
obtained from paper.
6. The combination of claim 2 wherein the compacted particles
consist essentially of vegetable fiber.
7. The combination of claim 6 wherein the compacted particles
consist essentially of particulate corn stalks.
8. The combination of claim 1 wherein the compact porous
carbonaceous body consists essentially of compacted particles of
carbon.
9. The combination of claim 1 wherein the compacted particles
consist essentially of coke.
10. The combination of claim 1 wherein the compacted particles
consist essentially of petroleum coke.
11. The combination of claim 1 wherein the compacted particles
consist essentially of coal coke.
12. The composition of claim 1 wherein the weight ratio of
hydrocarbons to alcohol is from about 20:1 to about 1:1 and the
alcohols are predominantly alcohols having from about eight to
about 24 carbon atoms per molecule.
13. The composition of claim 1 wherein the weight ratio of
hydrocarbons to alcohol is from about 20:1 to about 1:1 and the
alcohols are predominantly alcohols having from about 20 to about
24 carbon atoms per molecule.
14. The composition of claim 1 wherein the weight ratio of alcohols
having up to 18 carbon atoms per molecule to alcohols having 20 and
more carbon atoms per molecule is about 1:1.
15. The composition of claim 1 wherein the hydrocarbons are
predominantly olefinic hydrocarbons.
16. The composition of claim 1 wherein olefin/paraffin weight ratio
is about 2:1.
17. The composition of claim 1 wherein the olefins are
predominantly straight chain alpha olefins.
18. The composition of claim 1 wherein the straight chain alpha
olefins are about two-thirds of the total olefins on a weight
basis.
19. The composition of claim 1 wherein the paraffins are
predominantly straight chain.
20. The composition of claim 1 wherein the paraffins include about
10 percent by weight of branched chain paraffins.
21. The composition of claim 1 wherein the hydrocarbon/alcohol
weight ratio is about 3/1.
22. The composition of claim 1 wherein the hydrocarbon/alcohol
weight ratio is about 3/1 and the alcohols are predominantly
alcohols having from 20 to 24 carbon atoms per molecule.
23. The composition of claim 1 wherein the hydrocarbon/alcohol
weight ratio is about 1/1, about half of the alcohols by weight
having from about 20 to about 24 carbon atoms per molecule.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention pertains to compositions of combustibles containing
mixtures of aliphatic olefins and paraffins and which preferably
contain some form of porous cellulose or carbon and significant
quantities of aliphatic alcohols. The alcohols preferred for
inclusion in the compositions are in two principal categories with
control of the proportioning of the alcohols between the two
categories being useful to enhance certain desired properties. One
category is mixed normal and branched primary alcohols which
include and range upward from about eicosanol to about
triancontanol, especially those ranging from eicosanol to
tetracosanol. The other category is mixed normal and branched
primary alcohols of lighter molecular weight than eicosanol ranging
from about butanol to about octadecanol with particular preference
for alcohols of the molecular weight from octanol to dodecanol.
Mixtures as regards molecular weight and branching appear to
provide more gradual "release" due to variations in physical
properties.
The compositions outlined in the foregoing have numerous uses but
of particular significance are those uses connected with fuels and
combustion enhanced "solid" fuels such as fireplace logs of wood,
natural as well as artificial; charcoal, in natural or compacted
form, such as coke, and the like. The high content of olefinic and
alcoholic molecules appears to enhance luminosity and minimize
soot. In certain instances as in the production of light or of heat
for cooking, certain categories of the compositions are useful as
principal or as sole fuels because of properties of ease of
ignition, of complete but prolonged combustion and of virtual
absence of characteristic "natural petroleum" odors. Where the
combustion is largely of a decorative or convenience nature as
frequently is the case with the combustion of natural or manmade
logs or briquettes in a fireplace or grill, certain compositions of
the present invention provide logs which have improved ignition
properties and enhanced resistance to deterioration caused by
various factors such as insects, moisture, fungus, and the like.
Certain categories of the compositions are useful in
controlled-release combustion enhancement; particularly with dense
logs such as some natural wood logs or strongly compressed manmade
logs based on oak, fir or pine sawdust or chips. In many instances,
it is difficult to maintain combustion of logs without controlled
release combustion adjuvants as with large individual logs in
fireplaces of where the logs are stored prior to use under
conditions where moisture pickup is not prevented. Problems of the
latter categories are minimized using teachings of the present
application.
2. Description of the Prior Art
In combustion applications such as those outlined in the foregoing,
petroleum-based materials of various forms and compositions have
been used in various ways for a long time. Such petroleum-based
materials are subject to certain limitations and have numerous
undesired characteristics. One of the principal undesired
characteristics in most instances is odor. As a practical matter,
one cannot use kerosene without imparting the widely-known
undesirable odor thereof to any environment involved. The present
class of materials is characterized by unique odor properties and
some of the compositions have desirable odors characteristic of
coconut oil. The significance of this is that the average user of
materials of the present class is familiar, and adversely so, with
the odor of kerosene but is unfamiliar with the odor of the present
material in such usage. Such a user soon comes to regard the
materials involving the present compositions as something different
and superior to "kerosene" containing materials, particularly with
respect to matters associated with clean burning, safety, and
absence of kerosene or gasoline odors.
Manmade logs based on various forms of cellulose such as compacted
sawdust or wood chips, are not only difficult to ignite but are
highly susceptible to rapid damage from moisture. Thus, in most
prior art involving manmade logs, it has been common practice to
dip or spray the manmade logs with "wax" molecular weight materials
of approximately 20-30 carbon atoms per molecule. In general, this
approach is of only limited effectiveness with regard to enhancing
the moisture resistance properties of the materials as a surface
coating because of cracks and pin holes and is not particularly
effective in long-term combustion enhancement or in ignition
because the waxes are surface coatings that are not particularly
easy to ignite and which melt rapidly and drop off when heat is
applied.
In some processes for making artificial logs, "wax" materials are
incorporated into the logs as they are being compressed so that the
wax type materials are caused to be present throughout the mass
rather than merely being present on the surface. Although this can
be fairly effective for combustion adjuvant purposes, the
compressing processes generally involve significant heat providing
hazardous manufacturing conditions and leading to recognition of a
need for a better manufacturing process.
SUMMARY
In accordance with the principles of the present invention,
compositions are provided which have highly desirable properties as
principal fuels or as adjuvants to enhance the ignition and/or
combustion of other fuel materials. The materials are characterized
by clean burning properties, freedom from "petroleum" odors either
prior to or during combustion and ease of application to co-present
natural as well as manmade combustible materials. Exemplary of the
natural materials usable with the present invention are natural
wood logs such as those cut from trees, particularly hardwood
materials such as oak, ash and the like which natural materials
readily absorb liquid compositions and components of the present
invention and which respond favorably to combustion as compositions
of the present invention.
The fireplace use of natural wood logs involves several
difficulties under ordinary circumstances. In the first place,
fireplace combustion is frequently a "decorative" operation with
the actual utilitarian purpose of developing heat being a secondary
result. Thus, there are many instances in which one does not desire
a roaring fire involving many logs simultaneously but rather
prefers the economy of a single easily and quickly ignited
long-burning log. Long-burning usually requires a dense natural log
of considerable size, say 6-10 inches diameter. An untreated oak
log of such size, alone, is difficult to ignite safely and to
maintain in combustion and normally requires considerable
preparation including the development of coals or fire from logs of
lesser size. When such large logs are used as parts of compositions
of the present invention, ignition is easy and the slow progressive
or controlled release of pore-contained or capillary-contained
liquid materials of the present invention prolongs and maintains
combustion even without prior or continued co-presence of coals and
heat baffling structures.
DISCUSSION
Typical compositions in accordance with the teachings of the
present invention contain a compact porous carbonaceous body of
organic or inorganic or a combination nature. Typical organic
nature materials are cellulose in forms of natural wood logs and
artificial or manmade bodies of a "log-type" configuration having
for example a circular, split circular, polygonal, rectangular or a
generally triangular or a semicircular cross section. Preferred
natural wood logs are those of the "furniture" category of "hard
woods" such as oak, ash, hickory; however, since the principal
matter of importance for a compact porous carbonaceous body for the
present in relationship to natural wood is the suitability for
combustion in a house-type fireplace where the environment is low
temperature as contrasted to an enclosed furnace. It is evident
that the principles of the present invention apply to materials
which are not necessarily considered hardwood for furniture
purposes, additional typical suitable woods being fir, spruce,
redwood, cypress, poplar, sycamore, cedar, pine, locust and the
like.
Manmade or artificial logs are typically some form of compact
natural-grown cellulose and which may or may not be of a
"reconstituted" variety such as wood pulp, reclaimed newspapers,
and magazines. Typical compacted natural cellulose materials are
based on some form of sub-divided wood such as sawdust, chips,
shavings, and the like. These materials are desired because of
their "waste" nature which is conducive to low cost. Typical
compacted natural cellulose materials are obtained from planing
refuse, sawmill waste, bark, leaves, and sub-divided vegetable
fibers. A typical sub-divided vegetable fiber is bagasse, which is
a residue of the milling of sugar cane after the bulk of the sugar
has been removed. Another vegetable fiber is corn stalks
particularly in particulate form produced by grinding, shredding,
pulverizing, and the like.
Other forms of compact porous carbonaceous bodies include
"inorganic" materials composed largely of carbon such as
by-products of the manufacture of carbon black, by-products of
petroleum refining operations, and residues resulting from the
generation of gas and other materials. In this last category of
carbon-base materials is included materials well known by
appearance or composition as petroleum or coal "coke," as charcoal
briquettes, and the like, used for cooking.
It will be recognized that the foregoing recitation of typical
compact porous carbonaceous bodies represents cellulose and carbon
materials which are combustible but which are in general not
particularly easy to ignite requiring either prolonged heating with
ignition materials such as loose chips of wood, paper and the like
or use in conjunction with a well-developed bed of fiery coals. It
will be recognized that one would not give even momentary
consideration to igniting such materials in the compacted form with
merely a match; however, when those materials are combined with
other materials as hereinafter recited to provide certain preferred
compositions according to the present invention, the resulting
compositions are capable of ignition quickly and cleanly upon the
mere contact with the flame of the match, yet they do not drop or
flash suddenly upon ignition.
The compositions of matter in accordance with the teachings of the
present invention include a combination of a compact porous
carbonaceous body and pore contained combustion and ignition
adjuvant consisting essentially of aliphatic hydrocarbons
preferably with aliphatic alcohols also present, the aliphatic
hydrocarbons containing only carbon and hydrogen and being mixtures
of olefins and paraffins having predominately from about eight to
about 24 carbon atoms per molecule and having an olefin/paraffin
weight per ratio from about 1:1 to about 10:1, the alcohols
containing predominantly only one hydroxyl group per molecule, said
group being primary, the alcohols having predominantly from about
four to about 30 carbon atoms per molecule, the weight ratio of
hydrocarbons to alcohol being from about 1:0 to about 1:1.
Particularly preferred compositions in accordance with the
foregoing are those wherein the weight ratio of hydrocarbons to
alcohol is from about 201 to about 1:1.
A further characterization of preferred compositions of matter
includes that wherein the olefin/paraffin weight ratio is about
2:1. In preferred compositions in accordance with the present
invention, the hydrocarbons are predominantly mono-olefinic,
particularly where the olefins are predominantly straight chain
alpha olefins. In certain preferred compositions of the present
invention the paraffins include about 10 percent by weight of
branched chain paraffins, the balance being unbranched.
EXAMPLE I
Fir sawdust or particle size ranging about one one-hundredth to
one-fourth inch resulting from planar mill operations (circular
saws, band saws, jointers, planers, shapers, etc.) is compressed
under pressure of approximately 25,000 lbs./sq. inch to a volume of
about one-third that of the loose material in a cylindrical form of
approximately 4 inches diameter. Upon cooling and removing the
pressure, the cylinders have considerable mechanical strength even
where the only binder is the residual resin in the sawdust.
(Finished length is approximately 16 inches). The compressed
sawdust artificial logs are usable for combustion purposes directly
but are difficult to ignite. The logs have a hard glossy exterior
surface but the artificial logs are highly susceptible to damage
from moisture because the surface is not impervious to moisture and
because a significant portion of the compression pressure is
retained as internal forces. Such a log disintegrates completely to
a loose soggy mass within approximately 5 minutes upon insertion in
water.
Artificial logs prepared as in the foregoing procedure were soaked
for 5 hours at 25.degree. C. in a preferred olefin-paraffin
composition having the following wt. percent analysis as determined
by Vapor Phase Chromatography.
VPC Analysis n- Br- n- Br- (Atoms/Molecule) Paraffins Paraffins
Olefins Olefins
__________________________________________________________________________
10 2.23 - 7.32 0.44 12 12.10 0.34 16.58 4.29 14 6.85 0.62 8.26 4.01
16 3.21 0.74 4.44 3.44 18 1.35 0.62 2.74 2.64 20 0.39 0.15 1.53
1.18 22 0.23 0.07 1.94 1.68 24 0.23 0.11 1.89 2.86 26 0.15 0.06
1.08 2.65 28 - - 0.21 1.37 26.74 2.71 45.99 24.56
__________________________________________________________________________
In a five-hour soak period, the artificial log which previously
weighed approximately 6 lbs picked up approximately 11/2 pounds of
the olefin-paraffin composition.
The foregoing log, although usable immediately, was allowed to
stand for approximately 24 hours to age and achieve uniformity of
distribution of the olefin-paraffin material. It was then placed on
a pair of andirons in a fireplace with no other combustible
material present. The log was ignited at both ends with a single
match. The log ignited quickly, the fire spreading across most of
the surface in about 1 minute. The log burned continuously with a
pleasantly luminous flame and with little visible smoke for about 2
hours and 15 minutes.
Without the foregoing olefin-paraffin mixture, it is usually
necessary to stack three logs together and break up a fourth to get
ignition.
EXAMPLE II
Example I is repeated with reconstituted fir, pine, and other types
of wood. Similar desirable results are obtained.
EXAMPLE III
Example I is repeated with natural oak, fir pine, etc., logs in
various sizes and shapes as material with which hydrocarbon and
alcohol adjuvant materials recited is combined. Similar long
burning and ease of ignition are experienced.
EXAMPLE IV
Example I is repeated with coke, natural and artificial, and with
charcoal briquettes as material with which hydrocarbon and alcohol
adjuvant materials recited are combined. Similar long burning and
ease of ignition are experienced.
EXAMPLE V
Example I is repeated with waste paper, magazines, newspapers,
bagasse, cornstalks as the material used to produce a compact
porous carbonaceous body with which hydrocarbon and alcohol
adjuvant materials are combined. Similar long burning and ease of
ignition are experienced.
EXAMPLE VI
The preceding examples are repeated wherein the adjuvant
compositions are according to the following ratios by weight.
Similar desirable results are obtained.
Adjuvant from about 5 to about 25 percent by weight of
pore-contained organic combustible consisting essentially of
aliphatic hydrocarbons and aliphatic alcohols in combinations of
the following tabulation:
Ratios: Hydrocarbon/Alcohol 100/0 95/5 90/10 85/15 80/20 75/25
70/30 60/40 50/50 Hydrocarbons: (predominantly C.sub.10.sup.-14)
Olefin/Paraffin 90/10 85/15 80/20 50/50 Alcohols Alcohols C.sub.8
-C.sub.18 Alcohols (C.sub.20 -C.sub.24) 1/0 3/1 2/1 1/1 1/2 1/3
0/1
example vii
example VI is repeated with hydrocarbons being predominantly eight
to 24 carbon atoms per molecule and alcohols being predominantly
four to 30 carbon atoms per molecule, the low and high alcohol
categories being split between C.sub.18 and C.sub.20 as in Example
VI. Similar desirable results are obtained.
EXAMPLE VIII
Compositions of paraffin, olefins and alcohols as tabulated in
Example VI are burned as sole fuels in a wick-type combustion
device, a glass chimney "kerosene" lantern. Excellent flame
luminosity is obtained with little soot and with absence of
characteristic "kerosene" odor. In this example the highest ratio
of hydrocarbon to alcohol is 95/5 (about 20/1).
* * * * *