Note: Descriptions are shown in the official language in which they were submitted.
CA 02348947 2001-06-O1
x17
Specifications / Background of the Invention
The ideal dendritic process, as described by Paul A Wender [ACS Chemical &
Engineering News page 27 01 08 2001] 1) has the capability to use readily
available,
diverse sources, low cost, mixed raw material, 2) has a short cycle time, 3)
has a net
positive energy balance, 4) requires no solvent, 5) has robust process
variables and a) is
multi-stepped in one reaction vessel, b) leaves no environmental footprint and
c)
generates controllable purified separated products in 100% yields while
involving as few
personnel and as little equipment as possible.
By dendritic is meant a simultaneous / all at once set of multi-stepped
reactions,
separations and isolation of purified streams of targeted variable products
from raw
material constituents in a single stage reaction vessel. An example is found
in Canadian
Patent 2249110. Others are described by C.R. Strauss in the Australian J.
Chemistry 52
83-96 (1999) and J. Haggin in Chemical and Engineering News 74 23 38 (1999).
The major constituents of 1) biosynthetic plant/animal tissue and 2) geo/ man
made
polymers are carbohydrates, lignin, waxes, lipids, proteins, kerogen, mineral
oils and
plastics.
The three states of matter are solids, liquids and gases. Depending on
pressure and
temperature the three phases can exist singly or in equilibrium with other
phases. Water
has, what is known as, three "co-existence curves". They consist of a solid /
gas
equilibrium called the sublimation curve, a liquid / gas equilibrium called
the vapour
pressure curve, and a solid / liquid equilibrium called the melting curve.
There also exists
a triple point where all three phases exist in equilibrium. The point on the
vapour-liquid
curve where the liquid and vapour become identical is called the critical
point. The
temperature at this point is called the "critical temperature" (Tc water
= 374°C) and
the pressure is called the "critical pressure"~(Pc water = 218
atmospheres). O.
Maass and E.W.R Steacie. An Introduction to the Principles of Physical
Chemistry pages
80-83 John Wiley and Sons Inc. 1939 ; http://www.kobelco.co.jp/p 108/
14/sfe01.htm
No gas can be liquefied above its Tc. As water is heated under pressure,
it slowly
begins to loose its H-bonding characteristics, act more and more like a lower
dielectric
constant solvent and become less dense. Above its Tc / Pc super
critical water
(SCW) has a dielectric constant of less than 5 and a density of 0.2 gm / ml.
Hence, SCW
as a supercritical fluid simultaneously acts both as a liquid and a gas with
the solvent
power of an organic liquid such as benzene.
CA 02348947 2001-06-O1
3, ~ 7
Classic organic reactions such as hydrolysis, bond cleavage and bond formation
can
occur in the sub-critical zone as described by Wideman L.G. et al USPat
4515713;
Lesutis H.P. et al Chem. Commun. 1999, 2063, and at or above the super
critical
temperature of water. B. Kuhlmann, E.M.Arnett, M. Siskin J. Org. Chem 1994,
59, 3098-
3101 C.R.Strauss Aust. J. Chem. 1000,52, 83-96.
Ester, thioester and amide hydrolysis is usually accompanied by
decarboxylation in
SCW. The following patents respectively teach the use of acid, basic and
neutral
catalysts in such reactions: Zeiler, A.C. USPat. 5344975, Theriot, K.J. et al.
USPat.
5329054, and Sealock, L.J. et al. USPat. 5630854.
Carbon - carbon and carbon - sulfur bond rupture followed by hydrogenation of
the
terminal ionic or free radical end is thermal hydrocracking [Gray M.R. et al.
Energy and
Fuels 6(4) 478-485 1992] and / or hydro-desulfurization [Whitehurst D.D. et
al. Adv. Catal.
42 345 (1998)). Patel, K.M. et al. USPat 4743357 teach the conversion of heavy
hydrocarbons into light hydrocarbons by water and an effective amount of
selected
catalyst material such as iron (II andlor III) oxides, sulfides or sulfates in
the absence of
externally added hydrogen; at a temperature greater than 340° and less
than
480°C. Pyrolysis without hydrogenation generates coke. Examples of
coking are
found in the thermal generation of methane gas, distillates and coke when
pyrolyzing
coal and wood. An excellent reference is found at http://www.newcastle.edu.au.
Amino acids under oxidative reaction conditions are known to denitrify. The
products of
the Akabori (J. Chem. Soc. Japan 52, 606 (1931), van Slyke (J. Chem. Soc. 99,
792 (1911)
and Strecker (Annelen 123, 363 (1862) reactions are aldehydes, ammonia and
carbon
dioxide. We detected ammonia, carbon dioxide, phenethyl amine and a tar when
subjecting phenyl alanine to SCW conditions at 430°C.
The array of products generated when subjecting reactants to SCW conditions,
is
separated by capture of gases, condensation of liquids in a distillation tower
and
crystallization / precipitation of solids. Examples of capture of gases are
precipitation of
carbon dioxide by lime, formation of amine salts by acids and condensation of
low
boiling hydrocarbons by cryogenic means.
An example of a distillation tower partitioning is the separation of gases and
liquids of
differing boiling points from each other. The accompanying table presents an
example of
hydrocarbon boiling ranges for a distillation tower.
CA 02348947 2001-06-O1
'I ~~7
Carbon Chain LengthClass Boiling Point
Range°
C
C5-Cl0 Gasoline 37 - 175
Cl0-Cl5Kerosene/Jet 175-275
Fuel
Cl2-C20Diesel 190-330
Cl4-C22Fuel Oil 230-360
C20-C30Lubricating >350
Oil
C22-C40Petroleum Jelly40-60 (m. pt.)
C25-C50Paraffin Wax 50-65(m.pt.)
C50+poly Tar/bitumen 4 0
cyclics ~ ~_-
_-
Aqueous glycerol solutions are known to be insoluble in hydrocarbons. [The
Merck Index
Entry 4493 ISBN # 0911970-1-2-3 (1996)). Diaz Z and Miller JH [USPat 4478612]
teach the
use of glycerol as a water-binding astringent in supercritical carbon dioxide.
SUMMARY DESCRIPTION OF THE INVENTION
One Step Dendritic Process
This invention relates to the reaction of variegate raw materials and the
separation and
isolation of the products. The invention takes advantage of the reduction in
the number
of profligate process steps, the cycle time far the reaction and the capacity
to separate
the products using a dendritic process.
An example follows. A mixture of nylon 6, nylon 6,6, nylon 6,10 and nylon 6,12
is
subjected to a high temperature in the presence of SCW. Hydrolysis of the
nylons
produces a mixture of c~ramino caproic acid, 1,6-diamino hexane, hexan-1,6-
dioic acid,
decan-1,10-dioic acid and dodecan-1,12-dioic acid. Decarboxlyation of the
amino acid
and the diacids generate fractionally distillable carbon dioxide + pentyl
amine + 1,6-
diamino hexane + butane + octane + decane. The amines are catalysts for the
reactions.
Other known catalysts such as acids, bases and iron oxides embedded in an
alumina-
silica matrix can be added to the reaction vessel. Hence in one reaction
vessel, water is
consumed and a mixture of four nylons generates two amines, three hydrocarbons
and
carbon dioxide.
Another example follows. Polyethylene is subjected to a high temperature in
the
presence of water and iron oxide embedded in an alumina-silica matrix or a
basic
CA 02348947 2001-06-O1
s~, 7
catalyst such as sulfide. Reductive thermolytic cleavage of carbon-carbon
bonds and
oxidation of the sulfide to sulfate ion gave C22 to C40 waxes or
fractionally
distillable Cl0 to C22 hydrocarbons respectively. Hence in one
reaction vessel,
water is consumed and a mixture of hydrocarbons is formed.
Still another example follows. A mixture of variegate source triglycerides and
lipids
(preferably with some protein contaminant) of animal and/or vegetable origin
is
subjected to a high temperature in the presence of water, with or without a
catalyst.
Hydrolysis of the proteins produces a mixture of amino acids. Hydrolysis of
the
triglycerides and lipids produces a mixture of C4 to C24 carboxylic
acids plus
glycerol. Decarboxlyation of the amino acids and the carboxylic acids generate
fractionally distillable carbon dioxide, amines, ammonia and C3 to
C23
hydrocarbons. The amines and ammonia are catalysts for the reactions. Other
known
catalysts such as acids, bases and iron oxides embedded in an alumina-silica
matrix can
also be added to the reaction vessel. Concomitant deamination and
decarboxylation of
the amino acid generate aldehyde, carbon dioxide and free ammonia. A further
embodiment of this example is that glycerol is a desiccant for the generated
hydrocarbons and absorbent for the ammonia. Thus the dry hydrocarbon phase can
be
separated before fractional distillation is carried out. Hence in one reaction
vessel, water
is consumed and a mixture of triglycerides, lipids, and protein is converted
to amines,
ammonia, desiccated hydrocarbons, glycerol and carbon dioxide.
Yet another example follows. Animal excrement and vegetable wastes that have a
fair
proportion of triglycerides, lipids and protein is subjected to a high
temperature in the
presence of water, with or without a catalyst. Hydrolysis of the proteins
produces a
mixture of amino acids. Hydrolysis of the triglycerides and lipids produces a
mixture of
carboxylic acids plus glycerol. Decarboxlyation of the amino acids and the
carboxylic
acids generate fractionally distillable carbon dioxide, amines, and C3 to
C23
hydrocarbons with little, if any, methane gas (Sealock Jr. L.J. et al USPat
5630854 teach
the generation of methane gas only). The amines are catalysts for the
reactions.
Concomitant de-amination and decarboxylation of the amino acid generate
aldehyde,
carbon dioxide and free ammonia. Other known catalysts such as acids, bases
and iron
oxides embedded in an alumina-silica matrix can also be added to the reaction
vessel. A
high proportion of protein naturally generates a higher ratio of amines to
hydrocarbons.
Capture and isolation of the putrid smelling amines and ammonia ensures an
odour free
process and nitrogen reduced residue. Solid insoluble coke residue (poly
saccharide
CA 02348947 2001-06-O1
4 / ~'7
derivation) and mineral salts are also obtained. Hence in one reaction vessel,
water is
consumed and human, swine, and bovine excrement is converted to carbon
dioxide,
amines, ammonia, hydrocarbons, glycerol, and nitrogen-depleted carbonaceous
compost. This odour/pathogen free residue can be used as a low-grade fuel or
compost.
A further example follows. Lake Asphalt Tar Sand that has a fair proportion of
carboxylic
acids is subjected to a high temperature in the presence of super critical
water and 20%
by volume used vegetable oil. Hydrolysis of ester content and decarboxlyation
of the
total acids plus reductive cleavage of high molecular weight hydrocarbons
followed by
separation of the solids by centrifugation generated a distillable ( 160 -
220° C)
hydrocarbon fraction and a fraction whose boiling point was greater than
220° C.
Solid insoluble residue (mineral salts) with an organo-sulfur contaminated tar
is also
obtained. Hence in one reaction vessel, water is consumed and tar sand plus
vegetable
oil is converted to carbon dioxide, hydrocarbons, glycerol and residual tar
contaminated
clay.
An additional example follows. Heavy oils that have been doctored with waste
lipid oil (as
a processing aid in the pipeline transport of crude) are subjected to a high
temperature in
the presence of SCW. Hydrolysis of the esters, decarboxlyation of the acids
and
reductive cleavage of high molecular weight hydrocarbons generated
fractionally
distillable desiccated lighter hydrocarbons, physically separable water-loaded
glycerol
and filterable solids. The solid insoluble residue contained mineral salts and
very heavy
tars. Hence in one reaction vessel, water is consumed and lipid doctored heavy
oil is
converted to carbon dioxide, hydrocarbons, and residual contaminant (V-Ni-Fe)
metals.
A still additional example follows. Waste canola vegetable oil was subjected
to a
500° C temperature in the presence of SCW. Hydrolysis of the esters,
decarboxlyation of the acids and thermal cleavage of generated hydrocarbons
gave
fractionally distillable desiccated lighter hydrocarbons, physically separable
water-
loaded glycerol and a filterable residue. Hence in one reaction vessel, water
is consumed
and vegetable oil is converted to carbon diaxide, glycerol and hydrocarbons,
A next to final example follows. Albert shale from Stoney Creek New Brunswick
was
subjected to a high temperature in the presence of SCW. Reductive thermolytic
cleavage
of carbon-carbon bonds gave Cl2 to C26 hydrocarbons as determined by
GC/MS.
A final example follows. Extracted lignin or black liquor from the Kraft
(sulfide +
carbonate) and Soda-AQ (carbonate) process was subjected to super critical
CA 02348947 2001-06-O1
~/~7
temperatures. Hydrolysis of the esters, decarboxlyation of the acids and
reductive
cleavage of high molecular weight hydrocarbons generated fractionally
distillable
hydrocarbons and physically separable precipitated carbonaceous solids. The
separated
aqueous fraction from the Kraft process contained a mixture of carbonate and
sulfate
ion. Trace sulfide ion was found. Hence in one reaction vessel, water is
consumed and
pulp black liquor is converted to carbon dioxide, hydrocarbons, carbonaceous
fuel and
green liquor without resorting to an energy intensive five stage evaporation
in order to
concentrate the black liquor.
This makes the environmentally more friendly Soda-AD process more financially
competitive than the Kraft-Sulfide process since the Soda-AQ carbonate need
not be
raised to 1200°C in order to convert sulfate to sulfide.
DETAILED DESCRIPTION OF THE PROCESS
In accordance with the present invention, a pressurized aqueous system is used
for the
transformation of higher molecular weight organic compounds into lower
molecular
weight hydrocarbons of reduced viscosity. The invention provides two methods
for
reducing the viscosity of organic raw materials. The first is by converting,
200-
300°C sensitive esters, thioesters, amides, and amino acids to "one
carbon
shorter" hydrocarbons and/or amines. The second is by thermolytic cracking of
the more
labile carbon-carbon and carbon-sulfur bonds at 400-500°C. Distillation
is used to
separate the lower viscosity constituents from each other. The combined
inorganic
phase and metal-tar contaminants separation is achieved by centrifugation.
The process of this invention can be conducted in batch or continuous fashion,
with
recycle of unconsumed starting materials, if required. The reaction is
conducted in a
single reactor zone. The materials of construction employed should be inert to
the
starting materials, intermediate reaction materials and the final products for
the reaction
process. The fabrication of the equipment should be able to withstand the
reaction
temperatures and pressures.
The present invention is a method for converting organic materials into lower
molecular
weight hydrocarbons. This is accomplished by injecting an organic raw material
in the
form of an aqueous mixture, preferably 10-50% by weight through a sixteenth
inch tube.
The amount of water present must be sufficient to provide hydrogen as needed
to
promote the formation of reduced hydrocarbons. A stirrer in the starting
materials
reservoir agitates the aqueous mixture of organic raw materials, water and
catalyst. A
CA 02348947 2001-06-O1
8 ~17
pump that feeds the raw material to the reactor can generate a pressure of 200-
250
atmospheres. The pressurized raw material is preheated to minimum 250°C
by
means of a heat exchanger before entry into the reactor. The reactor mass is
maintained
at a temperature of 400-525°C, preferably 430-500°C, as
predetermined by
TGA/MS analysis of the reaction raw material and a pressure that is
commensurate with
the temperature. An electric heater heats the autoclave with the capability to
maintain the
temperature of the twenty-foot length, sixteenth-inch diameter reactor-tube at
approximately 500°C. The system is provided with a cooling coil as it
exits the
autoclave area. Recovered energy is used to preheat fresh raw material as it
enters the
autoclave reaction chamber. Gas and liquid samples are taken after completion
of the
reaction and cool down.
In preferred embodiments of the inventions the following proportions of
components can
be used.
Experiment 1 - Continuous Process Mode.
Trimmed pork fat including rind and residual ._=w, which is not limiting to
the animal raw
materials that can be used in the process, is pulped. To the pulped fat is
added water
such that a 50% by weight fat to water mixture is prepared. Pulped pig fat is
pumped to
the reactor at a rate of 300 ml/hour under 218 atmospheres of pressure. The
pressurized
pulp is preheated to 250°C by means of a heat exchanger before entry
into the
reactor. The reactor is maintained at a temperature of 470°C.
Hydrolysis of the
triglycerides and proteins with sequential decarboxylation of the freshly
generated
carboxylic acid functional groups and possible oxidation of the free amine
occurs in the
twenty-foot length, sixteenth-inch diameter reactor-tube. Generated amine and
ammonia
provides a catalytic effect for the hydrolysis reaction and anti corrosive
protection of the
walls of the reactor. Energy recovered on cooling the exiting autoclave
products is used
to preheat fresh raw material as it enters the autoclave reaction chamber.
Gas, liquid and
solid products are refined as described below. The fractionally distilled
(less than
220°C) product of the reaction by Gel Permeation Chromatography was
mainly
Cl3, Cl5, and Cl7 alkanes, and glycerol. GC/MS confirmed the
presence
of Cl3, Cl5, Cl7 alkanes, and carbon dioxide. A second
experiment at
500°C caused thermal cracking. GC/MS showed the presence of C7 to
Cl4 alkenes plus C7 to Cl7 alkanes.
CA 02348947 2001-06-O1
DENDRITIC REACTION PROCESS
Raw material Carbon Dioxide --i gas or solid entrapment
+ Amines + Ammonia --~ gas, liquid or solid
entrapment
Water Hydrocarbons ~ fractional distillation
Catalyst Glycerol + water --~ phase separation
for + water soluble salts
3-10 minutes
Q ~ Solid compost ~ filtration
430-470°C
By solid entrapment is meant bubbling the gas fraction of the reaction mixture
first
through an acid solution (generates ammonia and amine salts) and then through
a lime
solution (precipitates calcium carbonate). Glycerol is a strong water
astringent. Water
laden glycerol is hydrocarbon insoluble and forms a separate phase.
Distillation of the
hydrocarbon phase shows no trace of water present.
Skin, ligament and some protein fractions of the pig fat carbonize under the
reaction
conditions. Physical filtration of the solids from the liquid phases provides
solid
compost that can be applied to the land as soil builder or burned as a fuel.
In another preferred embodiment of the invention the following proportions of
components can be used.
Experiment 2- Continuous Process Mode.
Partially de-watered pig excrement including floor washings, which is not
limiting to the
excrement source that can be used in the process, is prepared as a less than
20% by
weight solids mixture. A pump feeds the conditioned excrement to the reactor
at a rate of
300 ml/hour under 218 atmospheres of pressure. The pressurized excrement is
preheated
to 250°C by means of a heat exchanger before entry into the reactor.
The reactor
is maintained at a temperature of 430°C. Hydrolysis of the
triglycerides and
proteins with sequential decarboxylation of the freshly generated carboxylic
acid
functional groups (partial oxidation of the liberated amino acid is possible)
occurs in the
twenty-foot length, sixteenth-inch diameter reactor-tube. All pathogenic
material is
CA 02348947 2001-06-O1
t n ~f ~
sterilized and becomes part of the raw material. Generated amine and ammonia
provides
a catalytic effect for the hydrolysis reaction and anti corrosive protection
of the walls of
the reactor. Energy recovered on cooling the exiting autoclave products is
used to
preheat fresh raw material as it enters the autoclave reaction chamber. Gas,
liquid and
solid products are refined as described in experiment 1. The amine fraction is
composed
of ammonia from glycine; methyl amine from alanine, aspartic acid, asparagine
and ~3-
alanine; dimethyl amine from sarcosine; trimethyl amine from betaine; iso-
butyl amine
from valine; iso-pentyl amine from leucine; ethanol amine from serine; 1,2-
propanol
amine from threonine; 1,3-propanol amine from homo-serine; putrecine from
lysine,
arginine, and ornithine; histamine from histidine; phenethyl amine from phenyl
alanine;
tyramine from tyrosine; tryptamine from tryptophan; cysteamine from cysteine;
pyrollidine from proline.
Amines are odiferous compounds that are usually associated with excrement and
decomposing proteins. Putrecine (1,4-diamino butane) and cadaverine (1,5-
diamino
pentane) aptly derive their nomenclature from the latin - putrere or
putrefaction
and cadere or cadaver. Isolation and containment of the amines is one way to
achieve
abatement of foul odours. Partial oxidation of the amino acids to aldehyde and
ammonia
gave an aqueous solution containing 13.9g/1 N-NH3, a Total Kjeldahl
Nitrogen of
15.1g/1, trace N-NO2, trace N-NO3, 29.0g/1 Potassium and 1.11 g/1
Total
Phosphorous. The low phosphorous content in the aqueous phase is indicative of
insoluble phosphates in the residual solids. Attempted deamination of free
amine using
SCW was unsuccessful.
In still another preferred embodiment of the invention the following
proportions of
components can be used.
Experiment 3 - Continuous Process Mode.
Twenty percent by weight waste cooking oil (which is not limiting to the
amount of
triglycerides that can be used in the process) was added to the heavy-oil
bottoms
asphaltene fraction separated from Kern River crude. The viscosity reduced
mixture is
preheated to 250°C by means of a heat exchanger before being pumped
into the
reactor at a rate of 300 ml/hour under 218 atmospheres of pressure. The
reactor was
maintained at a temperature of 430°C. Hydrolysis of the triglycerides
and tramp
proteins with sequential decarboxylation of the freshly generated carboxylic
acid
functional groups occurred in a twenty-foot length, sixteenth-inch diameter
reactor-tube.
CA 02348947 2001-06-O1
/f
Generated amine provided a catalytic effect on the hydrolysis reaction. Energy
recovered
on cooling the exiting autoclave products is used to preheat fresh raw
material as it
enters the autoclave reaction chamber. Gas, liquid and solid products were
refined as
described above. The distillable hydrocarbon, which was not present in the
starting raw
materials, had a boiling point range fraction of 160 - 220.degrees.C
In yet still another preferred embodiment of the invention the following
proportions of
components can be used.
Experiment 4 - Continuous Process Mode.
Waste canola vegetable oil was subjected to a 500°C temperature in the
presence
of SCW. Hydrolysis of the esters, decarboxlyation of the acids and thermal
cleavage of
generated hydrocarbons gave fractionally distillable desiccated lighter
hydrocarbons,
physically separable water-loaded glycerol and a filterable residue. The
fraction, which
distilled between 60 and 220°C was shown by GC/MS to contain C4 -
Cl5 alkanes and alkenes. Trace amounts of Cl0 and Cll alkyl
benzene
was also detected. The non-distilled fraction above 220°C was shown by
FTIR to
contain free acid (1710 cm-1) and no starting material (1736 cm.sup: 1).
Preliminary experiments were carried out in a batch reactor. The reactor was
constructed
from a six-inch diameter stainless steel rod of seven-inch length. Eight half-
inch diameter
bolts were used to hold a cover head in place. A copper gasket was used to
maintain an
ultimate pressure of 250 atmospheres in the 40 ml volume well of the reactor.
Six
propane torches were used to heat the reactor to 430-470°C. Ice was
used to cool
the reactor once the reaction temperature was reached.
Experiment 5 Batch Process Mode
To 40 grams of Trinidadian Lake Asphalt Tar Sand (70% by weight clay) was
added 15 ml
of water. The temperature of the reactor was raised to 430°C. Upon
reaching 430,
the source of heat was shut down and cooling was started. Upon reaching room
temperature the reactor was opened. Trapped carbon dioxide escaped. The oily-
water
residual material was extracted with methylene chloride. The extract gave a
heavy oil that
boiled above 200°C. The residual clay contained 3% by weight tar. The
aqueous
phase contained trace amounts of sulfide (0.08 mg/I) and large amounts of
sulfate
(288mg/I).
CA 02348947 2001-06-O1
Experiment 6 - Batch Process Mode
To 20 grams of 57% aqueous butoxyethanol insoluble Athabasca heavy oil (i.e.
maltene
extracted asphaltene residuum; Number average molecular weight by Gel
Permeation
Chromatography 413; Polydispersity 3.78; Molecular range --400 - 10000 ) was
added 15
mls of water and 100 mg aspartic acid. The temperature of the reactor was
raised to
430°C. Upon reaching 430, the source of heat was shut down and cooling
was
started. Upon reaching room temperature the reactor was opened. Trapped carbon
dioxide and amine/ammonia escaped. The oily-water residual material was
partitioned
using 100m1 20% by volume butoxyethanol in water at 80°C. All of the
viscosity-
reduced oil dissolved in the top layer (57% butoxyethanol in water) and a
solid residue
collected at the bottom of the 10% butoxyethanol in water layer. The viscosity-
reduced
oil had a number average molecular weight of 277; Polydispersity 1.62;
Molecular range
-100 -1500 and a 17.37, 2.29 and 1.53 fold decrease in iron, nickel and
vanadium
respectively. The mostly carbon solid residue had much higher concentrations
of iron,
nickel, and vanadium.
Experiment 7 Batch - Process Mode
Crude light (Brut/Isthmus/Maya -35m1) oil that had a naphthenic acid portion
was
subjected to a high temperature in the presence of SCW with an amino acid
catalyst
causing decarboxlyation of the acids and reductive cleavage of higher
molecular weight
hydrocarbons. The starting density of the oil was 0.8923 g/ml at 20°C;
the final
density was 0.8633. Solid insoluble residue contained most of the V-Ni-Fe
metal.
Experiment 8 Batch - Process Mode
To 20 grams of low density polyethylene film was added 0.5 gm sodium sulfide
and 15
mls of water. The temperature of the reactor was raised to 460°C. Upon
reaching
460, the source of heat was shut off and cooling was started. Upon reaching
room
temperature the reactor was opened. The oily-water residual material was
partitioned
from the aqueous phase using 100m1-methylene chloride. Filtering it through a
pad of
basic aluminum oxide decolorized the methylene chloride solution. The kerosene
smelling light oil was tested for sulfur content. Analysis showed the oil
contained 0.1%
sulfur. The water phase was also analyzed for sulfide and sulfate content.
Greater than
98% of the sulfide had been converted to sulfate. A repeat reaction using 7.5%
ferric
oxide on alumina silicon dioxide as catalyst gave a waxy hydrocarbon product.
The
melting point was 25-30°C.
CA 02348947 2001-06-O1
f3/~~T
Experiment 9 - Batch Process Mode
To 25 grams of crushed Albert Shale (20% organic content) from New Brunswick
Canada
was added 10 mls of water. The temperature of the reactor was raised to
460°C.
Upon reaching 460, the source of heat was shut down and cooling was started.
Upon
reaching room temperature the reactor was opened. The oily-water residual
material was
partitioned from the aqueous phase using 100m1 methylene chloride. Oil was
obtained
upon evaporation of the solvent. GC/MS analysis indicated that the oil was
composed of
Cl2 to C26 saturated hydrocarbon.
Experiment 10 - Batch Process Mode
35 mls of used lubricating oil (a mixture of motor oil, grease, transmission
oil, gasoline,
ethylene glycol, water, floor sweepings, etc.) was placed in the reactor well.
The
temperature of the reactor was raised to 430°C. Upon reaching 430, the
source of
heat was shut down and cooling was started. Upon reaching room temperature the
reactor was opened. The oily-water residual material was gravity fed through
an S&S
qualitative No. 410 filter paper. Water remained in the oil-residue
impregnated filter
paper. The coloured oil filtrate was gravity fed through a ten centimeter long
one cm
diameter pad of dry Brockmann I, 150 mesh basic alumina in order to remove all
colour.
ICP analysis of the water white oil showed the following metals to be less
than 1 ppm:
aluminium, arsenic, barium, boron, cadmium, calcium, chromium, copper, iron,
lead,
magnesium, molybdenum, nickel, phosphorous, selenium, silicon, silver, sodium,
tin,
titanium, vanadium, and zinc.
Experiment 11 - Batch Process Mode
35 mls of 18% Kraft black liquor (sulfide-soda) was placed in the reactor
well. The
temperature of the reactor was raised to 430°C. Upon reaching 430, the
source of
heat was shut down and cooling was started. Upon reaching room temperature the
reactor was opened. The oily-water residual material was partitioned from a
solid phase
using 100 ml methylene chloride. Viscous oil was obtained upon evaporation of
the dried
methylene chloride solvent. GC/MS analysis indicated that the oil was composed
mostly
of polyaromatic material. Solid powered carbonaceous material (Total Organic
Carbon =
43.9%) was filtered from the reaction mixture. Examination of the water showed
that all of
the sulfide ions had been oxidized to sulfate and that most of the lignin
reaction products
had been precipitated out. Upon standing, the water white aqueous phase began
to take
on a brown colour - most likely oxidation of water-soluble phenolics.
CA 02348947 2001-06-O1
i~l ~7
Treatment of 18% Soda-AC~ black liquor under the same conditions gave a
greater yield
of lower boiling point range hydrocarbon and a slightly lesser yield of
carbonaceous
material.
ADVANTAGE OF OUR PROCESS
1. Simplicity of the equipment and Low capital costs, maintenance
the process fees
requiring fewer personnel and salaries.
2. One step dendritic separation of Smaller portable reactors
the organic, water with short
soluble and solid inorganic constituentscycle times.
3. Performing the reaction and separationEliminating the costs of
of profligate
constituents in one step. process steps.
4. Can use readily available, diverse Security against availability
mixed-source of raw
raw material materials sources and prices.
5. Reduction in the viscosity of the Increased pipeline flow capabilities
heavier oil at
fractions lower temperatures.
6. Up-grading the constituents by concentratingReduction of the oil volumes
which
metals into fewer product streams. require de-contamination
treatment.
7. Reducing odour producing organosulfurEliminates catalyst poisoning;
and Lowers
nitrogen compound products treatment costs, increases
social
acceptance
~ ~
8. Increases liquid volume yield Decreases coke yield.
9. Provides a drying agent when glycerolEliminates emulsion formation
is generated
10.Reduces the energy cost to delignifyProvides an alternate recovery
cellulose
pulps. Raises the cost competitivenessmethod for green liquor in
of the paper
Soda-AD process making
11.Uses wastes as a raw material sourceEliminates wastes including
and leaves
no environmental footprint pathogenic ones
