U.S. patent application number 09/934318 was filed with the patent office on 2002-11-21 for dendritic process for the catalytic reduction of heavy oils, kerogens, plastics, bio-masses, sludges and organic wastes to light hydrocarbon liquids, carbon dioxide and amines.
Invention is credited to Herrbach, Paul, Tullio, Venanzio Di.
Application Number | 20020173682 09/934318 |
Document ID | / |
Family ID | 23059347 |
Filed Date | 2002-11-21 |
United States Patent
Application |
20020173682 |
Kind Code |
A1 |
Tullio, Venanzio Di ; et
al. |
November 21, 2002 |
Dendritic process for the catalytic reduction of heavy oils,
kerogens, plastics, bio-masses, sludges and organic wastes to light
hydrocarbon liquids, carbon dioxide and amines
Abstract
The present invention pertains to a process for the catalytic
reduction of heavy oils, kerogens, plastics, bio-masses, sludges
and organic wastes to light hydrocarbon liquids, carbon dioxide and
amines, all in a single reaction vessel. Disclosed are multiple
examples of an improved dendritic process for the reaction of
variegate raw materials, and the separation and isolation of the
products formed thereby. The invention takes advantage of the
reduction in the number of profligate process steps, the cycle time
for the reactions, and the capacity to separate the products using
a dendritic process. The invention thus directly addresses the need
in the art for an improved dendritic process, which is suitable for
application in the processing and recycling or disposal of waste
from numerous and variable sources, such as, for example,
agricultural, industrial and municipal waste products, and
including, but not limited to, various wastes that are toxic or
potentially hazardous to human or animal health or the
environment.
Inventors: |
Tullio, Venanzio Di; (Perth,
CA) ; Herrbach, Paul; (Cadieux, CA) |
Correspondence
Address: |
BROWN & MICHAELS, PC
400 M & T BANK BUILDING
118 NORTH TIOGA ST
ITHACA
NY
14850
US
|
Family ID: |
23059347 |
Appl. No.: |
09/934318 |
Filed: |
August 21, 2001 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
60277087 |
Mar 19, 2001 |
|
|
|
Current U.S.
Class: |
585/240 ;
208/241; 208/390; 208/952 |
Current CPC
Class: |
C10G 2300/805 20130101;
C10G 2300/1037 20130101; C10G 31/08 20130101; Y02P 30/40 20151101;
Y02P 30/446 20151101; C10G 1/00 20130101; C10G 11/00 20130101; C10G
1/10 20130101; C10G 1/04 20130101; C10G 3/45 20130101; C10G 3/60
20130101; C10G 2300/4043 20130101; Y02P 30/20 20151101; C10G
2300/1018 20130101; C10G 3/40 20130101; C10G 2300/1014 20130101;
C10G 2300/1003 20130101 |
Class at
Publication: |
585/240 ;
208/952; 208/241; 208/390 |
International
Class: |
C10B 057/00 |
Claims
What is claimed is:
1. A chemical process for the catalytic reduction of raw organic
materials that include higher molecular weight organic
compositions, comprising the steps of: a) introducing said organic
material into a pressurized aqueous reactor system having a pump
that can generate a pressure of about 200-250 atmospheres; b)
heating said mixture in said reactor system in the presence of
super-critical water under high pressure and temperature; c)
maintaining said organic material at a temperature of about
400-525.degree. C. for a sufficient period of time, such that said
organic material is chemically transformed into a mixture
comprising lower molecular weight liquid hydrocarbons of reduced
viscosity, carbon dioxide and, when protein or other nitrogenous
compounds are present in said organic material, amines; and d)
wherein said chemical transformation occurs in a single reactor
zone of said reactor system.
2. The process of claim 1, wherein said reactor system further
comprises one or more materials that are inert to said organic
materials, their intermediate reaction materials, and final
products of said process.
3. The process of claim 1, wherein said reactor system further
comprises cooling means exiting an autoclave area.
4. The process of claim 1, wherein hydrolysis and decarboxylation
occur at a temperature of about 200-430.degree. C.
5. The process of claim 4, wherein super-critical water with a
dielectric constant of .psi.=2-5 is miscible with hydrocarbons.
6. The process of claim 1, wherein said reactor is maintained at a
temperature of about 430-500.degree. C.
7. The process of claim 1, wherein said catalytic reduction
reactions occur simultaneously, independently, in concert or in
cascade fashion.
8. The process of claim 1, wherein said catalytic reduction
reactions occur within about 3-10 minutes.
9. The process of claim 1, further comprising the step of physical
filtration of solids from liquid phases.
10. The process of claim 1, further comprising the step of
separating lower viscosity constituents from each other by
fractional distillation.
11. The process of claim 1, further comprising the step of
separating combined inorganic phase and metals-tars-organo-sulfur
contaminants by centrifugation.
12. The process of claim 1, further comprising the step of adding
glycerol as a desiccant for drying generated hydrocarbons, and as
an absorbent for amines, such that said dried hydrocarbons can be
separated before fractional distillation of liquid phase
products.
13. The process of claim 1, further comprising the steps of
precipitating generated carbon dioxide by lime water, and trapping
amines as ammonium salts, thereby controlling amine odors.
14. The process of claim 1, wherein said organic matter is selected
from the group consisting of: a) plastics; b) petroleum crude heavy
oils; c) kerogens; d) tar sands; e) shale; f) bio-masses; g) animal
fats; h) triglycerides; i) lipids; j) animal excrement; k)
vegetable wastes; l) sludges; m) organic wastes; n) any similar
organic matter, which is suitable for use in said catalytic
reduction process.
15. The process of claim 1, wherein said organic material is added
in the form of an aqueous mixture of about 10-50% by weight.
16. The process of claim 1, further comprising the step of
recycling unconsumed organic materials within said reactor
system.
17. The process of claim 1, further comprising the step of
pre-heating said organic material to about 250.degree. C. or above,
before said organic material is introduced into said reactor
system.
18. The process of claim 17, further comprising the step of
recycling waste heat from said process to pre-heat said organic
material.
19. The process of claim 1, wherein animal or vegetable derived
pathogens are destroyed by sterilization at super-critical
temperatures and pressures.
20. The process of claim 1, wherein inorganic and cellulose
fractions of animal or vegetable waste are transformed into
nitrogen depleted carbonaceous compost, thereby providing solid
compost that can be applied to the land as soil builder or burned
as a fuel.
21. The process of claim 1, wherein the viscosity of said organic
material is reduced by conversion of 200-300.degree. C-sensitive
C.sub.n esters, thioesters, amides, or amino acids to C.sub.n-1
hydrocarbons and/or amines, respectively.
22. The process of claim 1, wherein the viscosity of said organic
material is reduced by thermolytic cracking of the more labile
carbon-carbon and carbon-sulfur bonds at 400-500.degree. C.
23. The process of claim 1, wherein, when present in said organic
material, amides in plastics or protein, esters in polyesters,
triglycerides or lipids, and resins in tar sands or petroleum heavy
oil are hydrolyzed into acids, alcohols and amines.
24. The process of claim 23, wherein C.sub.n carboxylic acids are
decarboxylated to form carbon dioxide and C.sub.n-1
hydrocarbons.
25. The process of claim 23, wherein amines, either added or
generated, catalyze hydrolysis of amides, esters, or
thioesters.
26. The process of claim 23, wherein amines, either added or
generated, inhibit the corrosive effects of water at supercritical
temperatures.
27. The process of claim 23, wherein a mixture of petroleum and
triglycerides generates glycerol that desiccates the hydrocarbon
phase.
28. The process of claim 23, further comprising the steps of
precipitating generated carbon dioxide by lime water, and trapping
amines as ammonium salts, thereby controlling amine odors.
29. The process of claim 23, wherein super-critical water
reductively hydrogenates the cleaved carbon-carbon and
carbon-sulfur terminal radicals without generating coke.
30. The process of claim 23, wherein carbon-carbon and
carbon-sulfur scission occurs at a temperature of 430-500.degree.
C.
31. The process of claim 30, wherein super-critical water with a
dielectric constant of .psi.=2-5 is miscible with hydrocarbons.
32. The process of claim 1, wherein carbon-carbon and carbon-sulfur
bonds in natural and synthetic polymers, oligomers, and natural
petroleum waxes, when present in said organic material, are
reductively cleaved to generate lower molecular weight hydrocarbons
and thiols.
33. The process of claim 32, wherein tramp metals precipitate out
because lower molecular weight hydrocarbons cannot solubilize
them.
34. The process of claim 32, wherein iron oxide, sulfide ion and
carbonate ion are catalysts.
35. The process of claim 33, wherein sulfide catalyst is oxidized
into sulfate ion.
36. The process of claim 1, wherein chemically solubilized wood
extracted lignin is chemically transformed into non-aqueous soluble
liquid hydrocarbon and solid carbonaceous fuel.
37. The process of claim 36, wherein Kraft sulfide ions are
oxidized into sulfate ion.
38. The process of claim 36, wherein black liquor need not be
concentrated in order to separate chemically solubilized lignin
from an aqueous phase.
Description
REFERENCE TO RELATED APPLICATIONS
[0001] This application claims an invention which was disclosed in
Provisional Application No. 60/277,087, filed Mar. 19, 2001,
entitled "A PROCESS FOR THE CATALYTIC REDUCTION OF HEAVY OILS,
KEROGENS, PLASTICS, BIO-MASSES, SLUDGES AND ORGANIC WASTE TO LIGHT
HYDROCARBON LIQUIDS, CARBON DIOXIDE AND AMINES". The benefit under
35 U.S.C. .sctn.119(e) of the United States provisional application
is hereby claimed, and the aforementioned application is hereby
incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The invention pertains to the field of organic chemistry.
More particularly, the invention pertains to a dendritic process
for the catalytic reduction of organic compositions.
[0004] 2. Description of Related Art
[0005] 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," consisting of a solid-gas
equilibrium (called the sublimation curve), a liquid-gas
equilibrium (called the vapor pressure curve), and a solid-liquid
equilibrium (called the melting curve). There also exists a "triple
point," at which all three phases exist in equilibrium. The point
on the vapor pressure curve where the liquid and vapor
concentration become identical is called the critical point. The
temperature at this point is called the "critical temperature"
(e.g., T.sub.cwater=374.degree. C.) and the pressure is called the
"critical pressure" (e.g., P.sub.c water=218 atmospheres). See,
e.g., O. Maass and E. W. R Steacie, An Introduction to the
Principles of Physical Chemistry (1939), pages 80-83, John Wiley
and Sons, Inc.; see
http://www.kobelco.co.jp/p108/p14/sfe01.htm.
[0006] No gas can be liquefied above its T.sub.c. For example, as
water is heated under pressure, it slowly begins to loose its
H-bonding characteristics, behaves more and more like a lower
dielectric constant solvent, and becomes less dense. Super-critical
water is the fluid that is formed when water is heated above its
T.sub.c. The density of super critical water can continuously be
controlled between gas-like and liquid-like values, by varying
pressure and temperature. Thus, super-critical water can have a
dielectric constant between 5 to 25, depending on conditions. This
corresponds to the dielectric properties of polar organic liquids
under normal conditions. This property partially explains the
ability of super-critical water to dissolve nonpolar organic
compounds. Above its T.sub.c/P.sub.c, super-critical water
(hereinafter referred to as "SCW") has a dielectric constant of
less than 5 and a density of 0.2 gm/ml. Hence, as a super-critical
fluid, SCW simultaneously behaves both as a liquid and a gas, with
the solvent power of an organic liquid, such as benzene.
[0007] The major constituents of 1) biosynthetic molecules, such as
those of plant and/or animal tissue, and 2) geological and/or
man-made polymers are: carbohydrates, lignin, waxes, lipids,
proteins, kerogens, mineral oils and plastics. It is known in the
prior art that classic organic reactions involving these
constituents, such as hydrolysis, bond cleavage and bond formation,
occur in the sub-critical zone, as described in U.S. Pat. No.
4,515,713, and at or above the super-critical temperature of water.
See, e.g. Kuhlmann et al., J. Org. Chem. 59: 3098-3101 (1994); C.
R. Strauss, Aust. J. Chem. 52: 83-96 (1999). For example,
hydrolysis of esters, thioesters and amides occurs in SCW, and is
usually accompanied by decarboxylation. See, e.g., U.S. Pat. No.
5,344,975, No. 5,329,054, and No. 5,630,854, which teach the use of
acidic, basic and neutral catalysts, respectively, in such
reactions.
[0008] It is further known in the prior art that carbon-carbon and
carbon-sulfur bond rupture, followed by hydrogenation of the
terminal ionic or free radical end, occur via processes such as
thermal hydrocracking (see, e.g., Gray et al, Energy and Fuels
6(4): 478-485 (1992)) and/or hydro-desulfurization (see, e.g.,
Whitehurst et al, Adv. Catal. 42: 345 (1998)). Pyrolysis without
further hydrogenation generates coke; examples of coking found in
the prior art include thermal generation of methane gas,
distillates and coke, during pyrolyzation of coal and wood (an
excellent reference is found at http://www.newcastle.ed- u.au). The
array of products so generated typically is separated by well known
methods, such as, for example, capture of gases, condensation of
liquids in a distillation tower, and crystallization and/or
precipitation of solids. Well known 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. A well known example of a distillation tower
partitioning is the separation of gases and liquids of differing
boiling points from each other. Table 1, below, presents an example
of hydrocarbon boiling ranges for a distillation tower.
1TABLE 1 Boiling Carbon Chain Length Class Point Range (.degree.
C.) C.sub.5-C.sub.10 Gasoline 37-175 C.sub.10-C.sub.15 Kerosene/Jet
Fuel 175-275 C.sub.12-C.sub.20 Diesel 190-330 C.sub.14-C.sub.22
Fuel Oil 230-360 C.sub.20-C.sub.30 Lubricating Oil >350
C.sub.22-C.sub.40 Petroleum Jelly 40-60 (m. pt.) C.sub.25-C.sub.50
Paraffin Wax 50-65 (m. pt.) C.sub.50 + poly cyclics Tar/bitumen
>400
[0009] It is known in the prior art that aqueous glycerol solutions
are insoluble in hydrocarbons. See, e.g., Merck Index Entry 4493
ISBN # 0911910-1-2-3 (1996). Further, U.S. Pat. No. 4,478,612
teaches the use of glycerol as a water-binding astringent in
supercritical carbon dioxide.
[0010] The term "dendritic process" is intended herein to refer to
a process comprising a simultaneous set of multi-stepped reactions,
and the separation and isolation of purified streams of targeted
variable products from raw material constituents in a single stage
reaction vessel. Examples of such are found in, e.g., Canadian
Patent No. 2,249,110; C. R. Strauss, Aust. J. Chem. 52: 83-96
(1999); and J. Haggin, Chemical and Engineering News 74 (23): 38
(1999), the complete disclosures of which are hereby incorporated
herein by reference.
[0011] An ideal dendritic process is described by Paul A Wender,
ACS Chemical & Engineering News, Jan. 8, 2001, page 27, the
complete disclosure of which is hereby incorporated herein by
reference. The ideal dendritic process has: 1) the capability to
use readily available, low cost, mixed raw materials from diverse
sources; 2) a short cycle time; 3) a net positive energy balance;
4) no requirement for an organic solvent; 5) 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.
SUMMARY OF THE INVENTION
[0012] The present invention pertains to a process for the
catalytic reduction of heavy oils, kerogens, plastics, bio-masses,
sludges and organic wastes to light hydrocarbon liquids, carbon
dioxide and amines, all in a single reaction vessel. Disclosed
herein are multiple examples of an improved dendritic process for
the reaction of variegate raw materials, and the separation and
isolation of the products formed thereby. The invention takes
advantage of the reduction in the number of profligate process
steps, the cycle time for the reactions, and the capacity to
separate the products using a dendritic process. The invention thus
directly addresses the need in the art for an improved dendritic
process, which is suitable for application in the processing and
recycling or disposal of waste from numerous and variable sources,
such as, for example, agricultural, industrial and municipal waste
products, and including, but not limited to, various wastes that
are toxic or potentially hazardous to human or animal health or the
environment.
[0013] In one embodiment, a mixture of synthetic polymers
comprising nylon 6, nylon 6,6, nylon 6,10 and nylon 6,12 is
subjected to a high temperature in the presence of SCW, thereby
producing a mixture of .omega.-amino 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, plus
pentyl amine, 1,6-diamino hexane, butane, octane, and decane. The
amines serve as catalysts for these reactions. Other known
catalysts, such as acids, bases and iron oxides embedded in an
alumina-silica matrix, optionally are added to the reaction vessel
for improved performance. Hence, in one reaction vessel, water is
consumed and a mixture of four nylon polymers generates two amines,
three hydrocarbons and carbon dioxide.
[0014] In another embodiment, polyethylene is subjected to a high
temperature in the presence of water and iron oxide embedded in an
alumina-silica matrix or a basic catalyst, such as sulfide.
Reductive thermolytic cleavage of carbon-carbon bonds and oxidation
of the sulfide to sulfate ion yields C.sub.22 to C.sub.40 waxes or
fractionally distillable C.sub.10 to C.sub.22 hydrocarbons,
respectively. Hence, in one reaction vessel, water is consumed and
a mixture of hydrocarbons is formed.
[0015] In an yet another embodiment, 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 C.sub.4 to C.sub.24 carboxylic acids, plus glycerol.
Decarboxlyation of the amino acids and the carboxylic acids
generate fractionally distillable carbon dioxide, amines, and
C.sub.3 to C.sub.23 hydrocarbons. The amines serve as catalysts for
these reactions. Other known catalysts, such as acids, bases and
iron oxides embedded in an alumina-silica matrix, optionally are
added to the reaction vessel for improved performance. Also
optionally, glycerol is added as a desiccant for the generated
hydrocarbons and absorbent for the amines. Thus, the dry
hydrocarbon phase optionally is 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, desiccated hydrocarbons, glycerol and carbon
dioxide.
[0016] In still another embodiment, 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 C.sub.4 to C.sub.24 carboxylic
acids, plus glycerol. Decarboxlyation of the amino acids and the
carboxylic acids generate fractionally distillable carbon dioxide,
amines, and C.sub.3 to C.sub.23 hydrocarbons, with little, if any,
methane gas. The amines serve as catalysts for these reactions.
Other known catalysts, such as acids, bases and iron oxides
embedded in an alumina-silica matrix, optionally are added to the
reaction vessel for improved performance. A higher proportion of
protein generates a higher ratio of amines to hydrocarbons. Capture
and isolation of the putrid smelling amines provides an odor-free
process and nitrogen reduced residue. Solid insoluble coke residue
(cellulose derived) and mineral salts also are obtained. Hence, in
one reaction vessel, water is consumed and human, swine, or bovine
excrement and plant matter are converted to carbon dioxide, amines,
hydrocarbons, glycerol, and nitrogen-depleted carbonaceous compost.
This odor and pathogen-free residue is suitable for use as a
low-grade fuel or compost.
[0017] In an additional embodiment, 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. Inherent clay
catalyst causes decarboxylation of the acids and reductive cleavage
of high molecular weight hydrocarbons, generating fractionally
distillable C.sub.12, plus other hydrocarbons. Solid insoluble
residue (mineral salts), and very heavy organo-sulfur contaminated
tars also are obtained. Hence, in one reaction vessel, water is
consumed and tar sand is converted to carbon dioxide, hydrocarbons,
and residual tar-contaminated clay.
[0018] In yet an additional embodiment, heavy oils that have a fair
proportion of carboxylic acids are subjected to a high temperature
in the presence of SCW, with an iron oxide catalyst or amino acid
catalyst, causing decarboxylation of the acids and reductive
cleavage of high molecular weight hydrocarbons. Fractionally
distillable C.sub.13 to C.sub.30 hydrocarbons is generated.
Optionally, the use of ash residue from Lake Asphalt Tar Sand as
catalyst in the reductive generation of lighter oils from heavy
crude causes the separation of metal contaminants and organo-sulfur
compounds from the lighter fractions. Solid insoluble residue
(mineral salts) containing very heavy tars and organo-sulfur
compounds also are obtained. Hence, in one reaction vessel, water
is consumed and heavy oil is converted to carbon dioxide,
hydrocarbons, and residual tar contaminated clay (in the case of
alumina-silica-iron oxide catalyst) or organo-sulfur tar
contaminant residual V--Ni--Fe metals (in the case of amino acid
catalyst).
[0019] In still an additional embodiment, heavy oils supplemented
with waste fats and lipids (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, decarboxylation of the
acids and reductive cleavage of high molecular weight hydrocarbons
thus generates fractionally distillable desiccated lighter
hydrocarbons, physically separable water-loaded glycerol, and
filterable solids. The solid insoluble residue contains mineral
salts and very heavy tars. Hence, in one reaction vessel, water is
consumed and lipid-supplemented heavy oil is converted to carbon
dioxide, hydrocarbons, and residual organo-sulfur tar contaminant
metals.
[0020] In a further embodiment, Albert shale from Stoney Creek, New
Brunswick is subjected to a high temperature in the presence of
SCW. Reductive thermolytic cleavage of carbon-carbon bonds yields
C.sub.12 to C.sub.26 hydrocarbons, as determined by GC/MS.
[0021] In yet a further embodiment, extracted lignin or black
liquor from the Kraft (sulfide plus carbonate) and Soda-AQ
(carbonate) process are subjected to super-critical temperatures.
Hydrolysis of the esters, decarboxylation of the acids and
reductive cleavage of high molecular weight hydrocarbons generates
fractionally distillable hydrocarbons and physically separable
precipitated carbonaceous solids. The separated aqueous fraction
from the Kraft process contains a mixture of carbonate and sulfate
ion, but no substantial sulfide ion. 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-AQ process more financially competitive than the
Kraft-Sulfide process, since the Soda-AQ carbonate need not be
raised to 1200.degree. C. in order to convert sulfate to
sulfide.
BRIEF DESCRIPTION OF THE DRAWING
[0022] FIG. 1 shows a flow chart depicting generally the process of
the present invention.
[0023] FIG. 2 shows a view of apparatus suitable for practicing the
process of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
[0024] The present invention pertains to a process for the
catalytic reduction of heavy oils, kerogens, plastics, bio-masses,
sludges and organic wastes to light hydrocarbon liquids, carbon
dioxide and amines, all in a single reaction vessel. More
particularly, disclosed herein are multiple examples of an improved
dendritic process for the reaction of variegate raw materials, and
the separation and isolation of the products formed thereby. The
invention takes advantage of the reduction in the number of
profligate process steps, the cycle time for the reactions, and the
capacity to separate the products using a dendritic process. The
invention thus directly addresses the need in the art for an
improved dendritic process, which is suitable for application in
the processing and recycling or disposal of waste from numerous and
variable sources, such as, for example, agricultural, industrial
and municipal waste products, and including, but not limited to,
various wastes that are toxic or potentially hazardous to human or
animal health or the environment.
[0025] 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 general methods
for reducing the viscosity of organic raw materials. The first is
by converting 200-300.degree. 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.degree. C.
Separating the lower viscosity constituents from each other is
accomplished by distillation. The combined inorganic phase and
metals-tars-organo-sulfur contaminants separation is achieved by
centrifugation.
[0026] The process of the invention optionally is conducted in
batch or continuous fashion, with recycling of unconsumed starting
materials, if required or desired. The reaction is conducted in a
single reactor zone. The materials of construction employed
preferably are inert to the starting materials, intermediate
reaction materials, and the final products for the reaction
process. The fabrication of the equipment should, of course, be
able to withstand the reaction temperatures and pressures.
[0027] The invention is suitable as a method for converting organic
materials into lower molecular weight hydrocarbons. In a preferred
embodiment, this is accomplished by injecting an organic raw
material in the form of an aqueous mixture, preferably about 10-50%
by weight, through a thin tube (e.g., {fraction (1/16)} inch). In
the preferred embodiment, 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 pump that can generate a pressure of 200-250
atmospheres feeds the raw material to the reactor. The pressurized
raw material is pre-heated to a minimum temperature of about
250.degree. C., preferably by means of a heat exchanger, before
entry into the reactor. The reactor mass is maintained at a
temperature of about 400-525.degree. C., preferably about
430-500.degree. C., for example, as predetermined by TGA/MS
analysis of the reaction raw material and a pressure that is
commensurate with the temperature. A heater (preferably electric)
heats the autoclave with the capability to maintain the temperature
of the twenty-foot length, sixteenth-inch diameter reactor-tube at
approximately 500.degree. C. The system is provided with a cooling
coil as it exits the autoclave area. Recovered energy is used to
pre-heat fresh raw material as it enters the autoclave reaction
chamber. Gas and liquid samples are taken after completion of the
reaction and cool down.
[0028] Referring now to FIG. 2, apparatus suitable for practicing
the process of the present invention is shown. Feeding hopper 1
feeds into holding reservoir 2. High pressure pump 3 pumps the raw
material into the apparatus, with pressure being monitored by
pressure gauge 4. Primary heat exchanger 5 preheats the raw
materials. Power control 7 and power supply 8 allow for adjustment
of the amount of power delivered to heating coil 6, with
temperature meter/controller 9 controlling the temperature.
Secondary heat exchanger 10 provides additional heating, as
necessary. Back pressure 11 regulates back pressure in the system,
and gas/liquid separator allows for removal of gasses or liquids
from the system, as necessary. Temperature meter 13 and pressure
gauge 14 monitor temperature and pressure in the system. Gas
collection valve 15 allows for the collection of gasses, as
necessary, and liquid collection valve 15 allows for the collection
of liquids, as necessary. Heat transfer media pump 17 pumps heat
transfer media through the system.
[0029] The process of our invention teaches that:
[0030] a reaction vessel may contain diverse raw materials in
variable proportions, and that the product of one of the reactions
may be a catalyst or drying agent for the system as a whole,
[0031] the reactions may be independent or multi-stepped, occurring
in concert or cascade fashion,
[0032] the cycle time for the reactions is temperature/pressure
dependent and can be controlled in a minimal 3-10 minutes by
temperature/pressure regulation in the reaction vessel,
[0033] the temperature at which the reaction vessel is maintained
preferably is determined by TGA/MS analysis of the starting
materials,
[0034] the reaction products generated during TGA/MS analysis give
an indication of the heat levels and time period required for
individual reactions,
[0035] the TGA temperature ranges and slopes give a robustness
measure of the process variables,
[0036] the array of products formed is isolated by entrapment of
the gases, condensation of the liquids in an attached distillation
tower, and physical collection of the dry residual solids,
[0037] entrapment of carbon dioxide and amines may be by physical
or chemical means, such as physical
absorption/adsorption/de-sorption, condensation, crystallization
and chemical precipitation,
[0038] entrapment of the amines causes odor abatement,
[0039] through efficient reaction energy recovery and production of
a high calorific value product, a net positive energy balance is
attained,
[0040] by supplementing very heavy crude with waste animal and/or
vegetable oils, a much reduced viscosity and more easily
pipelineable mixture is formed,
[0041] lipid-supplemented heavy crude constitutes "diverse raw
materials in variable proportions" as described in the first point
made above,
[0042] depending on the aqueous content of the raw material, extra
water may or may not be required as solvent, and
[0043] no waste products, and hence no environmental footprint,
need be left.
[0044] Although several specific examples are described in detail
below, one skilled in the art will appreciate from the present
disclosure that the following examples are merely guides, which are
susceptible to substantial modification, and that the invention can
process a wide variety of input materials, including mixtures
thereof, for numerous different applications. In the various
embodiments of the invention described below, the following
proportions of components preferably are used.
[0045] Dendritic Reaction Process
[0046] The term "solid entrapment" is intended to refer to bubbling
a gas fraction of the reaction mixture first through a lime
solution (precipitates calcium carbonate) and then through an acid
solution (generates amine salts).
[0047] 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.
EXAMPLE 1
Continuous Process Mode
[0048] 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 C.sub.4 to C.sub.24 carboxylic
acids, plus glycerol. Decarboxlyation of the amino acids and the
carboxylic acids generate fractionally distillable carbon dioxide,
amines, and C.sub.3 to C.sub.23 hydrocarbons. The amines serve as
catalysts for these reactions. Other known catalysts, such as
acids, bases and iron oxides embedded in an alumina-silica matrix,
optionally are added to the reaction vessel for improved
performance. Also optionally, glycerol is added as a desiccant for
the generated hydrocarbons and absorbent for the amines. Thus, the
dry hydrocarbon phase optionally is 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, desiccated hydrocarbons, glycerol and carbon
dioxide.
[0049] In one example, trimmed pork fat, including rind and
residual flesh (which is not limiting to the source of 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 pre-heated to 250.degree. C. by means of a heat exchanger,
before entry into the reactor. The reactor is maintained at a
temperature of 470.degree. C. Hydrolysis of the triglycerides and
proteins with sequential decarboxylation of the freshly generated
carboxylic acid functional groups occurs in the twenty-foot length,
sixteenth-inch diameter reactor-tube. Generated amine 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 pre-heat fresh raw
material as it enters the autoclave reaction chamber. Gas, liquid
and solid products are refined as described above. 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.
EXAMPLE 2
Continuous Process Mode
[0050] 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 C.sub.4 to C.sub.24 carboxylic acids, plus glycerol.
Decarboxlyation of the amino acids and the carboxylic acids
generate fractionally distillable carbon dioxide, amines, and
C.sub.3 to C.sub.23 hydrocarbons, with little, if any, methane gas.
The amines serve as catalysts for these reactions. Other known
catalysts, such as acids, bases and iron oxides embedded in an
alumina-silica matrix, optionally are added to the reaction vessel
for improved performance. A higher proportion of protein generates
a higher ratio of amines to hydrocarbons. Capture and isolation of
the putrid smelling amines provides an odor-free process and
nitrogen reduced residue. Solid insoluble coke residue (cellulose
derived) and mineral salts also are obtained. Hence, in one
reaction vessel, water is consumed and human, swine, or bovine
excrement and plant matter are converted to carbon dioxide, amines,
hydrocarbons, glycerol, and nitrogen-depleted carbonaceous compost.
This odor and pathogen-free residue is suitable for use as a
low-grade fuel or compost.
[0051] In one example, partially de-watered pig excrement including
floor washings (which is not limiting to the amount or type of
excrement source that can be used in the process) is prepared as a
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 pre-heated to
250.degree. C. by means of a heat exchanger, before entry into the
reactor. The reactor is maintained at a temperature of 430.degree.
C. Hydrolysis of the triglycerides and proteins with sequential
decarboxylation of the freshly generated carboxylic acid functional
groups occurs in the twenty-foot length, sixteenth-inch diameter
reactor-tube. All pathogenic material is sterilized and becomes
part of the raw material. Generated amine 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 pre-heat fresh raw material as it
enters the autoclave reaction chamber. Gas, liquid and solid
products are refined as described in Example 1. The amine fraction
is composed of, for example, ammonia from glycine; methyl amine
from alanine, aspartic acid, asparagine and .beta.-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; putrescine from lysine, arginine, and
ornithine; histamine from histidine; phenethyl amine from phenyl
alanine; tyramine from tyrosine; tryptamine from tryptophan;
cysteamine from cysteine; pyrrolidine from proline.
[0052] Amines are odiferous compounds that are usually associated
with excrement and decomposing proteins. Putrescine (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 odors.
EXAMPLE 3
Continuous Process Mode
[0053] Heavy oils supplemented with waste fats or lipids (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, decarboxylation of the acids and reductive cleavage of high
molecular weight hydrocarbons thus generates fractionally
distillable desiccated lighter hydrocarbons, physically separable
water-loaded glycerol, and filterable solids. The solid insoluble
residue contains mineral salts and very heavy tars. Hence, in one
reaction vessel, water is consumed and lipid-supplemented heavy oil
is converted to carbon dioxide, hydrocarbons, and residual
organo-sulfur tar contaminant metals.
[0054] In one example, 10% by weight waste cooking oil (which is
not limiting to the amount or type of triglycerides that can be
used in the process) is added to wet crude. The pressurized mixture
is pre-heated to 250.degree. 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 is maintained at a
temperature of 430.degree. C. Hydrolysis of the triglycerides and
tramp proteins with sequential decarboxylation of the freshly
generated carboxylic acid functional groups occurs in a twenty-foot
length, sixteenth-inch diameter reactor-tube. Generated amine
provides a catalytic effect on the hydrolysis reaction. Energy
recovered on cooling the exiting autoclave products is used to
pre-heat fresh raw material as it enters the autoclave reaction
chamber. Gas, liquid and solid products are refined as described
above. The distilled hydrocarbon has a boiling range fraction of
60-220.degree. C., which is not present in the starting raw
materials.
[0055] Experiments were carried out in a batch reactor. The reactor
is constructed from a six-inch diameter stainless steel rod of
seven-inch length. Eight half-inch diameter bolts are used to hold
a cover head in place. A copper gasket is used to maintain an
ultimate pressure of 250 atmospheres in the 40 ml volume well of
the reactor. Six propane torches are used to heat the reactor to
430-470.degree. C. Ice is used to cool the reactor, once the
reaction temperature is reached.
EXAMPLE 4
Batch Process Mode
[0056] 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. Inherent clay catalyst causes
decarboxylation of the acids and reductive cleavage of high
molecular weight hydrocarbons, generating fractionally distillable
C.sub.12, plus other hydrocarbons. Solid insoluble residue (mineral
salts), and very heavy organo-sulfur contaminated tars also are
obtained. Hence, in one reaction vessel, water is consumed and tar
sand is converted to carbon dioxide, hydrocarbons, and residual
tar-contaminated clay.
[0057] In one example, to 40 grams of Trinidadian Lake Asphalt Tar
Sand (70% by weight clay) is added 15 ml of water. The mixture is
introduced into the reactor and the temperature of the reactor is
raised to 430.degree. C. Upon reaching 430.degree. C., the source
of heat is shut down and cooling is started. Upon reaching room
temperature, the reactor is opened, and trapped carbon dioxide is
allowed to escape. The oily-water residual material is extracted
with methylene chloride. Distillation of the extract yields a heavy
oil that boils above 200.degree. C. The residual clay contains 3%
by weight of tar.
EXAMPLE 5
Batch Process Mode
[0058] Heavy oils that have a fair proportion of carboxylic acids
are subjected to a high temperature in the presence of SCW, with an
iron oxide catalyst or amino acid catalyst, causing decarboxylation
of the acids and reductive cleavage of high molecular weight
hydrocarbons. Fractionally distillable C.sub.13 to C.sub.30
hydrocarbons is generated. Optionally, the use of ash residue from
Lake Asphalt Tar Sand as catalyst in the reductive generation of
lighter oils from heavy crude causes the separation of metal
contaminants and organo-sulfur compounds from the lighter
fractions. Solid insoluble residue (mineral salts) containing very
heavy tars and organo-sulfur compounds also are obtained. Hence, in
one reaction vessel, water is consumed and heavy oil is converted
to carbon dioxide, hydrocarbons, and residual tar contaminated clay
(in the case of alumina-silica-iron oxide catalyst) or
organo-sulfur tar contaminant residual V--Ni--Fe metals (in the
case of amino acid catalyst).
[0059] In one example, to 20 grams of 57% aqueous butoxyethanol
insoluble Athabasca heavy oil (i.e., maltene extracted asphaltene
residuum) is added 15 ml of water and 100 mg aspartic acid. The
mixture is introduced into the reactor and the temperature of the
reactor is raised to 430.degree. C. Upon reaching 430.degree. C.,
the source of heat is shut down and cooling is started. Upon
reaching room temperature, the reactor is opened, and trapped
carbon dioxide and ethyl amine are allowed to escape. The
oily-water residual material is partitioned using 100 ml 20% by
volume butoxyethanol in water at 80.degree. C. All of the viscosity
reduced oil dissolves in the top layer (57% butoxyethanol in water)
and a solid residue collects at the bottom of the 10% butoxyethanol
in water layer.
EXAMPLE 6
Batch Process Mode
[0060] Polyethylene is subjected to a high temperature in the
presence of water and iron oxide embedded in an alumina-silica
matrix or a basic catalyst, such as sulfide. Reductive thermolytic
cleavage of carbon-carbon bonds and oxidation of the sulfide to
sulfate ion yields C.sub.22 to C.sub.40 waxes or fractionally
distillable C.sub.10 to C.sub.22 hydrocarbons, respectively. Hence,
in one reaction vessel, water is consumed and a mixture of
hydrocarbons is formed.
[0061] In one example, to 20 grams of low density polyethylene film
is added 0.5 gm sodium sulfide in 15 ml of water. The mixture is
introduced into the reactor and the temperature of the reactor is
raised to 460.degree. C. Upon reaching 460.degree. C., the source
of heat is shut off and cooling is started. Upon reaching room
temperature, the reactor is opened. The oily-water residual
material is partitioned from the aqueous phase using 100 ml
-methylene chloride. Filtering it through a pad of basic aluminum
oxide decolorizes the methylene chloride solution. The kerosene
smelling light oil is tested for sulfur content. The water phase is
analyzed for sulfide and sulfate content. Performing the reaction
using Lake Asphalt clay residue as catalyst yields a waxy product.
The melting point is 25-30.degree. C.
[0062] In another embodiment, a mixture of synthetic polymers
comprising nylon 6, nylon 6,6, nylon 6,10 and nylon 6,12 is
subjected to a high temperature in the presence of SCW, thereby
producing a mixture of .omega.-amino 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, plus
pentyl amine, 1,6-diamino hexane, butane, octane, and decane. The
amines serve as catalysts for these reactions. Other known
catalysts, such as acids, bases and iron oxides embedded in an
alumina-silica matrix, optionally are added to the reaction vessel
for improved performance. Hence, in one reaction vessel, water is
consumed and a mixture of four nylon polymers generates two amines,
three hydrocarbons and carbon dioxide.
EXAMPLE 7
Batch Process Mode
[0063] Albert shale from Stoney Creek, New Brunswick is subjected
to a high temperature in the presence of SCW. Reductive thermolytic
cleavage of carbon-carbon bonds yields C.sub.12 to C.sub.26
hydrocarbons, as determined by GC/MS.
[0064] In one example, to 25 grams of crushed Albert Shale (20%
organic content) is added 10 ml of water. The temperature of the
reactor is raised to 460.degree. C. Upon reaching 460.degree. C.,
the source of heat is shut down and cooling is started. Upon
reaching room temperature, the reactor is opened. The oily-water
residual material is partitioned from the aqueous phase using 100
ml methylene chloride. Oil is obtained upon evaporation of the
solvent. GC/MS analysis indicates that the oil is composed of
C.sub.12 to C.sub.26 saturated hydrocarbon.
EXAMPLE 8
Batch Process Mode
[0065] Extracted lignin or black liquor from the Kraft (sulfide
plus carbonate) and Soda-AQ (carbonate) process are subjected to
super-critical temperatures. Hydrolysis of the esters,
decarboxylation of the acids and reductive cleavage of high
molecular weight hydrocarbons generates fractionally distillable
hydrocarbons and physically separable precipitated carbonaceous
solids. The separated aqueous fraction from the Kraft process
contains a mixture of carbonate and sulfate ion, but no substantial
sulfide ion. 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-AQ
process more financially competitive than the Kraft-Sulfide
process, since the Soda-AQ carbonate need not be raised to
1200.degree. C. in order to convert sulfate to sulfide.
[0066] In one example, 35 ml of 18% Kraft black liquor
(sulfide-soda) is placed in the reactor well. The temperature of
the reactor is raised to 430.degree. C. Upon reaching 430.degree.
C., the source of heat is shut down and cooling is started. Upon
reaching room temperature ,the reactor is opened. The oily-water
residual material is partitioned from a solid phase using 100 ml
methylene chloride. Viscous oil is obtained upon evaporation of the
dried methylene chloride solvent. GC/MS analysis indicates that the
oil is composed mostly of polyaromatic material. Solid powered
carbonaceous material is filtered from the reaction mixture.
Examination of the water shows that all of the sulfide ions are
oxidized to sulfate ions, and that most of the lignin reaction
products are precipitated out. Upon standing, the water white
aqueous phase begins to take on a brown color, most likely due to
oxidation of the water-soluble phenolics. Treatment of 18% Soda-AQ
black liquor under the same conditions gives a greater yield of
lower boiling point range hydrocarbon and a slightly lesser yield
of carbonaceous material.
[0067] Several advantages of the invention are listed below in
Table 2.
2TABLE 2 1. Simplicity of the equipment and the process Low capital
costs, requiring fewer personnel maintenance fees and salaries 2.
One step dendritic separation of the organic, Smaller portable
water soluble and solid inorganic constituents reactors with short
cycle times 3. Performing the reaction and separation of
Eliminating the constituents in one step costs of profligate
process steps 4. Can use readily available, diverse mixed- Security
against source raw materials availability of raw materials sources
and prices 5. Reduction in the viscosity of the heavier oil
Increased pipeline fractions flow capabilities at lower
temperatures 6. Up-grading the constituents by concentrating
Reduction of the oil metals into fewer product streams volumes
which re- quire de-contam- ination treatment 7. Reducing odor
producing organosulfur and Eliminates catalyst nitrogen compound
products poisoning; Lowers treatment costs, increases social
acceptance 8. Increases liquid volume yield Decreases coke yield 9.
Provides a drying agent when glycerol is Eliminates emulsion
generated formation 10. Reduces the energy cost to delignify
cellulose Provides an alter- pulps; raises the cost competitiveness
of the nate recovery Soda-AQ process method for green liquor in
paper making 11. Uses wastes as a raw material source and
Eliminates wastes, leaves no environmental footprint including
pathogenic organisms
[0068] Accordingly, it is to be understood that the embodiments of
the invention herein described are merely illustrative of the
application of the principles of the invention. Reference herein to
details of the illustrated embodiments is not intended to limit the
scope of the claims, which themselves recite those features
regarded as essential to the invention.
* * * * *
References