Methods for adding value to heavy oil

A process of the conversion of a heavy hydrocarbon into a lighter hydrocarbon utilizing a soluble transition metal salt and synthesis gas which includes soot particles and other impurities is disclosed. The inclusion of solid particles, such as soot, carbon black, silica fines has been found to decrease the formation of sediment during the reaction process.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention is generally related to the refining and processing 
of high density or heavy crude oil. More specifically, the invention 
pertains to an improved process for upgrading a heavy crude oil feedstock 
into an oil that is less dense or lighter that the original heavy crude 
oil feedstock. 
2. Background 
A variety of enhanced oil recovery (EOR) techniques permit the recovery of 
heavy oils from otherwise unproductive wells, including steam flooding, 
carbon dioxide flooding, and fire flooding. During EOR, a surfactant is 
typically used which causes the formation of underground oil/water 
emulsions. After being pumped to the surface, the oil and water portions 
of the emulsions are separated, after which the oil is passed on for 
further processing and the water is reused in the oil recovery operation. 
Processes used in the upgrading of heavy oils to give lighter and more 
useful oils and hydrocarbons are generally of the carbon rejection or 
hydrogen addition type. Both procedures employ high temperatures (usually 
greater than 400.degree. C.) to "crack" the long chains or branches of the 
hydrocarbons that make up the heavy oil. In the carbon rejection process, 
the heavy oil is converted to lighter oils and coke. The formation of coke 
is prevented, however, in the hydrogen addition process by the addition of 
high pressure hydrogen. In some carbon rejection processes, the coke is 
used elsewhere in the refinery to provide heat or fuel for other 
processes. Both processes result in an upgrading of the heavy oil 
feedstock to less dense or lighter oils and hydrocarbons. 
A process for the thermal and catalytic rearrangement of heavy oils and 
other similar feedstocks is described by de Bruijn et al. in U.S. Pat. 
Nos. 5,104,516 and 5,322,617, the contents of which are hereby 
incorporated by reference. In the disclosed processes, a heavy oil/water 
or feedstock/water emulsion is reacted with synthesis gas in the presence 
of a catalyst to reduce the viscosity and density of heavy oil thus making 
it more amenable for transportation by a pipeline. The disclosed process 
provides for the recovery of hydrogen and carbon dioxide gases as 
by-products and the recycling of carbon monoxide back into the 
rearrangement process. Use of a bifunctional catalyst present in about 
0.03 to about 15% under conditions and pressures that facilitate both the 
water gas shift reaction and the rearrangement of hydrocarbons is 
described. The bifunctional catalyst includes an inorganic base and a 
catalyst containing a transition metal such as iron, chromium, molybdenum 
or cobalt. 
The water gas shift reaction is an industrial process in which carbon 
monoxide (CO) and water (H.sub.2 O), in the form of steam, are reacted in 
the presence of a catalyst to give carbon dioxide (CO.sub.2) and hydrogen 
(H.sub.2) as shown in the following equation: 
EQU CO(g)+H.sub.2 O(g)CO.sub.2 (g)+H.sub.2 (g) 
In the process disclosed by de Bruijn et al. the water gas shift reaction 
is used to generate the hydrogen used to rearrangement of the hydrocarbons 
within the feedstock, and also to produce excess gas which is recovered as 
by-products. As disclosed, the source of CO may be carbon monoxide mixed 
with water, synthesis gas or generated in-situ from the decomposition of 
methanol. 
Synthesis gas (syngas) is a mixture of hydrogen (H.sub.2) and carbon 
monoxide (CO) typically in a range of ratios between about 0.9 to about 
3.0. It is commonly made by the controlled combustion of methane, coal, or 
napthas with oxygen to give a mixture of gases including hydrogen 
(H.sub.2), carbon monoxide (CO), carbon dioxide (CO.sub.2), hydrogen 
sulfide (H.sub.2 S), carbonyl sulfide (COS), and others. It is 
conventional to "clean-up" the produced combustion gases to give pure 
synthesis gas. A critical prerequisite for the use of syngas in reactions 
catalyzed by transition metals is the removal of sulfur containing 
compounds, such as H.sub.2 S or COS, formed from sulfur compounds in 
natural hydrocarbons or coal. In addition, soot generated during the 
combustion process is removed using water-based washing or scrubbing 
techniques thus cooling the syngas significantly. 
The process disclosed by de Bruijn et al., also known as CANMET technology, 
suffers from significant deficiencies when practiced on an industrial 
scale. Specifically, the CANMET technology: 
(1) Lacks a suitable source for synthesis gas within the process scheme; 
(2) Generates waste products such as coke, heavy oil residues, and spent 
catalyst that must be disposed of in an environmentally conscious manner; 
(3) Generates water highly contaminated with hydrocarbons that require 
significant treatment before being released to the environment; 
(4) Requires an economic source of heat for the upgrading/rearrangement 
reactions; 
(5) Prefers a separate sulfiding step to activate the catalysts utilized in 
the upgrading/rearrangement reactions; 
(6) Is limited by the slow kinetics of the water gas shift reaction; and, 
(7) Has problems with the stability and breakdown of the heavy oil/water 
emulsion feedstock. 
SUMMARY OF THE INVENTION 
The present invention is directed to an improved process for upgrading a 
heavy crude oil into a lighter, low density oil. One embodiment of the 
inventive process involves creating a heavy oil and water feedstock 
emulsion; reacting the feedstock emulsion with a hydrogen containing gas 
in the presence of a catalytic amount of a transition metal catalyst, and 
optionally particulate fines, to give a product stream including a lighter 
oil, a heavy oil residue and a hydrocarbon contaminated water; and 
separating from the product stream the lighter oil, the heavy oil residue 
and the hydrocarbon contaminated water. In another embodiment of the 
inventive process a heavy oil and water feedstock emulsion is created and 
reacted with a crude, hot synthesis gas in the presence of a catalytic 
amount of a transition metal catalyst to give a product stream including a 
lighter oil, a heavy oil residue and a hydrocarbon contaminated water. The 
product stream is separated to give a lighter oil, a heavy oil residue and 
a hydrocarbon contaminated water. A second emulsion is formed between the 
heavy oil residue and the hydrocarbon contaminated water, the second 
emulsion being stabilized by surfactants. The heavy oil residue may 
optionally be processed in a high shear environment so as to reduce 
viscosity. The second emulsion is utilized as a feedstock in a partial 
oxidation unit to produce the crude, hot synthesis gas which is used as 
previously noted above. 
The invention is also directed to a method of enhancing the stability of an 
emulsion of heavy oil and water and to the composition of the resulting 
stabilized heavy oil/water emulsion fuel.

DESCRIPTION OF ILLUSTRATIVE EMBODIMENTS 
Process flow diagrams of embodiments of the present invention are given in 
FIG. 1 and FIG. 2. In these flow diagrams, it should be understood that 
components, such as the upgrading unit (110 & 210), the emulsion mixer and 
preheater (116 & 216) and the partial oxidation/gasification unit (212), 
have been represented as boxes for the sake of simplicity of illustration. 
One of ordinary skill in the art should understand and appreciate that 
implementation of the actual process will be more detailed and will also 
depend upon the scale, cost, quality and quantity of feedstock, reactor 
pad space available and other factors. 
Turning now to FIG. 1., a preheated heavy oil/water emulsion (114) is 
introduced into the upgrading unit (110) at an appropriate point depending 
upon unit design. The heavy oil/water emulsion is made in an emulsion 
mixer and preheater (116) into which heavy oil (118) and water (120) are 
mixed into an emulsion having a ratio of heavy oil to water in the range 
of between about 99.99:0.01 to about 70:30. Typically the heavy oil/water 
emulsion is preheated to a temperature in the range of between about 
300.degree. C. and 350.degree. C. During this step it is believed that the 
water interacts with polar moieties of the heavy oil, thus at least 
partially upgrading the heavy oil. Further it is believed that during this 
step the heavy oil of the feedstock emulsion is prepared for the 
temperatures used in the upgrading reactor without coking or retrogressive 
reactions. 
A surfactant or a mix of surfactants (122) may be included in the heavy 
oil/water feedstock emulsion to increase the stability of the emulsion. 
Suitable surfactants include both water and oil soluble surfactants. A 
suitable surfactant or mixture of surfactants include surfactants having a 
hydrophilic-lipophilic balance in the range of between about 2 and about 
10 and mixtures thereof. When a single surfactant is used, sufficient 
amounts are used to obtain a stable emulsion. Typically this concentration 
of single surfactant falls in the range of between about 50 ppm and about 
2% of the emulsion. It has been found that when a combination of 
surfactants is used, the total amount of surfactant added is typically 
less than the amount used for any single surfactant. Thus, when a 
combination of surfactants are used to achieve a stabilized emulsion, the 
total surfactant concentration typically falls in the range of between 
about 100 ppm and about 1% of the emulsion. 
Hydrogen containing gas is (124) is introduced into the upgrading unit at 
an appropriate point. This hydrogen containing gas may be generated in 
another part of the refinery or it may be purchased "over the fence" from 
a vendor. Thus before introduction into the upgrading unit, such "over the 
fence" hydrogen should be preheated using suitable heating means known to 
one skilled in the art. 
In one embodiment, the hydrogen containing gas (124) is hot, crude 
synthesis gas. As used herein, the term "hot, crude synthesis gas" is 
intended to mean a mixture of hydrogen (H.sub.2) and carbon monoxide (CO) 
gases known in the art as synthesis gas or syngas which has not been 
conventionally processed. Synthesis gas may be produced in a partial 
oxidation unit or a gasification unit by the oxidation of a hydrocarbon 
fuel in the presence of oxygen or the partial oxidation of a hydrocarbon 
in the presence of steam. The resulting mixture of gases and soot 
particles exit the gasification unit at approximately 1482.degree. C. 
(2700.degree. F.) after which they are substantially cooled and processed 
to remove all but the H.sub.2 and CO. In the context of the present 
invention and disclosure, however, this crude synthesis gas is cooled to a 
temperature appropriate to the operation of the upgrading unit. Thus in 
relation to conventional synthesis gas, the synthesis gas used in the 
process of the present invention can be characterized as being "crude and 
hot." 
Within the upgrading unit (110), the heavy oil is converted into the 
desired light oil end product. The upgrading unit (110) itself may 
comprise either a single or multiple reactor units either in parallel or 
in series. In one preferred embodiment, the upgrading unit comprises two 
trains of two reactors in series. Typically, a supplementary charge of the 
heavy oil/water emulsion feedstock is injected into the reaction stream at 
a point between the series of reactors so that the two reactors operate at 
approximately the same temperature. The reactors are operated in the 
temperature range of between about 400.degree. C. and about 440.degree. 
C.; a pressure range of between about 400 psi and about 2000 psi and at a 
flow rate in the range of between about 5 gal./day and about 100,000 
BBL/day. In one preferred embodiment, the reactor is designed for upflow 
operation with each reactor having its own inlet distributor system. Other 
reactor designs may be suitable and thus used within the scope of the 
present invention. 
Complex chemical reactions occur inside the reactors that constitute the 
upgrading unit. However, the overall chemical reaction is represented by 
the following unbalanced general equation: 
##STR1## 
Although not intending to be limited by any particular theory, it is 
believed that two reactions are occurring within the upgrading unit 
reactors. The first is the water gas shift reaction discussed above. This 
reaction is used to generate in-situ hydrogen which is utilized in the 
hydrocracking of the hydrocarbons constituting the heavy oil. It is this 
second reaction, the hydrocracking of the hydrocarbons constituting the 
heavy oil, that is believed to generate a majority of the product light 
oil. 
The catalyst (125) may be introduced into the reactors of the upgrading 
unit (110) in a number of ways including as a mixture with the heavy 
oil/water feedstock, co-injection with the heavy oil/water feedstock or 
direct injection into the upgrading reactor by itself. 
The catalyst (125) used in the upgrading unit preferably contains a 
transition metal, transition metal-containing compound or mixtures thereof 
in which the transition metal is selected from the Group V, VI and VIII 
elements of the Periodic Table of Elements. More preferably, the 
transition metal is selected from the Group in which the metal is 
vanadium, molybdenum, iron, cobalt, nickel or combinations thereof. Both 
water soluble and oil soluble transition metal compounds may be used in 
the catalyst, including metal naphthanates, metal sulfates, ammonium salts 
of polymetal anions, MOLYVAN (TM) 855 a proprietary material containing 7 
to 15% molybdenum commercially available from R. T. Vanderbilt Company, 
Inc. of Norwalk, Conn., molybdenum HEX-CEM which is proprietary mixture 
containing 15% molybdenum 2-ethylhexanote available from Mooney Chemicals, 
Inc. of Cleveland Ohio and other similar compounds. In addition, a 
transition metal-containing waste stream, for example, from a 
polyolefin/methyl t-butyl ether process containing between 2 and 10% 
molybdenum in an organic medium which principally is composed of 
molybdenum glycol ethers, is suitable as a source of catalyst. This latter 
compound may be purchased from Texaco Chemical Company, Port Neches Plant, 
Tex. 
In one embodiment of the present invention, hydrogen sulfide offgas is 
recycled back into the process so as to presulfide the catalyst. In one 
such embodiment, at least a portion the hydrogen sulfide gas generated 
during the reaction product separation process is reintroduced into the 
upgrading unit. Preferably this hydrogen sulfide gas is mixed with the 
heavy oil and water emulsion prior to injection into the reactor. This 
presulfiding is believed to increase the yield of the desire light oil 
products boiling below 1000.degree. F. 
It has been found, that the use of a crude, hot synthesis gas containing 
soot particles introduces sufficient catalyst into the reactors of the 
upgrading unit. The addition of the soot particles, which may contain 
inorganics including nickel and vanadium, has been found to increase the 
yield, and decrease the density of the final light oil product. 
Experiments were conducted in which soot containing inorganic particles 
including nickel and vanadium was added to the synthesis gas used in the 
upgrading reaction in order to investigate the impact of the added soot on 
the heavy oil upgrading process. The starting material heavy oil typically 
has an API gravity of about 12.5 and a sulfur content of about 6.9%. Upon 
reaction of a portion of a heavy oil/water emulsion in the upgrading 
process of the present invention, in the presence of soot, a molybdenum 
based catalyst, such as the MOLYVAN (TM) family of catalysts, and a 
mixture containing vanadium and nickel compounds, the API gravity is 
increased to a value in the range of between about 22 and about 30 and the 
sulfur content is decreased to a value in the range of between about 2.0% 
to about 4.0%. However, upon reacting a second portion of the same heavy 
oil/water emulsion in the presence of only soot and the vanadium and 
nickel catalyst mixture, the API gravity increased to about the same 
degree and the sulfur content reduced to a similar range. These results 
clearly demonstrate that the use of gasification soot alone is able to 
upgrade the heavy oil without the need for supplemental catalyst. 
In addition to the above described enhancement of the upgrading reaction, 
the inclusion of the soot particles with the synthesis gas eliminates the 
expensive soot removal step that is typically a part of the gasification 
process. Further, by using the soot as a catalyst in the upgrading 
reaction, the cost of disposing of the soot is saved. 
As an alternative to or in addition to soot, other additives such as coke 
fines, coal fines, pure sand fines, iron oxide fines, modified iron oxide, 
activated carbon or mixtures thereof may be optionally added to enhance 
the upgrading reactions. As used herein, the term "fines" is used to 
describe particles having a size in the range of between about 0.01 .mu.m 
(1.times.10.sup.-8 m) to about 0.5 mm (5.times.10.sup.-4 m) and preferably 
in the range of between about 1 .mu.m (1.times.10.sup.-6 m) and 50 .mu.m 
(5.0.times.10.sup.-5 m). This particulate matter (FIG. 1, number 115; FIG. 
2, number 215), i.e. fines, may be added to the reaction mixture during 
the formation of the heavy oil/water emulsion (114 & 214 respectively) 
feedstock. It is believed that the addition of these additives leads to 
the improvement of the upgrading reactions by minimizing mesophase 
formation during the reactions. The fines provide sites for the formation 
of coke precursors so as to inhibit the growth of coke deposits on the 
reactor walls or pathways which may otherwise lead to reactor plugging. 
A second benefit derived from the use of hot, crude synthesis is the 
in-situ activation and sulfiding of the transition metal catalyst. Sulfur 
containing gases in the synthesis gas, or offgas generated from the heavy 
crude may be used in this presulfiding step. Presulfiding has been found 
to improve the overall upgrading reaction chemistry. Experiments conducted 
in the absence and the presence of H.sub.2 S or CS.sub.2 in the reaction 
have shown that the presence of the sulfur compounds improves the quality 
of the light oil product, such as increased distillate yield and 
asphaltene content. 
One skilled in the art will appreciate the cost and performance benefits of 
in-situ activation and sulfiding of the transition metal catalyst. Under 
the current state of the art, these steps are conducted as separate steps 
within the reactor or in a separate portion of the refinery facility. By 
conducting the activation/sulfiding step in-situ in accordance with the 
present invention, the reactor down-time needed to conduct the sulfiding 
steps in the upgrading reactor itself or the capital costs of separate 
facilities are eliminated. Additional cost savings may be realized by the 
elimination of the gas scrubbing steps conventionally conducted in the 
production of synthesis gas. 
The upgrading unit product stream (126) is a mixture including heavy oil 
residues (128), hydrocarbon contaminated water (130), and light oil (132). 
Conventional separation technology may be used to separate the components 
of the upgrading unit product stream. 
In a preferred embodiment of the present invention, the heavy oil residue 
and a portion of the hydrocarbon contaminated water are separated from the 
product stream in a hot separator and the light oil and the remaining 
hydrocarbon contaminated water are separated from each other in a cold 
separator. Useful gases derived from the separation process, including 
hydrogen, gaseous hydrocarbons, carbon monoxide, and carbon dioxide are 
recirculated and used in either the gasification unit or the upgrading 
unit. 
The light oil (132) produced in the upgrading process may be stabilized by 
bubbling nitrogen or some other inert gas through it so as to remove any 
dissolved gases. The light oil product may be utilized elsewhere in the 
refinery facility, stored on-site for use at a later date, or shipped to 
another refinery site. The heavy oil residues (128) and the hydrocarbon 
contaminated water (130) may be conventionally stored on-site and disposed 
of in an environmentally conscious manner. 
In another embodiment of the present invention, the heavy oil residue and 
hydrocarbon contaminate water waste-streams are recycled back into the 
upgrading process of the present invention or elsewhere in the refinery 
facility as shown in FIG. 2. It should be noted that 
components/elements/designations are the same as those utilized in FIG. 1, 
except that the number has been increased by 100, i.e. the upgrading unit 
in FIG. 1 is 110, whereas the upgrading unit in FIG. 2 is 210, and so 
forth. The heavy oil residues (228) and the hydrocarbon contaminated water 
waste streams are mixed together along with at least one surfactant (236) 
in a second emulsion mixer (234) to form a stabilized hydrocarbon 
contaminated water/heavy oil residue (HCW/HOR) emulsion fuel (240). The 
HCW/HOR emulsion fuel (240) can be used as at least a portion of the 
feedstock for the partial oxidation unit (212) also known as a 
gasification unit. One skilled in the art will understand that 
supplementary gasification fuel may be required by the gasification unit 
in order to generate sufficient amounts of crude, hot synthesis gas used 
in the upgrading unit 210. 
In one such embodiment, the HCW/HOR emulsion fuel, a temperature moderator 
(if required e.g. H.sub.2 O, CO.sub.2), and a stream of free-oxygen 
containing gas are introduced into the reaction zone of a free-flow 
unobstructed downflowing vertical refractory lined steel wall pressure 
vessel where the partial oxidation reaction takes place for the production 
of synthesis gas. A typical gas generator is shown and described in 
coassigned U.S. Pat. No. 3,544,291, which is incorporated herein by 
reference. 
A two, three or four stream annular type burner, such as shown and 
described in coassigned U.S. Pat. Nos. 3,847,564, and 4,525,175, which are 
incorporated herein by reference, may be used to introduce the feedstreams 
into the partial oxidation gas generator. With respect to U.S. Pat. No. 
3,847,564, free-oxygen containing gas, for example in admixture with 
steam, may be simultaneously passed through the central conduit and outer 
annular passage of the burner. The free-oxygen containing gas is selected 
from the group consisting of substantially pure oxygen i.e. greater than 
95 mole % O.sub.2, oxygen-enriched air i.e. greater than 21 mole % 
O.sub.2, and air. The free-oxygen containing gas is supplied at a 
temperature in the range of about 100.degree. F. to 1000.degree. F. The 
HCW/HOR emulsion fuel is passed into the reaction zone of the partial 
oxidation gas generator by way of the intermediate annular passage at a 
temperature in the range of about ambient to 650.degree. F. In another 
embodiment, a stream of vent gas may be simultaneously introduced into the 
free-flow gas generator by way of a separate passage in the burner and 
reacted by partial oxidation simultaneously with the partial oxidation 
reaction of the HCW/HOR emulsion fuel. 
The burner assembly is inserted downward through a top inlet port of the 
noncatalytic synthesis gas generator. The burner extends along the central 
longitudinal axis of the gas generator with the downstream end discharging 
a multiphase mixture of fuel, free-oxygen containing gas, and temperature 
moderator such as water, steam, or CO.sub.2 directly into the reaction 
zone. 
The relative proportions of fuels, free-oxygen containing gas and 
temperature moderator in the feedstreams to the gas generator are 
carefully regulated to convert a substantial portion of the carbon in the 
fuel feedstream, e.g., up to about 90% or more by weight, to carbon 
oxides; and to maintain an autogenous reaction zone temperature in the 
range of about 1800.degree. F. to 3500.degree. F. Preferably the 
temperature in the gasifier is in the range of about 2400.degree. F. to 
2800.degree. F., so that molten slag is produced. The pressure in the 
partial oxidation reaction zone is in the range of about 1 to 30 
atmospheres. Further, the weight ratio of H.sub.2 O to carbon in the feed 
is in the range of about 0.2-3.0 to 1.0, such as about 0.5-2.0 to 1.0. The 
atomic ratio of free-oxygen to carbon in the feed is in the range of about 
0.8-1.5 to 1.0, such as about 0.9-1.2 to 1.0. By the aforesaid operating 
conditions, a reducing atmosphere comprising H.sub.2 +CO is produced in 
the reaction zone along with nontoxic slag. 
The dwell time in the partial oxidation reaction zone is in the range of 
about 1 to 15 seconds, and preferably in the range of about 2 to 8 
seconds. With substantially pure oxygen feed to the gas generator, the 
composition of the effluent gas from the gas generator in mole % dry basis 
may be as follows: H.sub.2 10 to 60, CO 20 to 60, CO.sub.2 5 to 60, 
CH.sub.4 0 to 5, H.sub.2 S+COS 0 to 5, N.sub.2 0 to 5, and Ar 0 to 1.5. 
With air feed to the gas generator, the composition of the generator 
effluent gas in mole % dry basis may be about as follows: H.sub.2 2 to 20, 
CO 5 to 35, CO.sub.2 5 to 25, CH.sub.4 0 to 2, H.sub.2 S+COS 0 to 3, 
N.sub.2 45 to 80, and Ar 0.5 to 1.5. Unconverted carbon, ash, or molten 
slag are contained in the effluent gas stream. The effluent gas stream is 
called crude synthesis gas and may be recycled without further processing 
in the above noted upgrading reaction. 
Advantageously, in the extremely hot reducing atmosphere of the gasifier, 
the toxic elements in any inorganic matter from the fuel materials are 
captured by the noncombustible constituents present and converted into 
nontoxic nonleachable slag. This permits the nontoxic slag to be sold as a 
useful by-product. For example, the cooled slag may be ground or crushed 
to a small particle size e.g. less than 1/8" and used in road beds or 
building blocks. 
Another facet of the present invention is the formulation of the HCW/HOR 
emulsion fuel used above as a feedstock for the gasification unit or as a 
fuel for a oxidation unit. It was found that to utilize this emulsion fuel 
as a feedstock, the emulsion needed to be stabilized. As used herein, a 
stabilized emulsion fuel is characterized by maintaining an emulsion state 
for at least 1 hour, however stable emulsions have been made with a 
stability of greater than 30 days. 
In order to achieve stability in the HCW/HOR emulsion fuel, it was 
discovered that a mixture of surfactants is more effective at stabilizing 
the emulsion than current state of the art, single surfactant emulsions. 
The stabilized HCW/HOR emulsion fuel of the present invention is a mixture 
including hydrocarbon contaminated water, heavy oil or heavy oil residues 
and at least two surfactants in a sufficient amount to stabilize the 
emulsion. The water used in forming the HCW/HOR emulsion fuel typically 
contains dissolved hydrocarbons, or suspended oils or coke in the range of 
between about 10 ppm to about 20%. The heavy oil residue may be the actual 
sidestream residue generated from the above upgrading process or similar 
processes, heavy oil refinery waste, heavy oil itself or mixtures thereof. 
The water and oil components are mixed together in a ratio of oil to water 
in the range of about 99.99:0.01 to about 70:30 in the presence of a 
plurality of surfactants to achieve a stable emulsion. Suitable 
surfactants include sorbitan trioleate (Span 85), sorbitan tristearate 
(Span 65), sodium laurel sulfate, other similar surfactants with a 
hydrophilic-lipophilic balance in the range of between about 2 to about 
10. The surfactants are blended together in a ratio in the range of 
between about 0.01 to about 0.99 before mixing with the emulsion. 
In addition to the use of surfactants, it has been found that the stability 
of the HCW/HOR emulsion fuel is improved if the heavy oil residue is 
processed in an advance homogenizer. By processing the heavy oil residue 
in such a manner, agglomerations of asphaltenes and other sediments are 
reduced in size which increases stability of the HCW/HOR fuel. In one 
embodiment a 450X-series machine manufactured by Ross is utilized. Unlike 
traditional homogenizers, the X-Series rotor and stator is composed of a 
matrix of interlocking channels. With the rotor turning at high speeds 
(i.e. tip speeds as high as 17,000 rpm) the X-series machine can produce 
emulsions comparable to those produced by a high pressure homogenizer. As 
shown below in TABLE 1, this results in a significant reduction in the 
viscosity of the heavy oil residue. 
TABLE 1 
______________________________________ 
Time (s) 
5 15 25 35 45 
______________________________________ 
Viscosity* (cP) of Unprocessed 
1300 1050 975 925 900 
Heavy Oil Residue 
Viscosity* (cP) of Processed 200 200 190 190 190 
Heavy Oil Residue 
______________________________________ 
*Viscosity measured using Bohlin Rheometer, 25.degree. C. 
Results generated using the above system on the heavy oil residue show a 
significant reduction in particle size of the asphaltenes and improved 
emulsion stability. The viscosity of the heavy oil residue is also 
improved as shown above which makes handling and storage much easier. 
In one embodiment of the present invention at least a portion of the 
HCW/HOR emulsion fuel is utilized as a fuel for a combustion unit that in 
turn provides heat for the reforming unit. This is particularly 
advantageous when gasification or partial oxidation is not the preferred 
source of hydrogen containing gas. A conventional combustion unit is used 
for this process. 
In yet another embodiment of the present invention, the fraction of the 
reaction product boiling below 1000.degree. F. is subjected to 
hydrotreating, while it is still hot. This process may be refereed to as 
secondary hydrotreating or integrated hydrotreating. The hydrotreating of 
the fraction of reaction product boiling below 1000.degree. F. is carried 
out using hydrotreating conditions, such as those described in co-assigned 
U.S. Pat. 5,436,215 the contents of which are hereby incorporated herein 
by reference. The hydrogenation process generally reacts the oil with 
hydrogen gas in the presence of a supported metal oxide catalyst under 
elevated temperatures and pressures. Catalysts which may be utilized in 
the integrated hydrotreating process of this embodiment may be selected 
for a number of commercial catalysts including Criterion TEX-2710 catalyst 
a commercially available molybdenum oxide/nickel oxide catalyst supported 
on alumnia and promoted with silica; Criterion HDS-2443 catalyst a 
commercially available molybdenum oxide/nickel oxide catalyst supported on 
alumnia and promoted with silica and phosphorous oxide; Criterion 424 
catalyst a commercially available molybdenum oxide/nickel oxide catalyst 
supported on alumnia and promoted with phosphorous oxide and other similar 
such catalysts. All of the proceeding catalysts are available from 
Criterion Catalysts of Houston Tex. 
The following examples are included to demonstrate embodiments of the 
invention. It should be appreciated by those of skill in the art that the 
techniques disclosed in the examples which follow represent techniques 
discovered by the inventors to function well in the practice of the 
invention, and thus can be considered to constitute preferred modes for 
its practice. However, those of skill in the art should, in light of the 
present disclosure, appreciate that many changes can be made in the 
specific embodiments which are disclosed and still obtain a like or 
similar result without departing from the spirit and scope of the 
invention. 
In the following Examples, the heavy oil feed was an Eocene oil having the 
characteristics shown in Table 2. below: 
TABLE 2 
______________________________________ 
Total Oil Composition: Feed Eocene Oil 
______________________________________ 
Density (API gravity) 
13.1 
% Total Distillates (BP &lt; 524.degree. C.) 49.0% 
% Asphaltenes 10.9% 
Fe (ppm) 3.3 
V (ppm) 73.0 
Ni (ppm) 27.6 
Cr (ppm) 8.1 
S (% wt) 6.57 
______________________________________ 
Example 1 
Feed Eocene oil was emulsified with 10% water utilizing Span 65 and Span 85 
as an emulsifier to stabilize the emulsion. To this mixture a sufficient 
amount of iron naphthanate, an oil soluble catalyst, and MOLYVAN (TM) were 
added to give a concentration of 100 ppm and 200 ppm respectively of each 
catalyst within the emulsion. In addition carbon powder was added to 
achieve a concentration of about 1000 ppm. The emulsion was reacted in a 
bench scale upflow tubular reactor with an equal mixture of carbon 
monoxide and hydrogen gas and a temperature of about 425.degree. C. and a 
pressure of about 1400 psig. The gas was introduced at a rate of about 500 
sccm. Additional conditions are given below in Table 3. 
TABLE 3 
______________________________________ 
Conditions Run # 118.7126.1 
Run #118.7126.2 
______________________________________ 
Run length (hr.) 
2 4 
LHSV 0.82 0.7 
Pump Speed (cc/min) 1.75 1.5 
Feed oil (ml) 210 180 
Gas Volume (cm.sup.3) 58.97 62.13 
Plugging NO NO 
______________________________________ 
The resulting light oil product was separated from the reaction product to 
give an oil having the properties in Table 4. 
TABLE 4 
______________________________________ 
Properties Run # 118.7126.1 
Run #118.7126.2 
______________________________________ 
Liquid Product 
Total Weight (gm) 190.3 158.7 
Density (API gravity) 22.3 22.0 
% Total Distillates 80 84.5 
(BP &lt; 524.degree. C.) 
% Desulfurization 45.4 49.2 
% Asphaltenes 4.9 3.5 
Fe (ppm) 2 2 
V (ppm) 44.7 45 
Ni (ppm) 16.6 14.1 
Cr (ppm) 5 5 
Gas Product 4.56 4.23 
H.sub.2 S (wt %) 
______________________________________ 
Upon review of the above, one of ordinary skill in the art should note that 
the API gravity of the liquid product is significantly increased 
indicating a lighter oil product. In addition a beneficial decrease in the 
asphaltene concentration and the concentration of both sulfur and metals 
is observed. 
Example 2 
Feed Eocene oil was emulsified with 10% water utilizing Span 65 and Span 85 
as an emulsifier to stabilize the emulsion. To this mixture a sufficient 
amount of MOLYVAN (TM) was added to give a concentration of 200 ppm of the 
catalyst within the emulsion. In addition carbon powder was added to 
achieve a concentration of about 1000 ppm. The emulsion was reacted in a 
bench scale upflow tubular reactor with an equal mixture of carbon 
monoxide and hydrogen gas and a temperature of about 425.degree. C. and a 
pressure of about 1400 psig. The gas was introduced at a rate of about 500 
sccm. Additional conditions are given below in Table 5. 
TABLE 5 
______________________________________ 
Conditions Run # 119.7156.1 
Run #119.7156.2 
______________________________________ 
Run length (hr.) 
2 4 
LHSV 0.82 0.7 
Pump Speed (cc/min) 1.75 1.5 
Feed oil (ml) 210 180 
Gas Volume (cm.sup.3) 60.61 64.04 
Plugging No No 
______________________________________ 
The resulting product was separated to give an oil and gaseous products 
having the properties in Table 6. 
TABLE 6 
______________________________________ 
Properties Run # 118.7126.1 
Run #118.7126.2 
______________________________________ 
Liquid Product 
Total Weight (gm) 178.8 149.2 
Density (API gravity) 22.0 26.7 
% Total Distillates 81 88.5 
(BP &lt; 524.degree. C.) 
% Desulfurization 45.7 51.4 
% Asphaltenes 5.1 2.9 
Fe (ppm) 2 2 
V (ppm) 49.4 35.7 
Ni (ppm) 17.5 10.7 
Cr (ppm) 5 5 
Gas Product 4.51 3.96 
H.sub.2 S (wt %) 
______________________________________ 
Upon review of the above, one of ordinary skill in the art should note that 
the API gravity of the liquid product is significantly increased 
indicating a lighter oil product. In addition a beneficial decrease in the 
asphaltene concentration and the concentration of both sulfur and metals 
is observed. 
Example 3 
Feed Eocene oil was emulsified with 10% water utilizing Span 65 and Span 85 
as an emulsifier to stabilize the emulsion. To this mixture a sufficient 
amount of iron naphthanate, an oil soluble catalyst, and MOLYVAN (TM) were 
added to give a concentration of 100 ppm and 200 ppm respectively of each 
catalyst within the emulsion. In addition silica sand was added to achieve 
a concentration of about 1000 ppm. The emulsion was reacted in a bench 
scale upflow tubular reactor with an equal mixture of carbon monoxide and 
hydrogen gas and a temperature of about 425.degree. C. and a pressure of 
about 1400 psig. The gas was introduced at a rate of about 500 sccm. 
Additional conditions are given below in Table 7. 
TABLE 7 
______________________________________ 
Conditions Run # 118.7126.1 
Run #118.7126.2 
______________________________________ 
Run length (hr.) 
2 4 
LHSV 0.82 0.7 
Pump Speed (cc/min) 1.75 1.5 
Feed oil (ml) 210 180 
Gas Volume (cm.sup.3) 58.91 59.7 
Plugging NO NO 
______________________________________ 
The resulting light oil product was separated from the reaction product to 
give an oil having the properties in Table 8. 
TABLE 8 
______________________________________ 
Properties Run # 118.7126.1 
Run #118.7126.2 
______________________________________ 
Liquid Product 
Total Weight (gm) 187 159.9 
Density (API gravity) 23.0 23.1 
% Total Distillates 77 77.5 
(BP &lt; 524.degree. C.) 
% Desulfurization 48.2 48.7 
% Asphaltenes 4.9 4.6 
Fe (ppm) 2 2 
V (ppm) 36.3 40.3 
Ni (ppm) 14.3 15.9 
Cr (ppm) 5 5 
Gas Product n/a 4.66 
H.sub.2 S (wt %) 
______________________________________ 
Upon review of the above, one of ordinary skill in the art should note that 
the API gravity of the liquid product is significantly increased 
indicating a lighter oil product. In addition a beneficial decrease in the 
asphaltene concentration and the concentration of both sulfur and metals 
is observed. 
Example 4 
Feed Eocene oil was emulsified with 10% water utilizing Span 65 and Span 85 
as an emulsifier to stabilize the emulsion. To this mixture a sufficient 
amount of MOLYVAN (TM) 885 was added to give a concentration of 1000 ppm 
of the catalyst within the emulsion. Particulate solids were not added to 
the reaction feed. The emulsion was reacted in a bench scale upflow 
tubular reactor with an equal mixture of carbon monoxide and hydrogen gas 
and a temperature of about 425.degree. C. and a pressure of about 1400 
psig. The gas was introduced at a rate of about 500 sccm. Additional 
conditions are given below in Table 9. 
TABLE 9 
______________________________________ 
Conditions Run # 117.7106.1 
Run #117.7106.2 
______________________________________ 
Run length (hr.) 
1.5 3 
LHSV 0.82 0.7 
Pump Speed (cc/min) 1.75 1.5 
Feed oil (ml) 157.5 135 
Gas Volume (cm.sup.3) 38.42 37.72 
Plugging NO NO 
______________________________________ 
The resulting light oil product was separated from the reaction product to 
give an oil having the properties in Table 10 
TABLE 10 
______________________________________ 
Properties Run # 117.7106.1 
Run #117.7106.2 
______________________________________ 
Liquid Product 
Total Weight (gm) 143 123.8 
Density (API gravity) 22.5 24.0 
% Total Distillates 79 84 
(BP &lt; 524.degree. C.) 
% Desulfurization 45.5 49.9 
% Asphaltenes 5.8 3.7 
Fe (ppm) 2 2 
V (ppm) 48 28.8 
Ni (ppm) 17.6 11.6 
Cr (ppm) 5 5 
Gas Product 2.60 2.57 
H.sub.2 S (wt %) 
______________________________________ 
Upon review of the above, one of ordinary skill in the art should note that 
the API gravity of the liquid product is significantly increased 
indicating a lighter oil product. In addition a beneficial decrease in the 
asphaltene concentration and the concentration of both sulfur and metals 
is observed. 
Example 5 
The following is a control example in which neither soluble catalyst nor 
particulate fines were included in the reactor feed. Feed Eocene oil was 
emulsified with 10% water utilizing Span 65 and Span 85 as an emulsifier 
to stabilize the emulsion. The emulsion was reacted in a bench scale 
upflow tubular reactor with an equal mixture of carbon monoxide and 
hydrogen gas and a temperature of about 425.degree. C. and a pressure of 
about 1400 psig. The gas was introduced at a rate of about 500 sccm. 
Additional conditions are given below in Table 11. 
TABLE 11 
______________________________________ 
Run Run Run 
Conditions 121-7256.1 121-7256.2 121-7256.3 
______________________________________ 
Run length (hr.) 
1.3 2.6 4 
LHSV 0.94 0.82 0.7 
Pump Speed 2 1.75 1.5 
(cc/min) 
Feed oil (ml) 156 136.5 120 
Gas Volume (cm.sup.3) 45.75 45.41 41.75 
Plugging YES YES YES 
______________________________________ 
The resulting light oil product was separated from the reaction product to 
give an oil having the properties in Table 12. 
TABLE 12 
______________________________________ 
Run Run Run 
Properties 121-7256.1 121-7256.2 121-7256.3 
______________________________________ 
Liquid Product 
Total Weight (gm) 145.7 112.8 108.8 
Density 23.6 27 27.1 
(API gravity) 
% Total Distillates 84 89.5 90 
(BP &lt; 524.degree. C.) 
% Desulfurization 48.9 54.3 53.6 
% Asphaltenes 6 3 2.7 
Fe (ppm) 2 2 2 
V (ppm) 40.7 15.6 15.4 
Ni (ppm) 15.7 6.2 5.5 
Cr (ppm) 5 5 5 
Gas Product 2.55 2.88 2.53 
H.sub.2 S (wt %) 
______________________________________ 
Upon review of the above, one of ordinary skill in the art should note that 
the reactor exhibits plugging due to the formation of sediment deposits 
inside the reactor. The formation of sediment deposits is undesirable 
because the build up of deposits changes the reactor volume and conditions 
o the reaction potentially creating a hazardous situation. In addition, if 
the reactor is to be run on a large industrial scale, periodic maintenance 
in order to clean the reactor would require considerable non-productive 
time periods. 
Spectroscopic characterization of the products of Example 4 and Example 5 
were conducted utilizing .sup.1 H nuclear magnetic resonance (NMR). Table 
13 compares the impact of the catalyst on the composition, in particular 
the degree of saturation of the upgraded product. 
TABLE 13 
______________________________________ 
Run # 117-1 121-1 117-2 
121-2 
______________________________________ 
Catalyst Yes No Yes No 
Total Aliphatic H 94.0 92.0 93.7 91.9 
Total Olefinic H 0.3 0.7 0.4 0.5 
Total Aromatic H 5.7 7.3 5.9 7.6 
Hetero-Aromatic H 0.2 0.2 0.1 0.2 
Tri-Aromatic H 0.6 0.6 0.6 0.7 
Di-Aromatic H 1.9 1.9 2.0 2.2 
Mono-Aromatic H 3.0 4.5 3.2 4.6 
.alpha.-H 11.8 13.5 11.9 13.8 
.alpha.-CH.sub.2 7.8 8.0 7.8 8.2 
.alpha.-CH.sub.3 3.6 5.0 3.7 5.1 
.beta.-H 56.7 53.0 56.4 52.8 
.beta.-CH.sub.2 13.1 13.1 12.6 12.4 
Paraffinic CH.sub.2 43.6 39.9 43.8 40.3 
.gamma.-H 25.5 25.6 25.4 25.3 
______________________________________ 
Upon review of the above results, one of skill in the art should observe 
that the presence of the catalyst is helpful in saturating the olefin and 
aromatic components of the oil thus yielding a higher total aliphatic 
content in the total liquid products. In contrast the runs in which the 
catalyst was not present generated significant amounts of coke and 
sediment which as previously noted leads to reactor plugging. 
Example 6 
Feed Eocene oil was emulsified with 10% water utilizing Span 65 and Span 85 
as an emulsifier to stabilize the emulsion. To this mixture a sufficient 
amount of MOLYVAN (TM) was added to give a concentration of 1000 ppm of 
the catalyst within the emulsion. In addition, a polymerized dimethyl 
silicone fluid antifoaming agent, Dow Corning 200 Fluid available from Dow 
Corning, was added to the reactor feed in an amount to give a 100 ppm 
concentration. Particulate solids were not added to the reactor feed. The 
emulsion was reacted in a bench scale upflow tubular reactor with an equal 
mixture of carbon monoxide and hydrogen gas and a temperature of about 
425.degree. C. and a pressure of about 1400 psig. The gas was introduced 
at a rate of about 500 sccm. Additional conditions are given below in 
Table 14. 
TABLE 14 
______________________________________ 
Conditions Run # 122-8086.1 
Run #122-8086.2 
______________________________________ 
Run length (hr.) 
1.5 3 
LHSV 0.82 0.7 
Pump Speed (cc/min) 1.75 1.5 
Feed oil (ml) 157.5 135 
Gas Volume (cm) 38.42 37.78 
Plugging NO NO 
______________________________________ 
The resulting light oil product was separated from the reaction product to 
give an oil having the properties in Table 15. 
TABLE 15 
______________________________________ 
Properties Run # 122-8086.1 
Run #122-8086.2 
______________________________________ 
Liquid Product 
Total Weight (gm) 148 123.8 
Density (API gravity) 21.3 23.6 
% Total Distillates n/a n/a 
(BP &lt; 524.degree. C.) 
% Desulfurization 44.0 45.2 
% Asphaltenes n/a n/a 
Fe (ppm) 2 2 
V (ppm) 55.4 46.4 
Ni (ppm) 20.8 15.1 
Cr (ppm) 5 5 
Gas Product 3.41 2.99 
H.sub.2 S (wt %) 
______________________________________ 
Upon review of the above, one of ordinary skill in the art should note that 
the API gravity of the liquid product is significantly increased 
indicating a lighter oil product. In addition a beneficial decrease in the 
asphaltene concentration and the concentration of both sulfur and metals 
is observed. In addition, the presence of the MOLYVAN catalyst in the 
reactor feed helps to prevent the formation of sediment in the reactor. 
Example 7 
As a comparison of the present invention with that utilizing a solid 
catalyst, then following example was carried out. Feed crude having an API 
gravity of 12.5 and 6.9% sulfur was mixed one of three catalyst and 
introduced into a bench scale upflow tubular reactor as described in the 
previous Examples. The reactions were carried out at 425.degree. C., a 
pressure of 1000 psig and using a 1:1 mixture of H.sub.2 :CO. TABLE 16 
below presents a comparison of the effect of each type of catalyst. 
TABLE 15 
______________________________________ 
Catalyst API gravity 
% S (by weight) 
______________________________________ 
Fe.sub.2 O.sub.3, solid (1% wt) 
23.1 3.85 
Fe.sub.2 O.sub.3 /SO.sub.4 (0.5% wt) 25.2 3.59 
Iron Naphthanate (250 ppm) 23.3 3.32 
______________________________________ 
One skilled in the art should recognize that the use of the oil soluble 
catalyst (iron naphthanate) in the absence of other particulate solids, 
gives a product with an API and sulfur content comparable to the product 
resulting from the use of conventional solid catalysts. 
Example 8 
Example 7 was repeated except that two different oil soluble catalysts were 
compared in the absence of particulate solids. The results are given in 
TABLE 16 below 
TABLE 16 
______________________________________ 
Catalyst API gravity 
% S (by weight) 
______________________________________ 
Starting material 12.5 6.9 
Mo as MOLYVAN (250 ppm) 27.5 2.96 
Iron Naphthanate (250 ppm) 23.3 3.32 
______________________________________ 
Upon review of the above results, one of skill in the art should recognize 
that the molybdenum based oil soluble catalyst was slightly more active 
than the iron based oil soluble catalyst even in the absence of 
particulate solids. 
Example 9 
An embodiment of the present invention was carried out in which condition 
of pressure and the ratio of hydrogen to carbon monoxide were changed. 
Feed crude having an API gravity of 12.5 and 6.9% sulfur was mixed with 
250 ppm of MOLYVAN and iron naphthanate and 6% water and introduced into a 
bench scale upflow tubular reactor as described in the previous Examples. 
The reactions were carried out under the condition noted below in TABLE 17 
along with the properties of the reaction product. 
TABLE 17 
______________________________________ 
Pilot Run #36 
Pilot run#39 
______________________________________ 
H2:CO ratio 1:1 3:1 
Temperature 430.degree. C. 425.degree. C. 
Pressure 1100 psig 1300 psig 
Properties of Product 
% wt Sulfur 3 3.19 
API gravity 25.8 23 
Distillate Fraction: 
(% volume) 
IBP-350.degree. F. 10.8 8.3 
350-500.degree. F. 19.9 16.7 
500-650.degree. F. 24.4 21.3 
650-1000.degree. F. 31.8 34.6 
1000.degree. F.+ 13.1 19.1 
______________________________________ 
In general, the products generated during run #36 showed a slightly 
improved API gravity over that generated by run #39. The former, however, 
was operated at 430.degree. C. compared to 425.degree. C. used for run 
#39. In addition, review of the data show that about 75% of the total 
liquid product has an API gravity of 30 or above. 
While the compositions and methods of this invention have been described in 
terms of preferred embodiments, it will be apparent to those of skill in 
the art that variations may be applied to the process described herein 
without departing from the concept, spirit and scope of the invention. All 
such similar substitutes and modifications apparent to those skilled in 
the art are deemed to be within the spirit, scope and concept of the 
invention as it is set out in the following claims.