Title of Invention	A METHOD FOR UTILIZING HYDROCARBON WASTE STREAM
Abstract	The fuel properties of petroleum hydrocarbon waste having an API gravity varying from about 5 to 30 are improved by heating the hydrocarbon to a temperature of about 35 °C to 90 °C and mixing the heated hydrocarbon stream with a suitable solvent to reduce the viscosity of the hydrocarbon, which is then separated by a centrifuge to obtain an aqueous phase stream, an oil phase stream, and a separated solids stream. The oil phase stream has a viscosity range of about 250 centipoise (cP) to about 1000 cP. The oil phase stream is utilized in a refinery, while a slurry fuel is prepared with the separated solids stream and aqueous phase stream as a feedstock for road asphalt, a fuel for a combustor, or a fuel for a gasification process. The oil phase stream is used for fuels and feedstock for making carbon fiber.

Title of Invention

A METHOD FOR UTILIZING HYDROCARBON WASTE STREAM

Abstract

The fuel properties of petroleum hydrocarbon waste having an API gravity varying from about 5 to 30 are improved by heating the hydrocarbon to a temperature of about 35 °C to 90 °C and mixing the heated hydrocarbon stream with a suitable solvent to reduce the viscosity of the hydrocarbon, which is then separated by a centrifuge to obtain an aqueous phase stream, an oil phase stream, and a separated solids stream. The oil phase stream has a viscosity range of about 250 centipoise (cP) to about 1000 cP. The oil phase stream is utilized in a refinery, while a slurry fuel is prepared with the separated solids stream and aqueous phase stream as a feedstock for road asphalt, a fuel for a combustor, or a fuel for a gasification process. The oil phase stream is used for fuels and feedstock for making carbon fiber.

Full Text	WO 2006/039714 PCT/US2005/035827 METHOD FOR UTILIZING HYDROCARBON WASTE MATERIALS AS FUEL AND FEEDSTOCK BACKGROUND OF THE INVENTION 1. Held of the Invention 5 [0001] The present invention relates to using hydrocarbon waste materials,- more specifically, heavy petroleum hydrocarbons including petroleum sludge, tank bottoms, or residue having an API gravity of about five to about thirty into useful feels and products. 2. Background of the Invention 10 [0002] Oil producers generate significant amounts of petroleum waste materials. For example, operating companies generate a significant volume of petroleum waste materials, including thousands of cubic meters of oily wastes annually, much of which are tank bottoms sludge and various refinery and production wastes. Furthermore, various amounts of non-leaded hydrocarbon products, waste solvents, and slop oil 15 waste materials are generated. These waste materials are often contaminated by water and insoluble solids. Some of these sludges contain between fifty to ninety percent oil. The annual disposal costs for these materials can be a significant operating expense to operating companies, which is lost. Much of these materials are now "land-farmed" creating potential environmental problems. In the "USA and elsewhere, 20 such disposal techniques are believed to have led to highly toxic superfund sites. Furthermore, local regulations are expected to limit or eliminate land farming in the near future. Therefore, it is important that proper steps are taken to utilize or dispose of such waste materials. [0003] Heavy residue, petroleum waste, and sludge materials are formed during 25 production, handling, and processing of the petroleum hydrocarbons. The transportation and use of the heavy hydrocarbons are difficult because of their high viscosity and poor stability. At ambient conditions, heavy hydrocarbons, such as a WO 2006/039714 PCT/US2005/035827 refinery residue, have an API gravity of about thirty or less. These oily materials are often contaminated with, solid or semi-solid waste materials and water. [0004] Due to improvements in the refining processes over the past fifty years, additional lighter products are "being recovered from every barrel of hydrocarbon 5 waste oil. Thus, the residue and heavy materials, such as bunker fuel, being produced in various refineries are undergoing significant changes in quality including a greater concentration of asphaltenes. The presence of a larger concentration of asphaltenes in fuels has a great impact on fuel usage in various applications. Asphaltenes are polar compounds that tend to agglomerate into very large structures in liquid hydrocarbons. 10 These agglomerates lead to viscosities that are much higher than if the asphaltenes were not structured. The asphaltene molecule appears to carry a core of approximately five stacked flat sheets of condensed aromatic rings, one above the other giving an overall height of sixteen to eighteen Angstroms. The average sheet diameter appears to range from six to fourteen Angstroms. The molecular weight of 15 petroleum asphaltenes can range from about 1,000 to 50,000. A refinery residue after it is extracted with a solvent exists in a solid state such that its viscosity cannot be measured, and one has to heat the material at a sufficiently high temperature (>100°C) to make this material into a low viscosity material suitable for transport. [0005] In storage tanks or tankers, fuel sludge, tank bottom, etc. are formed when 20 asphaltenes are separated from the fuel and deposited on the bottom of the tank. Furthermore, fuel sludges are formed when different fuels including residual fuels are blended when one of the components contains significant amount of asphaltene. In hydrocarbon waste upgraded by hydrotreating and hydrocracking processes, the relatively unreactive portion of the hydrocarbon waste, termed "residue," can be 25 formed, which requires further processing. Refinery wastes, tank bottoms sludge, waste solvents, slop oil, lube oil waste, and other hydrocarbon waste produced during refining are environmentally hazardous and can create a disposal problem. In blending of different hydrocarbon wastes or hydrocarbon waste products, asphaltene/resin ratio is altered and fuels become unstable as asphaltenes separate and 30 agglomerate. Furthermore, as stated earlier, fuel sludges are formed when different WO 2006/039714 PCT/DS2005/035827 fuels including residual fuels are blended, especially when one of the components contains higher amounts of asphaltenes. During transportation, asphaltenes deposit and clog reservoir pores and pipelines. Utilization of hydrocarbon waste involves various steps such as storage, transportation, and combustion, partial oxidation or 5 further refining and the like. The presence of asphaltenes can affect each of these steps. [0006] U.S. Pat. No. 5,133,781 issued to DeRosa et al. discloses a method of stabilizing asphaltenes in hydrocarbons by dissolving the asphaltenes in tetrahydrofuran, phosphochlorinating the asphaltenes, and then reacting the 10 phosphochlorinated-asphaltenes with equimolar amounts of aliphatic or aromatic alcohols. The 781 Patent stabilizes the asphaltenes for use in bituminous liquids until well into the refining process. [0007] Attempts have been made to convert sewage sludge waste into useful fuels. As an example, in U.S. Patent No. 5,356,540 issued to Khan, a pumpable aqueous 15 slurry of sewage sludge is produced by the step of dewatering the sewage sludge to produce an aqueous slurry having a solids content of about 10 to 25 wt. %. The aqueous slurry of sewage sludge is then pretreated to improve its slurrying characteristics by one or a combination of (a) heating, (b) hydrothermal treatment, and (c) heating, mixing and shearing the aqueous slurry of sewage sludge. The following 20 materials are then mixed together at a temperature in the range of about ambient to 400° F to produce a pumpable aqueous slurry having a solids content in the range of about 30 to 65 wt. %: (a) pretreated aqueous slurry of sewage sludge; (b) a nonionic water-soluble alkoxylated alkylphenol additive; and (c) sewage sludge-containing material and/or solid carbonaceous fuel-containing material to increase the solids 25 loading. When using the techniques taught by this patent with industrial hydrocarbon sludge streams, the effects are often limited in duration. [0008] Introduction into refining, partial oxidation (gasification), or combustion processes are possible avenues to dispose of petroleum hydrocarbons, such as tank bottoms sludge or residue. Having 5% by weight or greater asphaltene concentration WO 2006/039714 PCT/US2005/035827 in asphaltene-rich hydrocarbons, however, tends to cause difficulties in pumping, fuel injections, atomization, spray and combustion or partial oxidation. Asphaltene rich particles have a long burning time, which results in larger flame size. Combustion ignition is delayed for these fuels. la a combustion chamber, unbumed carbon and 5 soot are produced. Other difficulties include excessive wear in piston ring and cylinder liner; fracture of piston rings, and increased deposits on combustion chamber. During combustion, the presence of asphaltenes creates non-homogeneous fuel mixtures that result in a non-uniform spray pattern. Larger fuel particles containing asphaltenes do not atomize or vaporize contributing to incomplete combustion that 10 leads to deposits and various pollutants being formed in the combustion system. [0009] A need exists for a method of utilizing petroleum hydrocarbon wastes that will reduce disposal costs and risks associated with disposal of the hydrocarbon wastes. A goal is to provide a process that utilizes the hydrocarbon waste as a fuel source in a process that will not result in deleterious results within the process. A further goal is 15 to provide a process that efficiently utilizes the asphaltenes contained within hydrocarbon waste streams. SUMMARY OF THE INVENTION [0010] The present invention advantageously provides a method of utilizing petroleum sludge or a hydrocarbon waste stream as a fuel source without resulting in 20 deleterious results as a result of using such fuel source within the process. Costly pretreatment of the sludge or hydrocarbon waste stream, while acceptable, is not required in the present invention, which results hi a cost saving. [0011] In this process, hydrocarbon waste stream is heated and mixed with various additives at a temperature in a range of about 35° C to 90° C in the absence of air, 25 while being continuously passed through a centrifuge to separate material into various fractions, namely a separated solids, an aqueous phase, and an oil phase. [0012] Each of the separated solids fraction are preferably used as a fuel source. Separated solids fraction is mixed with water to produce a pumpable slurry fuel WO 2006/039714 PCT/US2005/035827 having a solids content in a range of about 50 to 60 wt. %. The water can be newly added water from an external source or a portion of aqueous phase or combinations thereof. Pumpable slurry fuel can be burned as fuel in a gasifier, furnace, boiler, incinerator, or the hike. Separated solids can also be used as an additive for asphalt. 5 Oil phase is preferably used as a fuel within a refinery. A heavier aromatic portion of the oil phase can serve as a feedstock for making carbon fiber. The suitable boiling fraction that can serve as a feedstock for making carbon fiber is the between 400°C and520°C. [0013] Fuel properties of hydrocarbon waste stream having an API gravity, varying 10 from about 5 to about 30 are improved by mixing the hydrocarbon waste stream with a diluent solvent sufficient to reduce the viscosity of the hydrocarbon to a range of about 250 centipoise (cP) to about 1000 cP. The mixing is preferably performed at a temperature of about 35°C to 100°C. The waste material is centrifuged, filtered, and separated into various products or fractions, namely separated solids, aqueous phase, 15 and oil phase. Separated solids contain substantial amounts of asphaltenes. Other additives can be added to hydrocarbon waste stream as described herein. [0014] In addition to the method embodiments, the apparatus useful to perform the methods described herein is also advantageous provided. BRIEF DESCRIPTION OF THE DRAWINGS 20 [0015] So that the manner in which the features, advantages and objects of the invention, as well as others which will become apparent, may be understood in more detail, more particular description of the invention briefly summarized above may be had by reference to the embodiment thereof which is illustrated in the appended drawings, which form a part of this specification. It is to be noted, however, that the 25 drawings illustrate only a preferred embodiment of the invention and is therefore not to be considered limiting of the invention's scope as it can admit to other equally effective embodiments. WO 2006/039714 PCT7US2005/035827 [0016] FIG. 1 is a simplified block diagram of a process for utilizing a hydrocarbon waste stream having an API gravity of about 5 to about 30 as a fuel source according to an embodiment of the present invention. DESCRIPTION OF THE PREFERRED EMBODIMENTS 5 [0017] The present invention advantageously provides a method of utilizing a petroleum waste stream having an API gravity varying from about 5 to about 30 as a fuel source. Table I includes an example composition for petroleum waste stream. Table I Component Feed wt %, moisture free basis S 1-7 C 70-87 H 7-10 N 0.1-2 H2O (uncentrifuged) 5-50 Density (API gravity) 5-30 Total Distillate (-524 C) 20-60 % Asphaltenes 10-40 10 [0018] Referring to FIG. 1, as an embodiment of the present invention, the method preferably includes the step of heating hydrocarbon waste stream 12 to a preferable preselected temperature range of between about 30 °C and about 100 °C in the absence of air. This step of heating lowers viscosity of hydrocarbon waste stream 12 creating warmed hydrocarbon waste stream 16. The step of heating hydrocarbon 15 waste stream 12 more preferably includes heating hydrocarbon waste stream 12 to a heated temperature within a range of about 50°C to about 100°C. [0019] After being heated, warmed hydrocarbon waste stream 16 is then mixed with a diluent solvent stream 18a to reduce a viscosity of warmed hydrocarbon waste stream 16 to a reduced viscosity. Once diluent solvent stream 18a has been added, warmed 20 hydrocarbon waste stream 16 is then centrifuged to produce oil phase stream 32, aqueous phase stream 20, and separated solids stream 28, jointly called produced WO 2006/039714 PCTYUS2005/035827 streams or fractions. Bach of these produced streams can be collected separately. Separated solids stream 28 contains substantial amounts of asphaltenes. Separated solids stream 28 and water are combined to produce a slurry fuel 30. The water can be newly added water from an external source 24 or a portion of aqueous phase 22 or 5 combinations thereof. Slurry fuel 30 preferably has a solids content of at least 50 weight percent. Slurry fuel 30 is preferably used to produce asphalt or as fuel for a gasification process. Slurry fuel 30 more preferably contains about 50 — 60 weight percent solids. Oil phase stream 32 preferably is used as a fuel source in refineries. At least a portion of oil phase 34 is preferably recycled as feed to the step of 10 centrifuging warmed hydrocarbon waste stream 16. A heavier aromatic portion of the oil phase stream 32 can serve as a feedstock for making carbon fiber. The suitable boiling fraction of the portion of the oil phase stream 32 that can serve as a feedstock for making carbon fiber is the between 400°C and 520°C. [0020] The amount of diluent solvent stream 18a added to warmed hydrocarbon waste 15 stream 16 can be chosen to reach a preselected viscosity of oil phase stream 32, or a . preselected concentration of asphaltenes in warmed hydrocarbon waste stream 16, based on the type of hydrocarbon waste stream 16. Alternately, the amount of diluent solvent 18a can be determined by optimizing these two factors. Amounts preferably in the range of about 0.005 to about 8 weight percent of diluent solvent stream 18a in 20 warmed hydrocarbon waste stream 16 are preferred. This advantageously provides desirable levels of stability of oil phase stream 32. More preferably, the range is between about 0.5 to about 5.0 weight of diluent solvent stream 18a in warmedhydrocarbon waste stream 16. Even more preferably, (he range is between about 1.0 to about 3.0 weight percent. With a warmed hydrocarbon waste stream 16 containing 25 a large concentration of asphaltenes, the concentration of diluent solvent stream 18a is preferably up to 25 weight percent. ■ [0021] Once diluent solvent stream 18ais added to wanned hydrocarbon waste stream 16, a viscosity of warmed hydrocarbon waste stream 16 is reduced. The desired or target viscosity of the oil phase stream 32 will depend on the ultimate use of oil phase 30 stream 32, keeping in mind that a viscosity within the preferably range of about 10 to "WO 2006/039714 PCT/US2005/035827 about 1000 centipoise (cP), and more preferably about 200 to about 900 cP, is preferred at 25 to 70 degree C for most transportation and utilization purposes. [0022] The viscosity of heavy hydrocarbon stream having an API gravity that ranges from about 5 to about 30 is significantly reduced by exposing the hydrocarbon stream 5 to a diluent solvent stream 18a, followed by separation of the produced streams as discussed above. The combined heating and mixing of warmed hydrocarbon waste stream 16 with the diluent solvent stream 18a produces a hydrocarbon fuel comprising oil phase stream 32 that has a viscosity level that can be conveniently transported through pipelines without deposit formation. Preferred 10 pipeline viscosities range from about 400 cP to about 1000 cP. [0023] Examples of preferred diluents for transportation of hydrocarbon waste oil or refinery waste or residue to a refinery or a utilization site are lighter components of petroleum, such as gasoline, naphtha, diesel fuel, and mixtures thereof, is general, the amount of viscosity reducing additive, or diluent solvent stream 18 a, is from about 5 15 weight percentage to about 50 weight percentage, and more preferably about 20 weight percentage to about 35 weight percentage, of warmed hydrocarbon waste stream 16. About 20 weight percentage to 35 weight percentage of diesel, gasoline and naphtha is typically sufficient to reduce the viscosity of warmed hydrocarbon waste stream 16 to less than about 1000 cP to less than about 600 cP at 35 °C. In 20 preferred embodiments of the present invention, hydrocarbon waste stream 12 is preferably selected from the group consisting of petroleum heavy hydrocarbon waste, tank bottom, petroleum heavy fractions, bunker fuel, petroleum sludge, refinery waste, and combinations thereof. [0024] Foreign materials or contaminants, such as sand, dirt, and the like, can exist in 25 hydrocarbon waste stream 12. The methods described herein optionally include the step of prefiltering hydrocarbon waste stream 12 prior to the step of heating hydrocarbon waste stream 12 to remove contaminants from hydrocarbon waste stream 12. Alternately, prefiltering can occur prior to centrifugation. WO 2006/039714 PCT/US2005y035827 [0025] la preferred embodiments of the present invention, diluent solvent stream 18a is preferably selected from the group consisting of gasoline, naphtha, kerosene, diesel fuel, and combinations thereof. Other suitable diluent solvents 18a will be apparent to those of skill hi the art and are to be considered within the scope of the present 5 invention. [0026] Slurry fuel 30 produced by mixing separated solids stream 28 with at least a portion of aqueous phase 22 can be used to produce road asphalt. Slurry fuel 30 can also be made by adding an external source of water 24 to separated solids stream 28 or a combination of an external water source 24 and at least a portion, of aqueous phase 10 22. An advantage of using aqueous phase stream 20 is that it reduces the disposal costs associated with disposing of aqueous phase stream 20. Slurry fuel 30 can also be used in gasification processes or combustion processes as a fuel. Separated solids stream 28 can be used as an additive in road asphalt. [0027] To improve the stability of hydrocarbon waste stream 12, an asphaltenes 15 dispersing agent 18b is preferably added to warmed hydrocarbon waste stream 16. In preferred embodiments of the present invention that include adding an asphaltenes dispersing agent 18b to warmed hydrocarbon waste stream 16, asphaltenes dispersing agent 18b is preferably selected from the group consisting of toluene, xylene, tetralin, furan, phenol, ethyl benzoate, butaldehyde, acetophenone, 20 cyclohexanone, and combinations thereof, Asphaltenes dispersing agent 18b is preferably added so that asphaltenes dispersing agent 18b has a concentration of about 0.1 weight percent to about 25 weight percent of warmed hydrocarbon waste stream 16 with dispersing agent, In addition to improving the stability of warmed hydrocarbon waste stream 16, asphaltenes dispersing agent 18b also advantageously 25 enhances the solubility of the asphaltenes, which enhances the yield of oil phase stream 32 that is recoverable from warmed hydrocarbon waste stream 16. Asphaltenes dispersing agent 18b is preferably added to warmed hydrocarbon waste stream 16 using conventional methods at any time during or after centrifugation of warmed hydrocarbon waste stream 16, depending on the nature of the waste. WO 2006/039714 PCT/US2005/035827 [0028] In preferred embodiments of the present invention, the invention includes the step of adding an emulsion breaker additive 18c to warmed hydrocarbon waste stream 16 so that emulsion breaker additive 18c has a concentration of less than 100 ppm. Chemical emulsion breaker additives 18c disrupt the interfacial tensions between oil 5 and water and allow droplets to coalesce and separate. Suitable emulsion breaker additives 18c for the present invention preferably include nonionic surfactants, polyglycols, polyglycol esters, ethoxylated resins, ethoxylated nonylphenols, polyhydric alcohols] sulfuric acid salts', \|and combinations thereof. A preferable nonionic surfactant preferably includes a polycrylamide polymer. If oil phase stream 10 32 is going to subsequently be used in oil field production, emulsion breaker additive 18c preferably has a concentration in a range of about 1 ppm to about 200 ppm. If oil phase stream 32 is going to subsequently be used in refinery desalting processes, emulsion breaker additive 18c preferably has a concentration in a range of about 5 ppm to about 20 ppm. 15 [0029] To facilitate separation of warmed hydrocarbon waste stream 16, a filter aid 18d can be added to warmed hydrocarbon waste stream 16 to aid in the separation of oil phase stream 32 and aqueous phase stream 20. Once added, filter aid 18d preferably has a concentration of less than 1 weight percent of warmed hydrocarbon waste stream 16. Filter aid 18d is preferably selected from the group consisting of 20 diatomite, siliceous materials, cellulose materials, and combinations thereof. Commercial filter aids 18d are available from companies, such as Aderco Chemical Products Inc. headquartered in Quebec. [0030] The extent of fuel properties improvements made to hydrocarbon waste stream 12 can be optimized based on the time/duration/type of additive and the nature and 25 type of additive as well as the degree of desired separation. The effect of viscosity reduction is retained for at least seven days. [0031] As another embodiment of the present invention, a method for utilizing a hydrocarbon waste stream having an API gravity varying from about 5 to about 30 is advantageously provided. In this embodiment, hydrocarbon waste stream 12 is heated 10 WO 2006/039714 PCT/US2005/035827 preferably in a temperature range of about 35° C to about 100 DC in the absence of air, and more preferably in a range of about 50°C to about 90°C. [0032] Warmed hydrocarbon waste stream 16 with then mixed with a solvent 18 that is preferably selected from the group consisting of diluent solvent stream 18 a, 5 asphaltenes dispersing agent 18b, emulsion breaker additive 18c, filter aid 18d, and combinations thereof. Warmed hydrocarbon waste stream 16 is then preferably centrifuged to produce oil phase stream 32, aqueous phase stream 20, and separated solids stream 28. [0033] Separated solids stream 28 and water 24 are mixed to form a slurry fuel 30 that 10 has a solids content at least 50 wt%. The water can be newly added water from an external source 24 or a portion of aqueous phase 22 or combinations thereof. Oil phase stream 32 can be used as a fuel in a refinery. Slurry fuel 30 can be used as an additive for asphalt. Slurry fuel 30 can also be used as fuel in combustion and gasification processes. At least a portion of oil phase 34 can be recycled within the 15 • process as a feed for the step of cenrrifuging warmed hydrocarbon waste stream 16. [0034] In addition to the method embodiments of the present invention, an apparatus embodiment is also advantageously provided, as shown in Fig. 1. In this embodiment, the apparatus 10 preferably includes a heater 14, a centrifuge 20, and a mixer 42. Heater 14 is preferably used for heating hydrocarbon waste stream 12 in the 20 temperature range between about 35°C and about 100°C in the absence of air. Mixer 42 is preferably used for mixing warmed hydrocarbon waste stream 16 with solvent 18 that is preferably selected from the group consisting of diluent solvent stream 18a, asphaltenes dispersing agent 18b, emulsion breaker additive 18c, a filter aid 18d, and combinations thereof. Centrifuge 20 is preferably used for centrifugmg warmed 25 hydrocarbon waste stream 16 to produce oil phase stream 32, aqueous phase stream 20, and separated solids stream 28. [0035] An additional mixer 44 can be provided for mixing separated solids stream 28 with at least a portion of aqueous phase 22 to produce slurry fuel 30 having a solids 11 WO 2006/039714 PCTYUS2005/035827 content at least 50 weight percent, and more preferably in the range of about 50 to about 60 weight percent. [0036] Heater 14, first mixer 42, and centrifuge 20 can be combined in a single three phase centrifuge 20. Other suitable types of equipment that can function as heater 14, 5 first mixer 42, second mixer 44, and centrifuge 20 will be known to those of skill in the art and are to be considered within the scope of the present invention. For example, embodiments including a mixer-can include any device capable of mixing two or more compounds together. [0037] In preferred embodiments of the present invention, the present invention 10 preferably includes a prefilter for prefiltering hydrocarbon waste stream 12 prior to heating hydrocarbon waste stream 12 to remove contaminants from hydrocarbon waste stream 12. [0038] Each of the fractions collected from the step of centrifuging warmed hydrocarbon waste stream 16 can be used in subsequent processes. For example, a 15 catalyst 40 preferably in a reactor 36 can be added to oil phase stream 32 to produce a fuel that can be used within refineries. Catalyst 40 is preferably selected from the group consisting of molybdenum, iron, cobalt, nickel, vanadium, and combinations thereof. The type of catalyst 40 that is added will depend upon the type of process in which the fuel will be used. Once added, catalyst 40 preferably has a concentration of 20 less than 1 weight percent of the produced fuel. [0039] As an advantage of the present invention, the processes described herein can be used with a variety of hydrocarbon waste streams and can be controlled based upon the ultimate final use of oil phase stream 32 and slurry fuel 30. As another advantage, the processes described herein convert substantially all of hydrocarbon waste stream 25 12 into useful produced streams. As a result, disposal costs normally associated with disposal of hydrocarbon waste stream 12 are virtually ehminated. [0040] Another advantage of the present invention is that the reduction of viscosity of hydrocarbon waste stream 12 lasts substantially longer than the reduction of viscosity 12 WO 2006/039714 PCT/PS2005/035827 obtained from the application of heat alone. The reduced viscosity attained through heating alone will revert to its original viscosity after the heat has been removed from hydrocarbon waste stream 12 and it has been allowed to cool to ambient temperature. Here, the reduction in viscosity lasts substantially longer than by heating alone. 5 [0041] While the invention has been shown or described in only some of its forms, it should be apparent to those skilled in the art that it is not so limited, but is susceptible to various changes without departing from the scope of the invention. [0042] For example, the centrifuging steps can be effectuated with a three-phase centrifuge, a series of centrifuges, or the like. As another example, slurry fuel 30 can 10 be used for other uses besides for asphalt. Other modifications, such as adding an external source of water to make slurry fuel 30, are to be considered within the scope of the present invention. As another example, the mixers can include a pipeline that enables two or more compounds to combine. WO 2006/039714 PCT/US2005/035827 What is claimed: 1. A method for utilizing a hydrocarbon waste stream having an API gravity varying from about 5 to about 30, the method comprising the steps of: (a) heating a hydrocarbon waste stream to a preselected temperature range of 5 between about 30 °C and about 100 DC in the absence of air to produce a heated hydrocarbon waste stream; (b) mixing the heated hydrocarbon waste stream with a diluent solvent stream to reduce viscosity of the heated hydrocarbon waste stream to a reduced viscosity; 10 (c) centrifuging the heated hydrocarbon waste stream to produce an oil phase stream, an aqueous phase stream, and separated solids stream; and (d) mixing the separated solids stream and water to produce a slurry fuel that has a solids content of at least 50 weight percent. 2. The method of claim 1, wherein the hydrocarbon waste stream is selected from the 15 group consisting of petroleum heavy hydrocarbon waste, tank bottoms, petroleum heavy fractions, bunker fuel, petroleum sludge, refinery waste, and combinations thereof. 3. The method of any of the proceeding claims, wherein at least a portion of the water is supplied by at least a portion of the aqueous phase stream to produce the 20 slurry fuel. 4. The method of any of the proceeding claims, wherein the separated solids stream comprise asphaltenes. 14 WO 2006/039714 PCTYUS2005/035827 5. The method of any of the proceeding claims, wherein the step of mixing the hydrocarbon waste stream with a diluent includes retaining the reduced viscosity for at least seven days. 6. The method of any of the proceeding claims, further including the step of 5 prefiltering the hydrocarbon waste stream prior to the step of heating the hydrocarbon waste stream to remove contaminants from the hydrocarbon waste stream. 7. The method of claim 6, further including the step of adding a filter aid to facilitate separation of the hydrocarbon waste stream and wherein the filter aid has a concentration of less than 1 weight percent. 10 8. The method of claim 7, wherein the filter aid is selected from the group consisting of diatomite, siliceous materials, cellulose materials, and combinations thereof. 9. The method of any of the proceeding claims, wherein the diluent solvent stream is selected from the group consisting of gasoline, naphtha, kerosene, diesel fuel, and combinations thereof. 15 10. The method of any of the proceeding claims, wherein the slurry fuel is used in a process selected from road asphalt production, a combustion process, and a gasification process. 11. The method of any of the proceeding claims, further including the step of adding an asphaltenes dispersing agent selected from the group consisting of toluene, xylene, 20 tetralin, furan, phenol, ethyl benzoate, butaldehyde, acetophenone, cyclohexanone, and combinations thereof to the heated hydrocarbon waste stream to improve the stability of the heated hydrocarbon waste stream, the asphaltenes dispersing agent 15 WO 2006/039714 PCT/US2005/035827 being added so that the asphaltenes dispersing agent has a concentration of about 0.1 weight percent to about 25 weight percent of the heated hydrocarbon waste stream. 12. The method of any of the proceeding claims, further including the step of adding an emulsion breaker additive selected from the group consisting of nonionic 5 surfactants, polyglycols, polyglycol esters, ethoxylated resins, ethoxylated nonylphenols, polyhydric alcohols, sulfuric acid salts, and combinations thereof. 13. The method of claim 12, wherein the emulsion breaker additive has a concentration in a range of about 1 ppm to about 200 ppm. 14. The method of claim 12, wherein the emulsion breaker additive has a 10 concentration in a range of about 5 ppm to about 20 ppm. 15. The method in any of the proceeding claims, further including the step of adding a catalyst selected from the group consisting of molybdenum, iron, cobalt, nickel, vanadium, and combinations thereof to the oil phase stream for use as a fuel, the catalyst being added so that the catalyst has a concentration of less than 1 weight 15 percent. 16. The method of any of the proceeding claims, wherein the hydrocarbon waste stream is heated to a temperature of about 50°C to 90°C. 17. The method of any of the proceeding claims, wherein the step of centrifuging the hydrocarbon waste stream includes utilizing a centrifuge wherein separate oil phase 20 stream, aqueous phase stream, and separated solids stream are collected. 16 WO 2006/039714 PCT/US2005/035827 18. The method of any of the proceeding claims, wherein the separated solids stream are used as an additive for road asphalt. 19. The method of any of the proceeding claims, wherein the reduced viscosity is in a range of about 10 cP to about 1000 cP. 5 20. The method of claim 19, wherein the reduced viscosity is in a range of about 200 cP to about 900 cP. ■ 21. A method for utilizing a waste hydrocarbon stream having an API gravity varying from about 5 to about 30, the comprising the steps of: (a) heating a hydrocarbon waste stream in the temperature range between 35 10 °C and about 100 °C in the absence of air to produce a heated hydrocarbon waste stream; (b) mixing the heated hydrocarbon waste stream with a solvent selected from the group consisting of a diluent solvent stream, a dispersant, an asphaltenes dispersing agent, an emulsion breaker additive, a filter aid, and 15 combinations thereof; (c) centrifuging the heated hydrocarbon waste stream to produce an oil phase stream, an aqueous phase stream, and separated solids stream; (d) mixing the separated solids stream and water to produce a slurry fuel having a solids content at least 50 weight percent; and 20 (e) utilizing the hydrocarbon oil as a fuel in a refinery. 22. The method of claim 21, further including the step of utilizing at least a portion of the hydrocarbon oil as a feedstock for making carbon fiber. 17 WO 2006/039714 PCT/US2005/035827 23. The method of claim 22, wherein the portion of the hydrocarbon oil has a boiling fraction in a range of about 400°C to about 520°C. 24. The method of claim 21, 22 or 23, wherein the hydrocarbon waste stream is selected from the group consisting of petroleum heavy hydrocarbon waste, tank 5 bottom, petroleum heavy fractions, bunker fuel, petroleum sludge, refinery waste, and combinations thereof. 25. The method of claim 21,22,23 or 24, further including the step of prefiltering the hydrocarbon waste stream prior to the step of heating the hydrocarbon waste stream to remove contaminants from the hydrocarbon waste stream. 10 26. The method of claim 21, 22, 23, 24 or 25, wherein the diluent solvent stream is selected from the group consisting of gasoline, naphtha, kerosene, diesel fuel, and combinations thereof. 27. The method of claim 26, wherein the step of adding the diluent solvent stream reduces viscosity of the heated hydrocarbon waste stream to a range of about 10 cP to 15 about 1000 cP. 28. The method of claim 27, wherein the step of adding the diluent solvent stream includes reducing the viscosity of the heated hydrocarbon waste stream for at least seven days. 29. The method of claim 27, wherein the step of adding the diluent solvent stream 20 reduces the viscosity of the heated hydrocarbon waste stream to a range of about 200 cP to about 900 cP. 18 WO 2006/039714 PCT/DS2005/035827 30. The method of claim 21, 22, 23,24, 25, 26, 27, 28 or 29, wherein the asphaltenes dispersing agent is selected from the group consisting of toluene, xylene, tetralrn, firran, phenol, ethyl benzoate, butaldehyde, acetophenone, cyclohexanone, and combinations thereof to the heated hydrocarbon waste stream to improve the stability 5 of the heated hydrocarbon waste stream, the asphaltenes dispersing agent being added so that the asphaltenes dispersing agent has a concentration of about 0.1 weight percent to about 25 weight percent of the heated hydrocarbon waste stream. 31. The method of claim 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, wherein the emulsion breaker additive is selected from the group consisting of nonionic 10 surfactants, polyglycols, polyglycol esters, ethoxylated resins, ethoxylated nonylphenols, polyhydric alcohols, sulfuric acid salts, and combinations thereof. 32. The method of claim 21,22,23,24,25,26,27,28,29,30 or 31, wherein the water comprises at least a portion of the aqueous phase stream to produce the slurry fuel and the slurry fuel is used as an additive for road asphalt. 15 33. An apparatus for utilizing a hydrocarbon waste stream having an API gravity varying from about 5 to about 30, the apparatus comprising: (a) a heater for heating a hydrocarbon waste stream in the temperature range between 35 C and about 100 °C in the absence of air to produce a heated hydrocarbon waste stream; 20 (b) a mixer for mixing the heated hydrocarbon waste stream with a solvent selected from the group consisting of a diluent solvent stream, a dispersant, an asphaltenes dispersing agent, an emulsion breaker additive, a filter aid, and combinations thereof; and 19 WO 2006/039714 PCT/DS2005/035827 (c) a centrifuge for centrifuging the heated hydrocarbon waste stream to produce an oil phase stream, an aqueous phase stream, and separated solids stream. 34. The apparatus of claim 33, further including a mixer for mixing the separated 5 solids stream with at least a portion of the aqueous phase stream to produce a slurry fuel having a solids content at least 50 weight percent 35. The apparatus of claim 33 or 34, wherein the heater, mixer, and the centrifuge are combined in a single three phase centrifuge. 36. The apparatus of claim 33, 34, or 35, further including a prefilter for prefiltering 10 the hydrocarbon waste stream prior to heating the hydrocarbon waste stream to remove contaminants from the hydrocarbon waste stream. 20 The fuel properties of petroleum hydrocarbon waste having an API gravity varying from about 5 to 30 are improved by heating the hydrocarbon to a temperature of about 35 °C to 90 °C and mixing the heated hydrocarbon stream with a suitable solvent to reduce the viscosity of the hydrocarbon, which is then separated by a centrifuge to obtain an aqueous phase stream, an oil phase stream, and a separated solids stream. The oil phase stream has a viscosity range of about 250 centipoise (cP) to about 1000 cP. The oil phase stream is utilized in a refinery, while a slurry fuel is prepared with the separated solids stream and aqueous phase stream as a feedstock for road asphalt, a fuel for a combustor, or a fuel for a gasification process. The oil phase stream is used for fuels and feedstock for making carbon fiber.

Full Text

WO 2006/039714 PCT/US2005/035827
METHOD FOR UTILIZING HYDROCARBON WASTE MATERIALS
AS FUEL AND FEEDSTOCK
BACKGROUND OF THE INVENTION
1. Held of the Invention
5 [0001] The present invention relates to using hydrocarbon waste materials,- more
specifically, heavy petroleum hydrocarbons including petroleum sludge, tank bottoms,
or residue having an API gravity of about five to about thirty into useful feels and
products.
2. Background of the Invention
10 [0002] Oil producers generate significant amounts of petroleum waste materials. For
example, operating companies generate a significant volume of petroleum waste
materials, including thousands of cubic meters of oily wastes annually, much of which
are tank bottoms sludge and various refinery and production wastes. Furthermore,
various amounts of non-leaded hydrocarbon products, waste solvents, and slop oil
15 waste materials are generated. These waste materials are often contaminated by water
and insoluble solids. Some of these sludges contain between fifty to ninety percent
oil. The annual disposal costs for these materials can be a significant operating
expense to operating companies, which is lost. Much of these materials are now
"land-farmed" creating potential environmental problems. In the "USA and elsewhere,
20 such disposal techniques are believed to have led to highly toxic superfund sites.
Furthermore, local regulations are expected to limit or eliminate land farming in the
near future. Therefore, it is important that proper steps are taken to utilize or dispose
of such waste materials.
[0003] Heavy residue, petroleum waste, and sludge materials are formed during
25 production, handling, and processing of the petroleum hydrocarbons. The
transportation and use of the heavy hydrocarbons are difficult because of their high
viscosity and poor stability. At ambient conditions, heavy hydrocarbons, such as a

WO 2006/039714 PCT/US2005/035827
refinery residue, have an API gravity of about thirty or less. These oily materials are
often contaminated with, solid or semi-solid waste materials and water.
[0004] Due to improvements in the refining processes over the past fifty years,
additional lighter products are "being recovered from every barrel of hydrocarbon
5 waste oil. Thus, the residue and heavy materials, such as bunker fuel, being produced
in various refineries are undergoing significant changes in quality including a greater
concentration of asphaltenes. The presence of a larger concentration of asphaltenes in
fuels has a great impact on fuel usage in various applications. Asphaltenes are polar
compounds that tend to agglomerate into very large structures in liquid hydrocarbons.
10 These agglomerates lead to viscosities that are much higher than if the asphaltenes
were not structured. The asphaltene molecule appears to carry a core of
approximately five stacked flat sheets of condensed aromatic rings, one above the
other giving an overall height of sixteen to eighteen Angstroms. The average sheet
diameter appears to range from six to fourteen Angstroms. The molecular weight of
15 petroleum asphaltenes can range from about 1,000 to 50,000. A refinery residue after
it is extracted with a solvent exists in a solid state such that its viscosity cannot be
measured, and one has to heat the material at a sufficiently high temperature (>100°C)
to make this material into a low viscosity material suitable for transport.
[0005] In storage tanks or tankers, fuel sludge, tank bottom, etc. are formed when
20 asphaltenes are separated from the fuel and deposited on the bottom of the tank.
Furthermore, fuel sludges are formed when different fuels including residual fuels are
blended when one of the components contains significant amount of asphaltene. In
hydrocarbon waste upgraded by hydrotreating and hydrocracking processes, the
relatively unreactive portion of the hydrocarbon waste, termed "residue," can be
25 formed, which requires further processing. Refinery wastes, tank bottoms sludge,
waste solvents, slop oil, lube oil waste, and other hydrocarbon waste produced during
refining are environmentally hazardous and can create a disposal problem. In
blending of different hydrocarbon wastes or hydrocarbon waste products,
asphaltene/resin ratio is altered and fuels become unstable as asphaltenes separate and
30 agglomerate. Furthermore, as stated earlier, fuel sludges are formed when different

WO 2006/039714 PCT/DS2005/035827
fuels including residual fuels are blended, especially when one of the components
contains higher amounts of asphaltenes. During transportation, asphaltenes deposit
and clog reservoir pores and pipelines. Utilization of hydrocarbon waste involves
various steps such as storage, transportation, and combustion, partial oxidation or
5 further refining and the like. The presence of asphaltenes can affect each of these
steps.
[0006] U.S. Pat. No. 5,133,781 issued to DeRosa et al. discloses a method of
stabilizing asphaltenes in hydrocarbons by dissolving the asphaltenes in
tetrahydrofuran, phosphochlorinating the asphaltenes, and then reacting the
10 phosphochlorinated-asphaltenes with equimolar amounts of aliphatic or aromatic
alcohols. The 781 Patent stabilizes the asphaltenes for use in bituminous liquids until
well into the refining process.
[0007] Attempts have been made to convert sewage sludge waste into useful fuels.
As an example, in U.S. Patent No. 5,356,540 issued to Khan, a pumpable aqueous
15 slurry of sewage sludge is produced by the step of dewatering the sewage sludge to
produce an aqueous slurry having a solids content of about 10 to 25 wt. %. The
aqueous slurry of sewage sludge is then pretreated to improve its slurrying
characteristics by one or a combination of (a) heating, (b) hydrothermal treatment, and
(c) heating, mixing and shearing the aqueous slurry of sewage sludge. The following
20 materials are then mixed together at a temperature in the range of about ambient to
400° F to produce a pumpable aqueous slurry having a solids content in the range of
about 30 to 65 wt. %: (a) pretreated aqueous slurry of sewage sludge; (b) a nonionic
water-soluble alkoxylated alkylphenol additive; and (c) sewage sludge-containing
material and/or solid carbonaceous fuel-containing material to increase the solids
25 loading. When using the techniques taught by this patent with industrial hydrocarbon
sludge streams, the effects are often limited in duration.
[0008] Introduction into refining, partial oxidation (gasification), or combustion
processes are possible avenues to dispose of petroleum hydrocarbons, such as tank
bottoms sludge or residue. Having 5% by weight or greater asphaltene concentration

WO 2006/039714 PCT/US2005/035827
in asphaltene-rich hydrocarbons, however, tends to cause difficulties in pumping, fuel
injections, atomization, spray and combustion or partial oxidation. Asphaltene rich
particles have a long burning time, which results in larger flame size. Combustion
ignition is delayed for these fuels. la a combustion chamber, unbumed carbon and
5 soot are produced. Other difficulties include excessive wear in piston ring and
cylinder liner; fracture of piston rings, and increased deposits on combustion chamber.
During combustion, the presence of asphaltenes creates non-homogeneous fuel
mixtures that result in a non-uniform spray pattern. Larger fuel particles containing
asphaltenes do not atomize or vaporize contributing to incomplete combustion that
10 leads to deposits and various pollutants being formed in the combustion system.
[0009] A need exists for a method of utilizing petroleum hydrocarbon wastes that will
reduce disposal costs and risks associated with disposal of the hydrocarbon wastes. A
goal is to provide a process that utilizes the hydrocarbon waste as a fuel source in a
process that will not result in deleterious results within the process. A further goal is
15 to provide a process that efficiently utilizes the asphaltenes contained within
hydrocarbon waste streams.
SUMMARY OF THE INVENTION
[0010] The present invention advantageously provides a method of utilizing
petroleum sludge or a hydrocarbon waste stream as a fuel source without resulting in
20 deleterious results as a result of using such fuel source within the process. Costly
pretreatment of the sludge or hydrocarbon waste stream, while acceptable, is not
required in the present invention, which results hi a cost saving.
[0011] In this process, hydrocarbon waste stream is heated and mixed with various
additives at a temperature in a range of about 35° C to 90° C in the absence of air,
25 while being continuously passed through a centrifuge to separate material into various
fractions, namely a separated solids, an aqueous phase, and an oil phase.
[0012] Each of the separated solids fraction are preferably used as a fuel source.
Separated solids fraction is mixed with water to produce a pumpable slurry fuel

WO 2006/039714 PCT/US2005/035827
having a solids content in a range of about 50 to 60 wt. %. The water can be newly
added water from an external source or a portion of aqueous phase or combinations
thereof. Pumpable slurry fuel can be burned as fuel in a gasifier, furnace, boiler,
incinerator, or the hike. Separated solids can also be used as an additive for asphalt.
5 Oil phase is preferably used as a fuel within a refinery. A heavier aromatic portion of
the oil phase can serve as a feedstock for making carbon fiber. The suitable boiling
fraction that can serve as a feedstock for making carbon fiber is the between 400°C
and520°C.
[0013] Fuel properties of hydrocarbon waste stream having an API gravity, varying
10 from about 5 to about 30 are improved by mixing the hydrocarbon waste stream with
a diluent solvent sufficient to reduce the viscosity of the hydrocarbon to a range of
about 250 centipoise (cP) to about 1000 cP. The mixing is preferably performed at a
temperature of about 35°C to 100°C. The waste material is centrifuged, filtered, and
separated into various products or fractions, namely separated solids, aqueous phase,
15 and oil phase. Separated solids contain substantial amounts of asphaltenes. Other
additives can be added to hydrocarbon waste stream as described herein.
[0014] In addition to the method embodiments, the apparatus useful to perform the
methods described herein is also advantageous provided.
BRIEF DESCRIPTION OF THE DRAWINGS
20 [0015] So that the manner in which the features, advantages and objects of the
invention, as well as others which will become apparent, may be understood in more
detail, more particular description of the invention briefly summarized above may be
had by reference to the embodiment thereof which is illustrated in the appended
drawings, which form a part of this specification. It is to be noted, however, that the
25 drawings illustrate only a preferred embodiment of the invention and is therefore not
to be considered limiting of the invention's scope as it can admit to other equally
effective embodiments.

WO 2006/039714

PCT7US2005/035827

[0016] FIG. 1 is a simplified block diagram of a process for utilizing a hydrocarbon
waste stream having an API gravity of about 5 to about 30 as a fuel source according
to an embodiment of the present invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
5 [0017] The present invention advantageously provides a method of utilizing a
petroleum waste stream having an API gravity varying from about 5 to about 30 as a
fuel source. Table I includes an example composition for petroleum waste stream.

Table I
Component Feed wt %, moisture free basis
S 1-7
C 70-87
H 7-10
N 0.1-2
H2O (uncentrifuged) 5-50
Density (API gravity) 5-30
Total Distillate (-524 C) 20-60
% Asphaltenes 10-40
10 [0018] Referring to FIG. 1, as an embodiment of the present invention, the method
preferably includes the step of heating hydrocarbon waste stream 12 to a preferable
preselected temperature range of between about 30 °C and about 100 °C in the
absence of air. This step of heating lowers viscosity of hydrocarbon waste stream 12
creating warmed hydrocarbon waste stream 16. The step of heating hydrocarbon
15 waste stream 12 more preferably includes heating hydrocarbon waste stream 12 to a
heated temperature within a range of about 50°C to about 100°C.
[0019] After being heated, warmed hydrocarbon waste stream 16 is then mixed with a
diluent solvent stream 18a to reduce a viscosity of warmed hydrocarbon waste stream
16 to a reduced viscosity. Once diluent solvent stream 18a has been added, warmed
20 hydrocarbon waste stream 16 is then centrifuged to produce oil phase stream 32,
aqueous phase stream 20, and separated solids stream 28, jointly called produced

WO 2006/039714 PCTYUS2005/035827
streams or fractions. Bach of these produced streams can be collected separately.
Separated solids stream 28 contains substantial amounts of asphaltenes. Separated
solids stream 28 and water are combined to produce a slurry fuel 30. The water can
be newly added water from an external source 24 or a portion of aqueous phase 22 or
5 combinations thereof. Slurry fuel 30 preferably has a solids content of at least 50
weight percent. Slurry fuel 30 is preferably used to produce asphalt or as fuel for a
gasification process. Slurry fuel 30 more preferably contains about 50 — 60 weight
percent solids. Oil phase stream 32 preferably is used as a fuel source in refineries.
At least a portion of oil phase 34 is preferably recycled as feed to the step of
10 centrifuging warmed hydrocarbon waste stream 16. A heavier aromatic portion of the
oil phase stream 32 can serve as a feedstock for making carbon fiber. The suitable
boiling fraction of the portion of the oil phase stream 32 that can serve as a feedstock
for making carbon fiber is the between 400°C and 520°C.
[0020] The amount of diluent solvent stream 18a added to warmed hydrocarbon waste
15 stream 16 can be chosen to reach a preselected viscosity of oil phase stream 32, or a .
preselected concentration of asphaltenes in warmed hydrocarbon waste stream 16,
based on the type of hydrocarbon waste stream 16. Alternately, the amount of diluent
solvent 18a can be determined by optimizing these two factors. Amounts preferably
in the range of about 0.005 to about 8 weight percent of diluent solvent stream 18a in
20 warmed hydrocarbon waste stream 16 are preferred. This advantageously provides
desirable levels of stability of oil phase stream 32. More preferably, the range is
between about 0.5 to about 5.0 weight of diluent solvent stream 18a in warmedhydrocarbon waste stream 16. Even more preferably, (he range is between about 1.0
to about 3.0 weight percent. With a warmed hydrocarbon waste stream 16 containing
25 a large concentration of asphaltenes, the concentration of diluent solvent stream 18a is
preferably up to 25 weight percent. ■
[0021] Once diluent solvent stream 18ais added to wanned hydrocarbon waste stream
16, a viscosity of warmed hydrocarbon waste stream 16 is reduced. The desired or
target viscosity of the oil phase stream 32 will depend on the ultimate use of oil phase
30 stream 32, keeping in mind that a viscosity within the preferably range of
about 10 to

"WO 2006/039714 PCT/US2005/035827
about 1000 centipoise (cP), and more preferably about 200 to about 900 cP, is
preferred at 25 to 70 degree C for most transportation and utilization purposes.
[0022] The viscosity of heavy hydrocarbon stream having an API gravity that ranges
from about 5 to about 30 is significantly reduced by exposing the hydrocarbon stream
5 to a diluent solvent stream 18a, followed by separation of the produced streams as
discussed above. The combined heating and mixing of warmed hydrocarbon
waste stream 16 with the diluent solvent stream 18a produces a hydrocarbon
fuel comprising oil phase stream 32 that has a viscosity level that can be
conveniently transported through pipelines without deposit formation. Preferred
10 pipeline viscosities range from about 400 cP to about 1000 cP.
[0023] Examples of preferred diluents for transportation of hydrocarbon waste oil or
refinery waste or residue to a refinery or a utilization site are lighter components of
petroleum, such as gasoline, naphtha, diesel fuel, and mixtures thereof, is general, the
amount of viscosity reducing additive, or diluent solvent stream 18 a, is from about 5
15 weight percentage to about 50 weight percentage, and more preferably about 20
weight percentage to about 35 weight percentage, of warmed hydrocarbon waste
stream 16. About 20 weight percentage to 35 weight percentage of diesel, gasoline
and naphtha is typically sufficient to reduce the viscosity of warmed hydrocarbon
waste stream 16 to less than about 1000 cP to less than about 600 cP at 35 °C. In
20 preferred embodiments of the present invention, hydrocarbon waste stream 12 is
preferably selected from the group consisting of petroleum heavy hydrocarbon waste,
tank bottom, petroleum heavy fractions, bunker fuel, petroleum sludge, refinery waste,
and combinations thereof.
[0024] Foreign materials or contaminants, such as sand, dirt, and the like, can exist in
25 hydrocarbon waste stream 12. The methods described herein optionally include the
step of prefiltering hydrocarbon waste stream 12 prior to the step of heating
hydrocarbon waste stream 12 to remove contaminants from hydrocarbon waste stream
12. Alternately, prefiltering can occur prior to centrifugation.

WO 2006/039714 PCT/US2005y035827
[0025] la preferred embodiments of the present invention, diluent solvent stream 18a
is preferably selected from the group consisting of gasoline, naphtha, kerosene, diesel
fuel, and combinations thereof. Other suitable diluent solvents 18a will be apparent to
those of skill hi the art and are to be considered within the scope of the present
5 invention.
[0026] Slurry fuel 30 produced by mixing separated solids stream 28 with at least a
portion of aqueous phase 22 can be used to produce road asphalt. Slurry fuel 30 can
also be made by adding an external source of water 24 to separated solids stream 28 or
a combination of an external water source 24 and at least a portion, of aqueous phase
10 22. An advantage of using aqueous phase stream 20 is that it reduces the disposal
costs associated with disposing of aqueous phase stream 20. Slurry fuel 30 can also
be used in gasification processes or combustion processes as a fuel. Separated solids
stream 28 can be used as an additive in road asphalt.
[0027] To improve the stability of hydrocarbon waste stream 12, an asphaltenes
15 dispersing agent 18b is preferably added to warmed hydrocarbon waste stream 16.
In preferred embodiments of the present invention that include adding an asphaltenes
dispersing agent 18b to warmed hydrocarbon waste stream 16, asphaltenes
dispersing agent 18b is preferably selected from the group consisting of toluene,
xylene, tetralin, furan, phenol, ethyl benzoate, butaldehyde, acetophenone,
20 cyclohexanone, and combinations thereof, Asphaltenes dispersing agent 18b is
preferably added so that asphaltenes dispersing agent 18b has a concentration of about
0.1 weight percent to about 25 weight percent of warmed hydrocarbon waste stream
16 with dispersing agent, In addition to improving the stability of warmed
hydrocarbon waste stream 16, asphaltenes dispersing agent 18b also advantageously
25 enhances the solubility of the asphaltenes, which enhances the yield of oil phase
stream 32 that is recoverable from warmed hydrocarbon waste stream 16.
Asphaltenes dispersing agent 18b is preferably added to warmed hydrocarbon waste
stream 16 using conventional methods at any time during or after centrifugation of
warmed hydrocarbon waste stream 16, depending on the nature of the waste.

WO 2006/039714 PCT/US2005/035827
[0028] In preferred embodiments of the present invention, the invention includes the
step of adding an emulsion breaker additive 18c to warmed hydrocarbon waste stream
16 so that emulsion breaker additive 18c has a concentration of less than 100 ppm.
Chemical emulsion breaker additives 18c disrupt the interfacial tensions between oil
5 and water and allow droplets to coalesce and separate. Suitable emulsion breaker
additives 18c for the present invention preferably include nonionic surfactants,
polyglycols, polyglycol esters, ethoxylated resins, ethoxylated nonylphenols,
polyhydric alcohols] sulfuric acid salts', |and combinations thereof. A preferable
nonionic surfactant preferably includes a polycrylamide polymer. If oil phase stream
10 32 is going to subsequently be used in oil field production, emulsion breaker additive
18c preferably has a concentration in a range of about 1 ppm to about 200 ppm. If oil
phase stream 32 is going to subsequently be used in refinery desalting processes,
emulsion breaker additive 18c preferably has a concentration in a range of about 5
ppm to about 20 ppm.
15 [0029] To facilitate separation of warmed hydrocarbon waste stream 16, a filter aid
18d can be added to warmed hydrocarbon waste stream 16 to aid in the separation of
oil phase stream 32 and aqueous phase stream 20. Once added, filter aid 18d
preferably has a concentration of less than 1 weight percent of warmed hydrocarbon
waste stream 16. Filter aid 18d is preferably selected from the group consisting of
20 diatomite, siliceous materials, cellulose materials, and combinations thereof.
Commercial filter aids 18d are available from companies, such as Aderco Chemical
Products Inc. headquartered in Quebec.
[0030] The extent of fuel properties improvements made to hydrocarbon waste stream
12 can be optimized based on the time/duration/type of additive and the nature and
25 type of additive as well as the degree of desired separation. The effect of viscosity
reduction is retained for at least seven days.
[0031] As another embodiment of the present invention, a method for utilizing a
hydrocarbon waste stream having an API gravity varying from about 5 to about 30 is
advantageously provided. In this embodiment, hydrocarbon waste stream 12 is heated

10

WO 2006/039714 PCT/US2005/035827
preferably in a temperature range of about 35° C to about 100 DC in the absence of air,
and more preferably in a range of about 50°C to about 90°C.
[0032] Warmed hydrocarbon waste stream 16 with then mixed with a solvent 18 that
is preferably selected from the group consisting of diluent solvent stream 18 a,
5 asphaltenes dispersing agent 18b, emulsion breaker additive 18c, filter aid 18d, and
combinations thereof. Warmed hydrocarbon waste stream 16 is then preferably
centrifuged to produce oil phase stream 32, aqueous phase stream 20, and separated
solids stream 28.
[0033] Separated solids stream 28 and water 24 are mixed to form a slurry fuel 30 that
10 has a solids content at least 50 wt%. The water can be newly added water from an
external source 24 or a portion of aqueous phase 22 or combinations thereof. Oil
phase stream 32 can be used as a fuel in a refinery. Slurry fuel 30 can be used as an
additive for asphalt. Slurry fuel 30 can also be used as fuel in combustion and
gasification processes. At least a portion of oil phase 34 can be recycled within the
15 • process as a feed for the step of cenrrifuging warmed hydrocarbon waste stream 16.
[0034] In addition to the method embodiments of the present invention, an apparatus
embodiment is also advantageously provided, as shown in Fig. 1. In this embodiment,
the apparatus 10 preferably includes a heater 14, a centrifuge 20, and a mixer 42.
Heater 14 is preferably used for heating hydrocarbon waste stream 12 in the
20 temperature range between about 35°C and about 100°C in the absence of air. Mixer
42 is preferably used for mixing warmed hydrocarbon waste stream 16 with solvent
18 that is preferably selected from the group consisting of diluent solvent stream 18a,
asphaltenes dispersing agent 18b, emulsion breaker additive 18c, a filter aid 18d, and
combinations thereof. Centrifuge 20 is preferably used for centrifugmg warmed
25 hydrocarbon waste stream 16 to produce oil phase stream 32, aqueous phase stream
20, and separated solids stream 28.
[0035] An additional mixer 44 can be provided for mixing separated solids stream 28
with at least a portion of aqueous phase 22 to produce slurry fuel 30 having a solids

11

WO 2006/039714 PCTYUS2005/035827
content at least 50 weight percent, and more preferably in the range of about 50 to
about 60 weight percent.
[0036] Heater 14, first mixer 42, and centrifuge 20 can be combined in a single three
phase centrifuge 20. Other suitable types of equipment that can function as heater 14,
5 first mixer 42, second mixer 44, and centrifuge 20 will be known to those of skill in
the art and are to be considered within the scope of the present invention. For
example, embodiments including a mixer-can include any device capable of mixing
two or more compounds together.
[0037] In preferred embodiments of the present invention, the present invention
10 preferably includes a prefilter for prefiltering hydrocarbon waste stream 12 prior to
heating hydrocarbon waste stream 12 to remove contaminants from hydrocarbon
waste stream 12.
[0038] Each of the fractions collected from the step of centrifuging warmed
hydrocarbon waste stream 16 can be used in subsequent processes. For example, a
15 catalyst 40 preferably in a reactor 36 can be added to oil phase stream 32 to produce a
fuel that can be used within refineries. Catalyst 40 is preferably selected from the
group consisting of molybdenum, iron, cobalt, nickel, vanadium, and combinations
thereof. The type of catalyst 40 that is added will depend upon the type of process in
which the fuel will be used. Once added, catalyst 40 preferably has a concentration of
20 less than 1 weight percent of the produced fuel.
[0039] As an advantage of the present invention, the processes described herein can
be used with a variety of hydrocarbon waste streams and can be controlled based upon
the ultimate final use of oil phase stream 32 and slurry fuel 30. As another advantage,
the processes described herein convert substantially all of hydrocarbon waste stream
25 12 into useful produced streams. As a result, disposal costs normally associated with
disposal of hydrocarbon waste stream 12 are virtually ehminated.
[0040] Another advantage of the present invention is that the reduction of viscosity of
hydrocarbon waste stream 12 lasts substantially longer than the reduction of viscosity

12

WO 2006/039714 PCT/PS2005/035827
obtained from the application of heat alone. The reduced viscosity attained through
heating alone will revert to its original viscosity after the heat has been removed from
hydrocarbon waste stream 12 and it has been allowed to cool to ambient temperature.
Here, the reduction in viscosity lasts substantially longer than by heating alone.
5 [0041] While the invention has been shown or described in only some of its forms, it
should be apparent to those skilled in the art that it is not so limited, but is susceptible
to various changes without departing from the scope of the invention.
[0042] For example, the centrifuging steps can be effectuated with a three-phase
centrifuge, a series of centrifuges, or the like. As another example, slurry fuel 30 can
10 be used for other uses besides for asphalt. Other modifications, such as adding an
external source of water to make slurry fuel 30, are to be considered within the scope
of the present invention. As another example, the mixers can include a pipeline that
enables two or more compounds to combine.

WO 2006/039714 PCT/US2005/035827
What is claimed:
1. A method for utilizing a hydrocarbon waste stream having an API gravity varying
from about 5 to about 30, the method comprising the steps of:
(a) heating a hydrocarbon waste stream to a preselected temperature range of
5 between about 30 °C and about 100 DC in the absence of air to produce a
heated hydrocarbon waste stream;
(b) mixing the heated hydrocarbon waste stream with a diluent solvent stream
to reduce viscosity of the heated hydrocarbon waste stream to a reduced
viscosity;
10 (c) centrifuging the heated hydrocarbon waste stream to produce an oil phase
stream, an aqueous phase stream, and separated solids stream; and
(d) mixing the separated solids stream and water to produce a slurry fuel that
has a solids content of at least 50 weight percent.
2. The method of claim 1, wherein the hydrocarbon waste stream is selected from the
15 group consisting of petroleum heavy hydrocarbon waste, tank bottoms, petroleum
heavy fractions, bunker fuel, petroleum sludge, refinery waste, and combinations
thereof.
3. The method of any of the proceeding claims, wherein at least a portion of the
water is supplied by at least a portion of the aqueous phase stream to produce the
20 slurry fuel.
4. The method of any of the proceeding claims, wherein the separated solids stream
comprise asphaltenes.
14

WO 2006/039714 PCTYUS2005/035827
5. The method of any of the proceeding claims, wherein the step of mixing the
hydrocarbon waste stream with a diluent includes retaining the reduced viscosity for at
least seven days.
6. The method of any of the proceeding claims, further including the step of
5 prefiltering the hydrocarbon waste stream prior to the step of heating the hydrocarbon
waste stream to remove contaminants from the hydrocarbon waste stream.
7. The method of claim 6, further including the step of adding a filter aid to facilitate
separation of the hydrocarbon waste stream and wherein the filter aid has a
concentration of less than 1 weight percent.
10 8. The method of claim 7, wherein the filter aid is selected from the group consisting
of diatomite, siliceous materials, cellulose materials, and combinations thereof.
9. The method of any of the proceeding claims, wherein the diluent solvent stream is
selected from the group consisting of gasoline, naphtha, kerosene, diesel fuel, and
combinations thereof.
15 10. The method of any of the proceeding claims, wherein the slurry fuel is used in a
process selected from road asphalt production, a combustion process, and a
gasification process.
11. The method of any of the proceeding claims, further including the step of adding
an asphaltenes dispersing agent selected from the group consisting of toluene, xylene,
20 tetralin, furan, phenol, ethyl benzoate, butaldehyde, acetophenone, cyclohexanone,
and combinations thereof to the heated hydrocarbon waste stream to improve the
stability of the heated hydrocarbon waste stream, the asphaltenes dispersing agent

15

WO 2006/039714 PCT/US2005/035827
being added so that the asphaltenes dispersing agent has a concentration of about 0.1
weight percent to about 25 weight percent of the heated hydrocarbon waste stream.
12. The method of any of the proceeding claims, further including the step of adding
an emulsion breaker additive selected from the group consisting of nonionic
5 surfactants, polyglycols, polyglycol esters, ethoxylated resins, ethoxylated
nonylphenols, polyhydric alcohols, sulfuric acid salts, and combinations thereof.
13. The method of claim 12, wherein the emulsion breaker additive has a
concentration in a range of about 1 ppm to about 200 ppm.
14. The method of claim 12, wherein the emulsion breaker additive has a
10 concentration in a range of about 5 ppm to about 20 ppm.
15. The method in any of the proceeding claims, further including the step of adding a
catalyst selected from the group consisting of molybdenum, iron, cobalt, nickel,
vanadium, and combinations thereof to the oil phase stream for use as a fuel, the
catalyst being added so that the catalyst has a concentration of less than 1 weight
15 percent.
16. The method of any of the proceeding claims, wherein the hydrocarbon waste
stream is heated to a temperature of about 50°C to 90°C.
17. The method of any of the proceeding claims, wherein the step of centrifuging the
hydrocarbon waste stream includes utilizing a centrifuge wherein separate oil phase
20 stream, aqueous phase stream, and separated solids stream are collected.
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18. The method of any of the proceeding claims, wherein the separated solids stream
are used as an additive for road asphalt.
19. The method of any of the proceeding claims, wherein the reduced viscosity is in a
range of about 10 cP to about 1000 cP.
5 20. The method of claim 19, wherein the reduced viscosity is in a range of about 200
cP to about 900 cP.
■ 21. A method for utilizing a waste hydrocarbon stream having an API gravity varying
from about 5 to about 30, the comprising the steps of:
(a) heating a hydrocarbon waste stream in the temperature range between 35
10 °C and about 100 °C in the absence of air to produce a heated hydrocarbon
waste stream;
(b) mixing the heated hydrocarbon waste stream with a solvent selected from
the group consisting of a diluent solvent stream, a dispersant, an
asphaltenes dispersing agent, an emulsion breaker additive, a filter aid, and
15 combinations thereof;
(c) centrifuging the heated hydrocarbon waste stream to produce an oil phase
stream, an aqueous phase stream, and separated solids stream;
(d) mixing the separated solids stream and water to produce a slurry fuel
having a solids content at least 50 weight percent; and
20 (e) utilizing the hydrocarbon oil as a fuel in a refinery.
22. The method of claim 21, further including the step of utilizing at least a portion of
the hydrocarbon oil as a feedstock for making carbon fiber.
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23. The method of claim 22, wherein the portion of the hydrocarbon oil has a boiling
fraction in a range of about 400°C to about 520°C.
24. The method of claim 21, 22 or 23, wherein the hydrocarbon waste stream is
selected from the group consisting of petroleum heavy hydrocarbon waste, tank
5 bottom, petroleum heavy fractions, bunker fuel, petroleum sludge, refinery waste, and
combinations thereof.
25. The method of claim 21,22,23 or 24, further including the step of prefiltering the
hydrocarbon waste stream prior to the step of heating the hydrocarbon waste stream to
remove contaminants from the hydrocarbon waste stream.
10 26. The method of claim 21, 22, 23, 24 or 25, wherein the diluent solvent stream is
selected from the group consisting of gasoline, naphtha, kerosene, diesel fuel, and
combinations thereof.
27. The method of claim 26, wherein the step of adding the diluent solvent stream
reduces viscosity of the heated hydrocarbon waste stream to a range of about 10 cP to
15 about 1000 cP.
28. The method of claim 27, wherein the step of adding the diluent solvent stream
includes reducing the viscosity of the heated hydrocarbon waste stream for at least
seven days.
29. The method of claim 27, wherein the step of adding the diluent solvent stream
20 reduces the viscosity of the heated hydrocarbon waste stream to a range of about 200
cP to about 900 cP.
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30. The method of claim 21, 22, 23,24, 25, 26, 27, 28 or 29, wherein the asphaltenes
dispersing agent is selected from the group consisting of toluene, xylene, tetralrn,
firran, phenol, ethyl benzoate, butaldehyde, acetophenone, cyclohexanone, and
combinations thereof to the heated hydrocarbon waste stream to improve the stability
5 of the heated hydrocarbon waste stream, the asphaltenes dispersing agent being added
so that the asphaltenes dispersing agent has a concentration of about 0.1 weight
percent to about 25 weight percent of the heated hydrocarbon waste stream.
31. The method of claim 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30, wherein the
emulsion breaker additive is selected from the group consisting of nonionic
10 surfactants, polyglycols, polyglycol esters, ethoxylated resins, ethoxylated
nonylphenols, polyhydric alcohols, sulfuric acid salts, and combinations thereof.
32. The method of claim 21,22,23,24,25,26,27,28,29,30 or 31, wherein the water
comprises at least a portion of the aqueous phase stream to produce the slurry fuel and
the slurry fuel is used as an additive for road asphalt.
15 33. An apparatus for utilizing a hydrocarbon waste stream having an API gravity
varying from about 5 to about 30, the apparatus comprising:
(a) a heater for heating a hydrocarbon waste stream in the temperature range
between 35 C and about 100 °C in the absence of air to produce a heated
hydrocarbon waste stream;
20 (b) a mixer for mixing the heated hydrocarbon waste stream with a solvent
selected from the group consisting of a diluent solvent stream, a dispersant,
an asphaltenes dispersing agent, an emulsion breaker additive, a filter aid,
and combinations thereof; and

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(c) a centrifuge for centrifuging the heated hydrocarbon waste stream to
produce an oil phase stream, an aqueous phase stream, and separated solids
stream.
34. The apparatus of claim 33, further including a mixer for mixing the separated
5 solids stream with at least a portion of the aqueous phase stream to produce a slurry
fuel having a solids content at least 50 weight percent
35. The apparatus of claim 33 or 34, wherein the heater, mixer, and the centrifuge are
combined in a single three phase centrifuge.
36. The apparatus of claim 33, 34, or 35, further including a prefilter for prefiltering
10 the hydrocarbon waste stream prior to heating the hydrocarbon waste stream to
remove contaminants from the hydrocarbon waste stream.
20

The fuel properties of petroleum hydrocarbon waste having an API gravity varying from about 5 to 30 are improved
by heating the hydrocarbon to a temperature of about 35 °C to 90 °C and mixing the heated hydrocarbon stream with a suitable
solvent to reduce the viscosity of the hydrocarbon, which is then separated by a centrifuge to obtain an aqueous phase stream, an oil
phase stream, and a separated solids stream. The oil phase stream has a viscosity range of about 250 centipoise (cP) to about 1000
cP. The oil phase stream is utilized in a refinery, while a slurry fuel is prepared with the separated solids stream and aqueous phase
stream as a feedstock for road asphalt, a fuel for a combustor, or a fuel for a gasification process. The oil phase stream is used for
fuels and feedstock for making carbon fiber.

A METHOD FOR UTILIZING HYDROCARBON WASTE STREAM

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