# Patent

## Title
Catalytic method to upgrade oil

## Abstract

A method to upgrade oil wherein an oil containing material is heated with a catalyst in a turbulent environment of less than about 1 volume percent oxygen to produce a vapor phase comprising an upgraded oil. Also disclosed is a thermal desorption process in which an oil contaminated substrate is contacted with an acidic reagent to form a peptizate, and the peptizate is mixed with a combustion effluent gas under turbulent conditions at a temperature above 200° C. to form the catalyst for the oil upgrading method.

## Background
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation of copending U.S. Ser. No. 14/167,401, filed Jan. 29, 2014, which is a continuation of U.S. Ser. No. 13/740,402, filed Jan. 14, 2013, now U.S. Pat. No. 8,641,895, which is a division of U.S. Ser. No. 13/180,379, filed Jul. 11, 2011, now U.S. Pat. No. 8,356,678, which claims priority benefit to U.S. Provisional Application No. 61/408,494, filed Oct. 29, 2010, which are hereby incorporated by reference herein.


FIELD OF THE INVENTION
This disclosure relates to the recovery of oil from solid substrates, to the upgrading of oil in a heterogeneous chemical-thermal desorption system and also to the catalytic upgrading of oil using the treated solid substrates.
The composition of many oil-based drilling muds typically includes the following compounds: (1) bentonite; (2) barite; (3) kerosene, diesel or other oil; (4) polymers; (5) sodium, calcium and potassium chlorides; (6) lime; and (7) water (invert emulsion). The inverse emulsion generally uses more oil than water. As used herein, the term “oil-based mud” also includes synthetic muds that are sometimes classified separately even though they contain appreciable amounts of hydrocarbons.
Conventional oil based drilling fluids may use oil containing as much as 30% aromatics or more, such as, kerosene, diesel or refined Group I or Group II base stocks, whereas synthetic drilling fluids may employ a hydrocarbon base stock with a higher viscosity (KV40 and/or KV100), a higher viscosity index (VI), a lower pour point, a lower specific gravity, a higher flash point and a lower content of functional groups such as hydroxide, aryls, substituted aryls, halogens, alkoxys, carboxylates, esters, acrylates, oxygen, nitrogen, carboxyl, and the like. On the other hand, Group III or Group IV (polyalphaolefins or PAO) base stocks can have a viscosity index of 120 or more, a kinematic viscosity of 3 to 3000 cSt at 100° C., a pour point of −20° C. or less, specific gravity less than 0.86 and a flash point of 200° C. or more.
In general, higher quality oils have lower aromatics and sulfur, and higher saturates, viscosity and viscosity index. Aromatics content is important in drilling applications since oil with a high aromatic content as reflected by a low aniline point can cause elastomers used in O-rings and gaskets to swell and fail. The use of higher quality oils in drilling fluids may also allow the drilling fluid to perform under more severe conditions, to last longer, to reduce wear on the drilling equipment, to use less energy, etc.
The physical nature of the oil based drill cuttings (OBDC) complicates the recovery of oil. Numerous attempts have been tried to recover or remove a high quality oil from the drill cuttings with limited success. For example, the industry has had a long-felt need to address one or more of the following problems in the prior art OBDC treatment processes: the quantity of oil recovered may be very low and/or the residual oil remaining in the solids too high; the process or processing equipment may require excessive amounts of energy, require a long treatment time, require large equipment not easily transported to a processing site, require excessive capital for expensive equipment, or entail excessive risk of explosion or other hazards; or the treated drill cuttings may have a pH less than 6 or more than 8, i.e., the drill cuttings may be too acidic or especially too alkaline for environmental disposal; or the quality of the oil obtained may not be suitable for re-use in drilling muds, especially synthetic grade muds requiring one or more of a higher flash point, viscosity and/or VI, and a lower pour point, specific gravity, aromatics content and/or functional group content, relative to the oil typically present in and/or recovered from an OBDC treatment process.
There exists a need for efficient ways to obtain high quality oil from solids such as OBDC while removing sufficient oil from the solids for environmental disposal.
SUMMARY OF THE INVENTION
The present disclosure is directed to a method and apparatus for processing a substrate comprising oil bound to a sorbent material, and in a particular embodiment, to the efficient recovery of high quality oil from oil based drill cuttings (OBDC) from drilling of oil and gas wells.
In an embodiment, a reclaimed oil obtained by one or more embodiments of a method according to the present disclosure comprises, relative to the oil in the bound liquid in the substrate, a lower aromatic content, improved rheological properties, improved handling properties, or a combination thereof, e.g., one or more of: a low total BTEX content as determined according to US EPA 8260, a high aniline point, a high flash point, a low viscosity as determined according to ASTM-D88, a low pour point, a low specific gravity, and a low functional group content.
In an embodiment, a method comprises processing a substrate comprising liquid bound on a solid sorbent material, wherein the liquid comprises oil or a mixture of oil and water, wherein the bound liquid comprises less than about 35 wt % of the substrate. The method comprises (a) peptizing a substrate with an acidic reagent under shear to obtain a peptizate having increased surface area; (b) mixing the peptizate with a combustion effluent gas under turbulent conditions in a thermal desorption zone to heat the peptizate and desorb at least a portion of the oil from the sorbent material; and (c) separating the mixture into a dilute phase and a dense phase, wherein the dilute phase comprises oil vapor. In an embodiment, the peptizing occurs at a temperature between about 70° C. and about 105° C., preferably up to about 100° C.
In an embodiment, the combustion effluent gas comprises less than 1 vol % oxygen, preferably a fuel rich, oxygen lean combustion effluent, and is introduced into the thermal desorption zone at a temperature greater than 300° C., preferably greater than 500° C.
In an embodiment, the sorbent material in the dense phase, i.e., the recovered solids stream has an oil content less than the oil content of the sorbent material in the substrate, preferably less than about 3 wt %, more preferably less than about 2 wt %, and especially less than about 1 wt %, based on the weight of the recovered solids. In an embodiment, the peptizate and/or the recovered solids comprise a pH between 6 and 8.
Also disclosed is an apparatus comprising a substrate feed zone to supply a charge of the substrate defined above to a peptizing zone. In an embodiment, an acid feed system is provided to supply an acid reagent to the peptizing zone. In an embodiment, the peptizing zone comprises one or more agitators to impart shear into the peptizing zone to produce a peptizate. In an embodiment, a transfer zone is provided to supply the peptizate from the peptizing zone to the thermal desorption zone. In an embodiment, a burner is disposed in fluid communication with the thermal desorption zone to supply a combustion effluent gas comprising less than 1 vol % oxygen to the thermal desorption zone at a temperature greater than 300° C. In an embodiment, the thermal desorption zone comprises one or more agitators to promote vapor-solid mixing. In an embodiment, a solids disengagement zone is provided in fluid communication between the thermal desorption zone and a vapor recovery system. In an embodiment, a solids outlet from a housing for the thermal desorption zone is provided adjacent the solids disengagement zone. In an embodiment, the method comprises further purification of the reclaimed oil.
Also disclosed is a transportable apparatus, comprising a feed hopper to supply a charge of the substrate defined above to a peptizer comprising a first fixed housing and one or more agitators. In an embodiment, an acid feed system is provided to supply an acid reagent to react with the substrate in the peptizer and form a peptizate. In an embodiment, a transfer zone is provided to supply the peptizate from the peptizer to an inlet end of a thermal desorber comprising a second fixed housing and one or more agitators, wherein the transfer zone provides a seal to fluidly isolate the peptizer from the thermal desorber. In an embodiment, a burner is provided in fluid communication with the thermal desorber to supply a combustion effluent gas comprising less than 1 vol % oxygen at a temperature greater than 300° C. at the inlet end. In an embodiment, the thermal desorber comprises an agitator to create turbulence and promote mixing and heat transfer. In an embodiment, a solids disengagement zone is provided at an outlet end of the thermal desorber opposite the inlet end for co-current operation to separate a dilute phase from a dense phase. In an embodiment, the apparatus also includes a vapor outlet and a solids outlet from the solids disengagement zone. In an embodiment, the apparatus includes a transportable platform on which the feed hopper, acid feed system, peptizer, burner, and thermal desorber are mounted, which may optionally be wheeled, wherein the mounted first platform has an overall width of less than 2.6 meters (102 inches), an overall length of less than 13.7 meters (45 feet) and an overall height of less than 4.1 meters (13.5 feet). In embodiments, a vapor recovery system is further provided in fluid communication with the vapor outlet to receive the dilute phase, wherein the vapor recovery system comprises at least one solids separator to remove entrained fines, at least one condenser to recover liquid and a gravity separator to obtain oil and water streams, wherein the vapor recovery system is mounted on the transportable platform with the thermal desorber, on another transportable platform or a combination thereof.
Also disclosed is a method, comprising heating an oil containing material with a catalyst in a turbulent environment comprising less than about 1 volume percent oxygen within a reactor at a temperature, pressure, and for a period of time sufficient to produce a vapor phase at an exit of the reactor comprising an upgraded oil. In an embodiment, the catalyst comprises particulates recovered from a thermal desorption process in which an oil contaminated substrate has been contacted with an acidic reagent to form a peptizate, and the peptizate is mixed with a combustion effluent gas under turbulent conditions at a temperature above 200° C. to form a light phase comprising desorbed oil and a dense phase from which the catalyst is recovered.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a block diagram of an embodiment of the method disclosed herein.
FIG. 2 is a schematic diagram of a chemical-direct thermal desorption apparatus for the upgrading, removal and recovery of oil from oil-based drill cuttings according to an embodiment;
FIG. 3 shows a perspective view of a peptizer according to one embodiment;
FIG. 4 schematically shows the generally longitudinal flow pattern inside the peptizer of FIG. 3;
FIG. 5 shows the rotation of the shafts and the transverse flow patterns inside the peptizer of FIGS. 3 and 4;
FIG. 6 shows a partial cut-away view of a thermal desorber according to an embodiment;
FIG. 7 shows a longitudinal sectional view in elevation of the thermal desorber of FIG. 6;
FIG. 8 is a sectional view showing the agitator paddles in the thermal desorber of FIG. 7 as seen along the lines 8-8;
FIG. 9 is a sectional view showing the agitator supports in the thermal desorber of FIG. 7 as seen along lines 9-9;
FIG. 10 is a schematic overview of a vapor recovery system according to one embodiment;
FIG. 11 is a schematic side elevation of a first transportable unit configured for operation according to an embodiment;
FIG. 12 is a schematic side elevation of a second transportable unit configured for operation according to an embodiment; and
FIG. 13 is a schematic plan view of the first and second transportable units of FIGS. 11-12 configured for transport according to an embodiment.



DETAILED DESCRIPTION
The present disclosure is directed to a method and apparatus for processing a substrate containing oil to upgrade and/or recover the oil therein, in particular, the treatment of oil based drill cuttings (OBDC) from the drilling of oil and gas wells. The instant disclosure is also directed to the treatment of oil based drill cuttings for environmental disposal. Although the skilled person will appreciate the method and apparatus can be used to treat other substrates, especially oil-containing substrates having a peptizable matrix component such as acid-reactive clays or minerals wherein the oil is bound to a solid sorbent material, the following description refers to OBDC as a nonlimiting example for illustrative purposes.
The process provides fast and efficient processing of OBDC which can be achieved with relatively small peptizing, combustion, desorption, solids recovery, vapor recovery and/or oil recovery process units and short residence times. The total processing time for the solids is on the order of minutes, for example. In an embodiment, the processing equipment can be transportable, e.g., skid-mounted or trailer-mounted, for transportation to the drilling site or other on-site processing location. The process provides in one embodiment a relatively high oil recovery, e.g., 50, 60, 70, 75 or even 80 percent or more of the oil in the OBDC or other substrate. Furthermore, in a specific embodiment, the recovered oil may surprisingly have improved properties relative to the oil in the OBDC, e.g., a higher viscosity and/or lower aromatic hydrocarbon concentration that of the oil present in the substrate.
In an embodiment, the oil in the bound liquid in the substrate comprises more than 2 wt % or more than 1 wt % aromatic hydrocarbons, by weight of the oil in the OBDC, and may contain as much as 20 wt %, 25 wt %, 30 wt % or more aromatic hydrocarbons, by weight of the oil in the OBDC, whereas the recovered oil comprises less aromatic hydrocarbons, preferably less than 2 wt % or more preferably less than 1 wt % total BTEX (benzene-toluene-ethlylbenzene-xylene) aromatic hydrocarbons, by weight of the recovered oil. As used herein, aromatics content is determined as the total BTEX (benzene-toluene-ethlylbenzene-xylene) according to US EPA 8260. In an embodiment, the viscosity of the recovered oil may be increased relative to the viscosity of the oil present in the substrate. In an embodiment, the recovered oil has a viscosity at 40° C. (KV40) of greater than 2 cSt, wherein the viscosity is determined according to ASTM-D88.
In an embodiment, the recovered oil is suitable for use in a drilling fluid. For example, the recovered oil in one embodiment is further processed by formulating a drilling fluid based on the oil, in one embodiment as the equivalent of a synthetic oil base stock. The drilling fluid can also be formulated with a brine component, e.g., as an internal phase, that is also recovered from the OBDC or a high-liquid (greater than 35 wt % liquids or where the liquid can be readily recovered by filtration, pressing, centrifugation or the like) water based or oil based drill cuttings or water based or oil based spent drilling fluids.
The exact mechanism for the improvement of the qualities and properties of the recovered oil are not known, but it is theorized that the oil may undergo various reactions in the low-oxygen or reducing atmosphere in the chemical-thermal treatment such as cracking, reforming, oligomerization, hydrogenation, dehydrogenation, coking, isomerization or the like, and further that the drill cuttings or other sorbent material, particularly by pretreatment or “activation” by the acid treatment in the peptizing step, may act as a catalyst for the conversion of the hydrocarbons to paraffinic and/or alicyclic hydrocarbons and/or conversion of heterohydrocarbon components to non-functionalized hydrocarbons. It is also theorized that the mechanism(s) may selectively favor reaction of the aromatic compounds and devolatilization of the paraffinic compounds. The invention is, however, not bound by any particular theory or reaction mechanism.
FIG. 1 shows a method 10 according to an embodiment of the present disclosure to separate and recover oil from a substrate feed 12 which may be OBDC and/or other oil-containing materials. The method 10 may include acid addition 14 and peptizing 16, wherein the substrate is contacted with an amount of an acidic reagent for a period of time, at a temperature, and under shear to react at least a portion of the substrate to produce a peptizate having an increased surface area compared to the substrate. The acidic reagent can include a mineral acid added in step 14 to the substrate at one or more stages before or during the peptizing step 16.
Combustion 18 provides a hot effluent gas at a temperature greater than 300° C. and comprising less than 1 vol % oxygen for mixing and desorption 20 to mix the peptizate with the hot gas under turbulent conditions to heat the substrate and desorb at least a portion of the oil. Solids recovery 22 may involve separating the mixture from the substrate mixing/desorption step 20 to obtain a dilute phase comprising vapor including devolatilized oil from the substrate and a dense phase comprising oil-lean solids 24. Solids recovery 22 may also include removal of entrained solids from the dilute phase with cyclonic separation, filtration, electrostatic precipitation, scrubbing or the like or any combination thereof.
In oil recovery step 26, oil 28 is recovered from the dilute phase vapors by, for example, condensation and gravity separation of the condensate into respective streams of oil 28 and an aqueous phase 30. If desired, the recovered oil stream 28 may be collected for further purification and/or use in the process, e.g., as a fuel in combustion step 18. In an embodiment, the oil purification may optionally include one or more additional processes to further purify the recovered oil for a particular end use. Examples include distillation, filtering, treatment with activated carbon, absorbents, adsorbents, and/or the like, reaction with various materials to remove and/or convert impurities contained therein, fractionation, ion exchange, and/or the like, depending on the desired properties of the oil and/or dependent on the intended use of the subsequently purified recovered oil.
FIG. 2 shows an embodiment of the apparatus, generally referred to as 32, wherein the substrate from substrate feed zone 34 and acid from acid feed system 36 are supplied to a peptizer 38 comprising a first housing 40 equipped with one or more high-shear agitators 42. The first housing 40 is preferably fixed and fluidly sealed. A transfer zone 44, preferably comprising a rotary valve 46 or other means to fluidly isolate the peptizing zone 38, is provided to supply the peptizate to an inlet end of thermal desorption zone 48 within second fixed housing 50 equipped with one or more turbulence-generating agitators 52. Burner 54 is provided to supply hot combustion effluent gas to the thermal desorption zone 48 to heat the peptizate and desorb oil from the sorbent material.
The second housing 50 is preferably a fixed horizontal cylinder equipped with a solids disengagement zone 54 opposite the inlet end of the thermal desorption zone 48 and a solids outlet 56 adjacent the disengagement zone 54 to receive disengaged solids therefrom. The solids disengagement zone 54 and solids outlet 56 are preferably spaced away from the agitator 52 to promote solid separation and settling, i.e., the agitator 52 preferably terminates adjacent the solids disengagement zone 54 and does not extend into the solids disengagement zone or above the solids outlet 56. The solids disengagement zone 54 may be provided with a hood 58 or other relatively large cross-sectional and/or low flow velocity plenum to promote solids settling and provide a solids-lean dilute phase for processing in vapor recovery system 60.
The Substrate
The substrate which is processed or treated according to various embodiments comprises liquid bound on or within a solid sorbent material, wherein the liquid comprises oil or a mixture of oil and water. Although the substrate to be treated is described herein with specific reference to drill cuttings as one example, and especially drill cuttings obtained from operations with oil-based drilling muds (oil based drill cuttings or OBDC), other contaminated or environmentally hazardous wastes or substrates can also be treated using the present methodology and apparatus, especially clay-containing wastes. Drill cuttings can contain large quantities of clay because the oil deposits and other strata typically have a high content of clay.
In one embodiment, the substrate can be provided by contacting a sorbent material containing acid-reactive component(s) with oil in a suitable oil-sorbent mixing device, for example, where the oil contains aromatics or has a relatively poor quality and it is desired to upgrade the oil according to the process of the present invention. In this embodiment, the process may include a separate oil-sorbent contacting step or the oil sorbent contacting may occur in the peptizer, e.g., in an oil-sorbent contacting zone upstream from the peptizing zone or a portion thereof. In an embodiment, the solids recovered from the thermal desorber can be recycled as the sorbent to the oil-sorbent contacting zone or step.
Suitable substrates include OBDC containing 50 wt % or less total liquids, based on the total weight of the substrate, wherein the substrate is generally free of free liquid, i.e., the liquid will not readily separate from the OBDC by gravity. In various embodiments, the substrate may contain less than or equal to about 35 wt % total liquids, less than or equal to about 30 wt % total liquids, less than or equal to about 25 wt % total liquids, less than or equal to about 20 wt % total liquids, less than or equal to about 15 wt % total liquids, or less than or equal to about 10 wt % total liquids, and may contain at least about 5 wt % oil, at least about 10 wt % oil, at least about 15 wt % oil or at least about 20 wt % oil, based on the weight of the substrate (liquid and sorbent). Substrates with greater amounts of oil can be processed according to the present embodiments, but, when economically possible, it may be desirable according to an embodiment to alternatively treat such substrates by other steps such as centrifugation, gravity settling, solvent extraction, or the like, prior to the instant process, to remove the bulk of the oil which may be readily removed by more conventional means.
If desired, in one embodiment, the substrate may be amended by the addition of lime or another acid-reactive component, e.g., where the substrate is deficient in acid-reactive components. OBDC normally have a pH in the range of about 10-12, and are sufficiently reactive with mineral acid to a pH in the intermediate peptized material and recovered devolatilized substrate of about 6-8. However, where the OBDC have an unusually low pH the process can benefit by the addition of alkaline earth, e.g. lime, to obtain a pH in the 10-12 range.
If desired, in another embodiment, the OBDC may optionally be pretreated, and/or treated in the peptizer, with a demulsifier such as dodecyl benzene sulfonate.
Peptizing
The peptizing of the substrate is a physical-chemical process in which the sorbent in the substrate is induced to quickly expand by contacting with one or more mineral acid reagents thereby increasing its volume to facilitate the disintegration or dispersion of agglomerated particles and expose surface area to facilitate the release of liquid in the subsequent thermal desorption step. Peptizing thus includes contacting the substrate with an amount of a mineral acid under high shear conditions within a peptizing zone.
In an embodiment, the mineral acid reagent, also referred to herein as the mineral acid, is added to the substrate in an amount sufficient to produce a peptizate having a pH between 6 and 8, preferably a pH between 6.5 and 7.5. The mineral acid may be added at between 1 wt % and 100 wt %, preferably between 2 wt % and 20 wt %, based on the total amount of substrate material present, to produce a peptizate. The mineral acid in one embodiment is typically added at 4 wt % to 10 or 12 wt %, based on the total weight of the substrate.
Importantly, the more water present in substrate the more acid is typically added. In an embodiment, the proportion of acid supplied to the peptizing zone can be employed as a temperature control tool in the thermal desorption zone, for example, if the steady state temperature of the thermal desorption zone increases or decreases due to decreased or increased water content of the OBDC supplied to the peptizer, then the acid addition rate may be respectively increased or decreased to account for the fluctuation. This can be an important control mechanism since the water content of the OBDC can vary considerably between and within batches, e.g., water may drain from the uppermost OBDC layers in the feed or storage hopper into the lower layers so that the lower layers may contain more water than the upper layers, or the upper layers may become wet from precipitation or humidity or other contact with water; and also because of the difficulty of adjusting the temperature of the combustion effluent gases supplied from the burner while maintaining low oxygen or substoichiometric oxygen:fuel ratios (fuel rich).
In addition, depending on the water content and the composition of the substrate, in one embodiment the amount of mineral acid added to produce a peptizate suitable for desorbing would result in a peptizate having a pH of less than 6. In an embodiment wherein the addition of an amount of mineral acid to produce a peptizate having a pH of 6 or less would not otherwise be suitable for desorption, additional acid and an alkaline reagent may be added to the peptizing zone in neutralizing amount, e.g., an amount of additional acid and alkaline reagent such as alkaline earth sufficient to produce a peptizate having a pH between 6 and 8. Where alkaline reagent is employed it is preferably added in an alternating stage or stages with the acid.
The acid may be diluted with water to achieve the desired result and/or control, but is preferably added as a concentrate or neat to obtain a higher temperature in the peptizate. Suitable mineral acids include, for example, sulfuric acid, oleum, phosphoric acid, nitric acid, hydrochloric acid, combinations thereof, and the like. In an embodiment, the mineral acid preferably comprises concentrated (98+wt %) sulfuric acid.
The mineral acid may be added to the substrate as it enters the peptizing zone, or may be added step wise in one or more stages during peptizing, under high shear mixing and/or kneading conditions. Examples of high shear conditions include those present in various kneaders, ribbon blenders, paddle mixers, and the like, known to one of skill in the art.
In an embodiment, the oil based drill cuttings and the mineral acid are contacted for a period of time and at conditions of temperature and shear sufficient to allow them to react chemically inasmuch as the OBDC are broken into smaller particles and/or a clay solid shale matrix may be expanded (e.g., intercalated, exfoliated, delaminated, opened, and/or the like) to permit the immigration of the inverse oil in water emulsion contained within the substrate to a point nearer to the surface of the particles.
In an embodiment, the substrate is preferably provided as a continuous stream into the peptizing zone. Peptizers such as those disclosed in my earlier patents U.S. Pat. Nos. 7,690,445, 7,481,878, 6,978,851 and 6,668,947, which are hereby incorporated herein by reference in their entireties for all purposes to the extent they are not inconsistent with the present disclosure, may be suitably employed. As shown in FIG. 3, in an embodiment, the peptizer 62 comprises the first housing 40 for the peptizing zone. The housing 40 is preferably fixed and includes an upper substrate inlet 64 at one end of the peptizer 62 and a lower solids outlet 66 (a discharge) at the other end of the peptizer 62. If desired, the acid may also be introduced in the inlet 64 with the solids. Optionally, peptizer 62 may include an upper exhaust vent 68 preferably in an upper surface adjacent substrate inlet 64, one or more additional ports 70 which may include steam inlets, acid reagent inlets, caustic reagent inlets, vapor outlets, liquid outlets, solids outlets, and/or the like, which may be located in an upper surface and/or a lower surface of peptizer 62 upstream of substrate inlet 64, between substrate inlet 64 and solids outlet 66 or downstream of the solids outlet as desired for co-current or countercurrent operation. In one embodiment, the vent 68 and port(s) 70, if present, are sealed so as to fluidly seal the peptizer 62, except that the vent 68 and port(s) 70 may be equipped with a pressure relief valve or rupture disk so as to prevent overpressuring the peptizer 62, e.g., in the event peptizer 62 is overheated above the boiling point of water or other liquid in the substrate, in which case the vent 68 or port 70 may be connected to the vapor recovery system 60 (see FIG. 2).
In an embodiment as best seen in FIGS. 3-5, the peptizer 62 comprises at least one agitator 72 to impart shear into the acid/substrate mixture. The agitator 72 may comprise a rotating shaft 74, preferably a pair of rotating shafts 74, longitudinally aligned in first fixed housing 40, which may be rotated in opposite or complementary directions. A plurality of paddles, pins, plows, blades and/or the like, referred to herein as blades 76, may be positioned along the length of shaft(s) 74. The blades 76 can be pitched to facilitate maximum shear conditions for agitation and/or movement of the solids in a forward and/or partial back-mixing within peptizer 62.
In embodiment, peptizer 62 is operated at a temperature of greater than or equal to about 50° C. and 200° C., preferably between about 70° C. and 100° C., more preferably between 75° C. and 90° C. In one embodiment, the peptizer 62 has a maximum operating temperature at or below the boiling point of the liquid bound to the substrate at an absolute pressure of 1.25 atmospheres, preferably below the boiling point of the bound liquid at atmospheric pressure; and in another embodiment, the peptizer 62 is operated at about atmospheric pressure, i.e., from about 0.9 to about 1.25 atmospheres absolute, or below atmospheric pressure, preferably from −0.1 to 0 atmospheres gauge. Subatmospheric pressure may be maintained in the peptizer 62, for example, by connecting vent 68 or a port 70 to an induced draft fan in vapor recovery system 60, or by sealing the inlet 64 and outlet 66 with suitable mechanical devices such as rotary valves which permit some vapor leakage or bypass from the peptizer 62 into a subatmospheric system such as where subatmospheric pressure is provided in thermal desorption zone 48 (see FIG. 2). In an embodiment, the peptizer 62 may heated or cooled to maintain the desired temperature. In a preferred embodiment, however, the peptizer 62 is insulated and operated adiabatically wherein the exothermic reaction between the acid reagent and acid-reactive materials in the substrate and/or heat of dilution of the acid reagent in the liquid present in the substrate feed provide internal heating. Where present, heating may occur through indirect heating e.g., via external application of a heat transfer medium, electrical heating, and/or the like.
FIGS. 4 and 5, respectively, show a schematic plan view of the movement of material in peptizer 62, and a schematic elevation of the movement of material in peptizer 62. The arrows in FIGS. 4 and 5 show the horizontal and vertical direction of the movement of the solids and the rotation of the shafts. If desired, baffles (not shown) may be positioned between adjacent blades 76. The peptizer 62 may further comprise a plurality of reactors or stages in sequence, either separate or within the same housing.
The internal design and construction materials for the peptizer 62 are preferably such as to resist extreme pH environments within the process, especially when heat is provided through direct or indirect heating of the peptizer 62 and/or via the exothermic reaction between the substrate and the mineral acid, the mineral acid and a caustic reagent, and/or the like. The peptizer is preferably comprised of stainless steel alloy.
The speed of the material throughput, as well as the specific materials used to manufacture the peptizer 62 may be selected to prevent the viscoelastic hydrocarbon and cuttings matrixes typical of oil based drill cuttings from sticking to the walls thereof. In an embodiment, the speed of agitator 72 is critical in creating particles suitable for the desorption step of the substrate contaminants. If the impeller speed is too slow, the substrate will not be adequately contacted with the reagents resulting in poor contact between the contaminated particles and the acid. If the speed of the impeller is too fast, energy is wasted with no improvement in reaction conditions including reduction in particle size and/or expanding of the particles of the substrate (i.e., the substrate) to be treated.
The moving speed at the tip of the blades 62 in one embodiment may ideally be between 2 and 8 m/s (7 and 26 ft/s) on rotation. More preferably, the tip speed is between 2 and 5 m/s (7 and 16 ft/s), and especially between 2.5 and 3.5 m/s (8 and 12 ft/s). As one example for a mixer treating 10 metric tons per hour of drill cuttings (5 m3/h or 180 ft3/h), the peptizer can have twin parallel shafts approximately 3 m (10 ft) long, running the length of the mixer, each with at least 30 paddles/shaft and a 0.4 m (1.3 ft) diameter. In another embodiment, the moving speed at the tip of the blades 62 is approximately 0.01 to 1 m/s, preferably about 0.2 m/s (0.7 ft/s) on the translation in both directions
In an embodiment, the total residence time of the substrate within the peptizer 62 is less than or equal to about 2 minutes, preferably the residence time within the peptizer is between about 10 and 120 seconds, preferably less than 100 seconds, preferably less than 90 seconds, preferably less than 80 seconds, preferably less than 70 seconds, preferably less than 60 seconds, preferably less than 50 seconds, preferably less than 40 seconds, with less than 30 seconds being more preferred.
As one example for a reactor treating 30 metric tons per hour of drill cuttings (15 m3/h), the peptizer 62 has twin parallel shafts approximately 3.66 m (12 ft) long with 74 paddles/shaft and a 457 mm (18-in.) diameter. The total reaction (residence) time preferably does not exceed 60-80 seconds inside the reactor. The reaction process requires vigorous agitation. The energy for agitation in the peptizer 62 desirably does not exceed 1.12 kW (1.5 hp) per each metric ton of treated matrix per hour. For example, to treat 30 metric tons per hour of contaminated drill cuttings, the total power required for driving the peptizer agitator is preferably 33.6 kW (45 hp) or less.
The temperature at the inlet of the peptizer 62, which represents the thermal equilibrium of the mixed feeds (ignoring any heats of reaction and/or dilution) is preferably ambient to slightly above ambient, e.g., 20 to 30° C., although in one embodiment the substrate, the acid reagent and/or other feeds may be preheated. The temperature of material within the peptizer may increase due to the heat generated by the reaction of the mineral acid with the substrate being treated, by the heat of dilution of the mineral acid in the water present in the substrate, and/or via (optional) application of heat to the peptizer itself. The temperature at the exit of peptizer is preferably greater than or equal to about 70° C., and preferably less than or equal to about 100° C.
Thermal Desorption
In an embodiment as shown in FIG. 2, the peptizate is transferred from the peptizing zone 38 through the transfer zone 44 into the second housing 50 comprising the thermal desorption zone 48. The thermal desorption zone 48 is in fluid communication with burner 54 which supplies combustion effluent gas. In an embodiment, the combustion effluent gas comprises less than 1 vol % oxygen and is supplied to the thermal desorption zone at a temperature greater than 300° C.
In an embodiment, the thermal desorption zone 48 comprises an agitator 52 to create turbulent conditions and promote rapid heat transfer. The peptizate is mixed with the combustion effluent gas under turbulent conditions in the thermal desorption zone 48 to heat the peptizate and desorb at least a portion of the oil from the sorbent material. The mixture exiting the thermal desorption zone 48 is separated into a dilute phase comprising oil vapor from the sorbent and a dense phase comprising the sorbent, wherein the dense phase has an oil content which is less than the oil content of the sorbent material present in the feed substrate and/or in the peptizate.
In an embodiment, the temperature of the combustion effluent gas is sufficient to provide a temperature of the vapor phase exiting the desorber in a range from a lower limit of 180° C., 200° C., 220° C., 235° C., or 250° C. to a higher upper limit of up to 500° C., 400° C., 350° C., or 300° C. In general, the thermal equilibrium temperature of the dense phase solids recovered from the desorber is about 10° C. to 50° C. less than the dilute phase vapor, preferably 20° C. to 40° C. less, more preferably 25° C. to 35° C. less. In an embodiment, slightly negative pressure, for example, 0.8 to 0.99 atmospheres absolute or −0.01 to −0.2 atmospheres gauge, is continuously maintained in the thermal desorption zone, e.g., by withdrawing vapor or a dilute solids phase via an induced draft fan in the vapor recovery system 60, and if desired a safety valve such as a pressure relief valve and/or rupture disk can be provided in the case of overpressure, e.g., the safety valve can be calibrated at about 0.1 MPa gauge (about 14.7 psig) or 0.05 MPa gauge (7.35 psig) or 0.03 MPa gauge (4.4 psig) or 0.02 MPa gauge (3 psig).
In an embodiment, the average residence time in the thermal desorption zone 38 of the dense phase (e.g., the solids present in the peptizate) is less than or equal to about 5 minutes, preferably less than or equal to about 4 minutes, with less than or equal to about 3 minutes being still more preferred. In an embodiment, the average residence time in the thermal desorption zone of the dilute phase is less than 1 minute. In an embodiment, the temperature and residence time in the thermal desorption zone is sufficient to produce a processed solid having less than or equal to about 3 wt % residual oil, preferably less than or equal to about 2.5 wt % residual oil, preferably less than or equal to about 2 wt % residual oil, preferably less than or equal to about 1.5 wt % residual oil, preferably less than or equal to about 1 wt % residual oil, preferably less than or equal to about 0.5 wt % residual oil present, based on the total amount of solids and oil in the dense phase.
In an embodiment, the dense phase has an average amount of residual oil which represents greater than or equal to about a 50% reduction in oil compared to the oil content in the original substrate, preferably greater than or equal to about a 60% reduction, preferably greater than or equal to about a 70% reduction, preferably greater than or equal to about an 80% reduction, preferably greater than or equal to about a 90% reduction, preferably greater than or equal to about a 95% reduction in oil content compared to the oil content of the original substrate.
In another important embodiment, the oil is selectively devolatilized in the thermal desorption step and/or otherwise upgraded to improve one or more of the properties of the recovered oil relative to the oil in the OBDC or other substrate, such as, for example, lower aromatics content, lower sulfur content, lower functional group content, higher saturates, higher viscosity, higher viscosity index, and any combination thereof. Without being bound by theory, reactions that may occur in the thermal desorber include cracking, hydrocracking, steam cracking, hydrogenation, dehydrogenation, isomerization, etc. The combustion effluent gas may contain reactive species such as, for example, hydrogen, hydrocarbons, steam, carbon monoxide, carbon dioxide, and the like. In one embodiment, the combustion effluent gas is free of oxygen, e.g., less than 1 vol % oxygen, preferably less than 0.1 vol % oxygen.
In one embodiment, the OBDC or other substrate may act as a catalyst or as a support for catalysts, e.g., the peptization with acid may expose or form catalytically active surfaces in the sorbent material. In a further embodiment, the OBDC or other substrate may be amended by the addition of a catalyst such as one or more of zeolites, aluminates, silicates, aluminum silicates, noble metals, etc., added in the peptization step or in the thermal desorber.
In one embodiment of a method, oil to be upgraded may be contacted with the substrate and then subjected to turbulent, low oxygen, thermal desorption. In this embodiment, the solids recovered from the thermal desorber may be recycled for use as the substrate, or the substrate may be OBDC which are not saturated or are supersaturated with oil or an oil-water mixture, or the substrate may be a clay-containing solid or a solid containing any acid-reactive mineral or an oil upgrading catalyst. The oil may be a single phase or it may be an emulsion or invert emulsion. For example, the oil can be a waste oil, sludge, emulsion, etc., or a petroleum fraction. The oil-substrate mixture is optionally peptized with an acid reagent and/or optionally preheated to 70-100° C.
In an embodiment, a suitable thermal desorption zone may be dimensioned and arranged to process about 20 metric tons/hr of pretreated or peptized ODBC to produce a final material comprising less than or equal to about 2.5 wt % oil, less than or equal to about 1.5 wt % oil, or less than or equal to about 1 wt % oil, based on the total weight of the output material. In an embodiment, at least a portion of the oil present in the dilute phase is recovered in the vapor recovery system 60, and in various embodiments, the recovered oil comprises at least 50 wt % of the oil originally present in the substrate, or at least 60 wt % of the oil originally present in the substrate, or at least 65 wt % of the oil originally present in the substrate, or at least 70 wt % of the oil originally present in the substrate, or at least 75 wt % of the oil originally present in the substrate, or at least 80 wt % of the oil originally present in the substrate, or at least 85 wt % of the oil originally present in the substrate.
In an embodiment, heat is supplied directly to the thermal desorption zone 48 in the form of combustion effluent gas by the burner 54 which is discharged into the thermal desorption zone. In an embodiment, the burner 54 preferably includes a combustion chamber positioned such that the hot combustion effluent gas enters the thermal desorption zone 48, but the burner is spaced away from the thermal desorption zone such that the flame does not impinge directly on the sorbent so as to avoid excessive pyrolysis or combustion of the oil present in or with the peptizate. In an embodiment, the burner 54 may operate at stoichiometric or sub-stoichiometric oxygen levels to control the amount of oxygen entering the thermal desorption zone to avoid or limit combustion or other oxidation of the oil present in or with the peptizate. In an embodiment, oxygen is desirably excluded from the combustion effluent by setting the desired fuel rate to the burner, adjusting the air or oxygen-enriched air supplied to find the maximum flame temperature, and then slightly reducing the air or oxygen-enriched air to reduce the flame temperature, e.g., 5° C., 10° C., 20° C. or 30° C. below the maximum flame temperature. For example, the burner in one embodiment is supplied with 90 to 99 percent of stoichiometric air, preferably 95 to 98 percent of stoichiometric air.
If desired, a temperature moderator such as supplemental water and/or steam may be injected into the combustion effluent gas to moderate the temperature within the thermal desorption zone 48 to avoid overheating of the material being treated therein. Any suitable fuel supply may be used, e.g., natural gas, fuel oil, recovered process oil, or a combination thereof. The combustion effluent gas may be supplied to the thermal desorption zone at a temperature from about 300° C. to about 1200° C.
In an embodiment, as shown in FIGS. 6-9, the thermal desorption zone 48 is located within a desorber 100 which includes a generally cylindrical fixed housing 102. The peptizate inlet 104 and solids outlet 106 are preferably controlled by respective rotary valves 108, 110 (see FIG. 6) or other similar device to prevent oxygen from entering and/or hydrogen, carbon monoxide and hydrocarbon vapors from exiting the otherwise fluidly sealed desorber 100. An agitator 112 comprises a rotating shaft 114 and a plurality of radially extending paddle assemblies 116. The shaft 114 is centrally located, extends longitudinally through the desorber 100 and is supported by end bearings 118 and intermediate bearings 120 carried on bearing support assemblies 122. The end bearings 118 should be sealed to inhibit fluid communication outside the desorber 100.
As shown in FIGS. 8-9, the housing 110 may optionally be refractory-lined and include, for example, a coaxial steel outer wall 124 and/or one or more refractory linings such as outer refractory layer 126, inner refractory layer 128 and surface layer 130. The outer refractory layer 126 in one embodiment is a concrete layer formed from steel-reinforced gypsum cement, and inner layer 128 in an additional or alternate embodiment comprises a cast refractory or refractory bricks. Skin layer 130 is disposed between an inner surface of layer 128 and the cylindrical surface defined by the rotation of the paddle assemblies 116 about the shaft 114, and may be formed in situ by the deposition of substrate particles which become baked onto the surface of layer 128. Additional insulation materials e.g., cast or brick refractory materials, insulation, sound abatement materials, and the like, may be employed inside or outside the unit to further improve the efficiency of the unit by attenuating the escape of heat.
In an embodiment, the combustion effluent gas 132 may enter the desorber 100 at a hot gas inlet 134 located in a lower portion of the inlet end below the peptizate inlet 104 and pass co-currently with the solids to gas outlet 136 located above the solids outlet 106. Co-current flow facilitates movement of the solid particles toward the exit location and also facilitates temperature moderation in the thermal desorption zone, which may be helpful to avoid or minimize coke or carbon formation from oil residue which can otherwise occur if the temperature within the thermal desorption zone 48 is too high, which can in-turn inhibit mass transfer and lead to losses in the amount of oil that can be recovered. The presence of coke or carbon deposits on the treated solids can also discolor the treated solids, e.g., gray or black, which may serve as an indication to one of skill in the art that the internal temperature is too high for a particular application. In an alternate embodiment, the gas and solids may enter and exit from opposite ends in a countercurrent configuration.
In an embodiment, the shaft 114 is preferably rotated such that the tip speed of the paddle assemblies 116 is between 0.1 and 20 m/s, preferably between 0.5 and 10 m/s, more preferably between 1 and 8 m/s, and more preferably between 2 and 6 m/s. The rotation creates turbulence within the thermal desorption zone to improve the gas-solid contact of the substrate undergoing the desorption step with the hot gases and thus to promote heat and mass transfer, reducing the residence time required to complete the desired heat and mass transfer within the thermal desorption zone. Insufficient agitation can increase the residence time needed or reduce the efficiency of the oil recovery. Too much agitation can unnecessarily increase the power requirements, speed wear and tear on the equipment and produce excessive fines which are undesirably entrained in the dilute phase and can lead to problems with fines removal or plugged lines and equipment in the vapor recovery system 60.
The paddle assemblies 116 can be pitched as desired to advance the solids material through the desorber 100, but are preferably not pitched. Similarly the desorber 100 can be sloped to facilitate or inhibit the movement of solids through the unit, but is preferably level. The turbulence in the desorber 100 and the relatively high velocity of the gas through the unit are preferably sufficient to advance the solids to the solids outlet 106. The space above the solids outlet 106, which is preferably located through a lower surface of the desorber 100, is desirably free of rotating paddle assemblies 116 so as to promote solids disengagement from the dilute phase or vapor. Solids disengagement is also promoted by providing an exit conduit or hood 58 of relatively large cross sectional area so as to reduce the flow velocity and allow solids to settle, i.e., where the fines entrainment is limited to particles having a terminal velocity which is less than the velocity of the exiting vapor. Increasing the height of the hood 58 and limiting agitation in the space below and/or adjacent to the vapor outlet 136 can also be beneficial to promoting solids disengagement.
The dilute phase produced in the thermal desorption zone may comprise fluidized solid particles of the sorbent and other materials. It is generally desirable to minimize solids entrainment in the dilute phase. Therefore, in one embodiment, the desorber 100 comprises a solids disengagement zone 54 having a relatively low velocity and turbulence relative to other areas of the thermal desorption zone, which allows entrained particles to drop out of the dilute phase before exiting the thermal desorption zone. The solids disengaged in the solids disengagement zone are returned to the solids adjacent a bottom surface of the thermal desorption zone and discharged from the thermal desorption zone at a solids discharge 51. In an embodiment, solids discharge 51 may comprise a desorber outlet rotary valve 44. Disengagement zone 96 may also comprise an impingement plate, demister or similar devices (not shown), to facilitate solids disengagement from the dilute phase.
In an embodiment, the first fixed housing and the second fixed housing are located in a single housing, separated from one another. In another embodiment, the thermal desorption zone is a different type of reactor which achieves the same mass and energy transfer under high shear or turbulent conditions to mix and heat the solids being treated with the combustion effluent gas, such as, for example, a fluid bed reactor, a moving bed reactor, a riser reactor, any combination thereof, or the like.
The solids are recovered from the thermal desorber below the solids disengagement zone. A rotary valve may be used to inhibit gas from escaping from the desorber and air from entering the desorber. If desired, the solids may be sprayed with water for cooling and/or dust control or to enhance the desired water content of the solids. In one embodiment, the recovered solids from the thermal desorber have a particle size distribution comprising 90 wt % or more of the particles having a mesh size greater than 200 mesh, e.g., 90 wt % or more greater than 74 microns, and alternatively or additionally at least 80 wt % of the particles having a mesh size less than 40 mesh, e.g., 80 wt % or more smaller than 420 microns. The solids may be further processed to remove additional oil, or may be disposed of, e.g. solids containing less than 1 wt % oil can usually be disposed of in an environmentally responsible manner.
Vapor and Oil Recovery
In an embodiment, the dilute phase exiting the solids disengagement zone of the thermal desorber may comprise some entrained fines, desorbed hydrocarbons (e.g., oil) and water (steam), in addition, of course, to the combustion gas effluent and any gaseous reaction products. The dilute phase may also comprise combustion gas produced by the burner. The dilute phase may further include particulate matter, which is entrained in the dilute phase during thermal desorption. The dilute phase leaving the thermal desorber is typically at a temperature between 100° C. and 800° C., preferably greater than or equal to about 150° C., preferably between 180° C. and 350° C., more preferably about 180° C. to about 325° C. or more preferably between 200° C. and 300° C. The volume the dilute phase depends on the feed rate through the thermal desorption zone, the temperature of the thermal desorption zone, the amount initially present in the substrate, the amount of materials added during the process, and the like.
In an embodiment, dilute phase may be further processed in a vapor recovery system 60 comprising various separation and purification devices, heat exchange devices, gas-liquid contact devices, scrubbers, decanters, and the like, to remove particular matter present in the dilute phase, to condense and recover the hydrocarbons and/or water present in the dilute phase, to recover heat present in the dilute phase for subsequent use in the process or elsewhere, and/or the like.
Represented generally as 60 in FIG. 2, and as shown in FIG. 10, vapor recovery system 60 may include one or more of a cyclone 150, knock down tower 152 or other gas-solids separator or combination thereof, and/or the like, to remove any entrained particulate solids. If solids, especially sub 4-micron particles, are not removed and are present in the oil-water condensate, a rag emulsion may form which can be difficult to remove. The cyclone may include a number of stages, e.g., primary, secondary, tertiary cyclone stages, etc., wherein each successive stage removes smaller and smaller particles. Suitable gas-solid separators in various embodiments may alternatively or additionally include gravity settling chambers, impingement separators, cyclone separators, mechanical centrifugal separators, granular-bed separators, bag filters, scrubbers, electrostatic precipitators, air filters, and the like, including combinations.
The fines-lean vapor from the cyclone 150 and/or tower 152 may be further treated to remove hydrocarbons and other condensables via heat recovery and condensation. For example, the vapor may be cooled and condensate removed at a temperature above the boiling point of water in high temperature condenser 154, and then cooled and condensed in a low temperature condenser 156 at a temperature below the boiling point of water. The condensate from high temperature condenser 154 comprises hydrocarbons having a boiling point above that of water, and is preferably essentially free of water, e.g., less than 1000 ppmw water or less than 100 ppmw water, and may be collected in a recovered oil tank 158. The condensate from the low temperature condenser 156 may contain both oil and water and can be collected in a gravity separator 160 for recovery of respective oil and water streams. The oil stream from separator 160 may be collected together with other recovered oil in tank 158, or it may be a separate product stream of hydrocarbons with a relatively low boiling point or other specified characteristics. The water from the separator 160 may be further treated for disposal if needed, or recirculated as process or cooling water.
The non-condensed vapors from condenser 156 may optionally be exhausted via induced draft fan 162 and scrubber 164 to remove any residual particulates, NOx, SOx, CO, CO2, other pollutants or the like. Alternatively or additionally, the vapor may be burned as fuel gas or, since it may contain appreciable amounts of hydrogen, carbon monoxide and/or carbon dioxide, used as a synthesis gas for any suitable process that can utilize the gaseous reactants therein.
In an embodiment, at least a portion of the heat contained in the dilute phase exiting the thermal desorption zone, or anywhere along the vapor separation system, may be recovered. In an embodiment, recovered heat may be used to preheat the air used to produce the combustion effluent gas for the process. This may be done using a gas-gas indirect heat exchanger (not shown), a steam condensation loop (not shown), or the hot gases may be supplemented with oxygen and utilized again in the combustion process (not shown).
Transportability
In an embodiment, the apparatus may be portable. The various components may be mounted on one or more platforms, also referred to in the art as “skid mounted”, “truck mounted”, or the like, such that the apparatus may be transported on a US Interstate highway either as a single unit, or on a plurality of platforms which are interconnected at the intended destination. The platforms may include wheels, brakes, signals and the like (e.g., truck mounted on a flat-bed trailer) suitable for transport on a US Interstate highway, or the platforms may be mountable on a truck bed or rail car (skid mounted). In an embodiment, the one or more platforms are dimensioned and arranged for transportation such that each of the mounted platforms has a total width of less than 2.59 meters (102 inches), a total length of less than 13.71 meters (45 feet) and a total height of less than 4.27 meters (14 feet).
In an embodiment, the first and second housings and the burner are mounted on a first platform such that the mounted first platform has a total width of less than 2.6 meters (102 inches), a total length of less than 13.7 meters (45 feet) and a total height of less than 4.2 meters (13.5 feet). In embodiments, the vapor recovery system is mounted on the first platform, or is mounted on a second platform of similar overall dimensions.
In one representative configuration as seen in FIGS. 11-14, wheeled trailer 200 configured for operation in FIG. 11 has mounted thereon peptizer 202 positioned on support structure 203 over desorber 204, forced draft fan 206 connected to firebox 208 and gas outlet pipe 210. Also, in operation conveyors 212, 214 are positioned to supply OBDC to feed hopper 216 and to remove solids from the discharge from desorber 204. Wheeled trailer 218 configured for operation in FIG. 12 has mounted thereon cyclone 220, knock-out tower 222, high temperature condenser 224, low temperature condenser 226 and induced draft fan 228 positioned on support structure 230. In operation the desorber gas outlet pipe 210 is connected to the cyclone inlet pipe 232, and a conveyor 234 may be provided to remove fines from the bottom of the cyclone 220.
In transport mode as shown in FIGS. 13-14, the major equipment, e.g., peptizer 202, desorber 204, fan 206, firebox 208, cyclone 220, tower 222, condensers 224, 226 and fan 228, may be mounted in operating position and configuration, and, if desired, connecting lines such as connector piece 236 and more portable equipment such as conveyors 212, 214, 234 may be disconnected and secured to the trailers 200, 218 where there is space allowed. If desired or if needed, some of the major equipment pieces may also be disassembled and secured on the trailers 200, 218 to accommodate height, width or length restrictions.
Upon arrival at the site for treatment of ODBC, the conveyers 212, 214, 234, transfer line 236 and any other disassembled equipment are connected and installed for operation. Oil collection, gravity settling, water collection, etc., may be accomplished using fixed or portable tanks, e.g., tank trucks. When the solids treatment is completed, the rig can be configured for transport and trucked to a new job location.
Accordingly, the invention provides the following embodiments:

    E1. A method comprising:
    
        heating an oil containing material with a catalyst in a turbulent environment comprising less than about 1 volume percent oxygen within a reactor at a temperature, pressure, and for a period of time sufficient to produce a vapor phase at an exit of the reactor comprising an upgraded oil;
        the catalyst comprising particulates recovered from a thermal desorption process in which an oil contaminated substrate has been contacted with an acidic reagent to form a peptizate and the peptizate is mixed with a combustion effluent gas under turbulent conditions at a temperature above 200° C. to form a light phase comprising desorbed oil and a dense phase from which the catalyst is recovered.
    
    
    E2. The method of Embodiment E1, further comprising contacting the oil contaminated substrate with the acidic reagent to form the peptizate, mixing the peptizate with the combustion effluent gas under turbulent conditions above 200° C. to form the light phase and the dense phase, and recovering the catalyst from the dense phase.
    E3. A method comprising:
    
        recovering catalyst as particulates from a dense phase of a thermal desorption process comprising contacting an oil contaminated substrate with an acidic reagent to form a peptizate, and mixing the peptizate with a combustion effluent gas under turbulent conditions at a temperature above 200° C. to form a light phase comprising desorbed oil and the dense phase from which the catalyst is recovered; and
        heating an oil containing material with the catalyst in a turbulent environment comprising less than about 1 volume percent oxygen within a reactor at a temperature, pressure, and for a period of time sufficient to produce a vapor phase at an exit of the reactor comprising an upgraded oil.
    
    
    E4. The method of any one of Embodiments E1 to E3, wherein the oil contaminated substrate utilized in the thermal desorption process comprises oil based drill cuttings.
    E5. The method of any one of embodiments E1 to E4, wherein the combustion effluent gas of the thermal desorption process comprises less than about 1 volume percent oxygen.
    E6. The method of any one of embodiments E1 to E5, wherein the upgraded oil comprises a lower aromatic content relative to the oil present in the oil containing material.
    E7. The method of any one of embodiments E1 to E6, wherein the upgraded oil comprises a lower sulfur content relative to the oil present in the oil containing material.
    E8. The method of any one of embodiments E1 to E7, wherein the upgraded oil comprises a lower functional group content relative to the oil present in the oil containing material.
    E9. The method of any one of embodiments E1 to E8, wherein the upgraded oil comprises a higher viscosity, a higher viscosity index, or both, relative to the oil present in the oil containing material.
    E10. The method of any one of embodiments E1 to E9, wherein the oil containing material comprises water.
    E11. The method of any one of embodiments E1 to E10, wherein the oil containing material is combined with water, catalyst, or both prior to said heating of the oil containing material.
    E12. The method of any one of embodiments E1 to E11, wherein water, steam, and/or catalyst is injected into the reactor simultaneous with said heating of the oil containing material.
    E13. The method of any one of embodiments E1 to E12, wherein the vapor phase exits the reactor at a temperature of greater than about 180° C. and less than 500° C.
    E14. The method of any one of embodiments E1 to E13, wherein the pressure in the reactor is from about 0.9 to about 1.25 atmospheres, absolute.
    E15. The method of any one of embodiments E1 to E14, wherein the oil containing material is a waste oil.
    E16. The method of any one of embodiments E1 to E15, wherein the oil containing material is an emulsion.
    E17. The method of any one of embodiments E1 to E16, wherein the oil containing material is a petroleum fraction.
    E18. The method of any one of embodiments E1 to E17, wherein the oil containing material is a sludge.
    E19. The method of any one of embodiments E1 to E18, wherein the oil containing material is a drilling fluid.
    E20. The method of any one of embodiments E1 to E19, further comprising condensing the vapor phase to recover the upgraded oil.
    E21. The method of any one of embodiments E1 to E20, wherein the upgraded oil is essentially free of water or comprises less than about 1000 ppm by weight water.
    E22. The method of any one of embodiments E1 to E21, wherein the upgraded oil comprises a total BTEX less than 2 wt % or less than 1 wt %.
    E23. The method of any one of embodiments E1 to E22, wherein the upgraded oil comprises a viscosity at 40° C. (KV40) greater than 2 cSt.
    E24. The method of any one of embodiments E1 to E23, wherein the upgraded oil comprises:
    
        (1) a total BTEX content less than 1 wt % as determined according to US EPA 8260;
        (2) an aniline point of 68° C. or greater as determined by ASTM-D611;
        (3) flash point of 95° C. or more as determined by ASTM-D93;
        (4) a viscosity of 2 cSt or more at 40° C. as determined according to ASTM-D88;
        (5) a pour point of −15° C. or below as determined according to ASTM D-92;
        (6) a specific gravity of 0.86 or less as determined according to ASTM-D1298; and
        (7) a sulfur content of 0.08 wt % or less as determined according to ASTM-1552.
    
    


EXAMPLES
The peptizing step in one embodiment is important to the success of the instant process. In Comparative Example 1, an oil based drill cuttings (OBDC) substrate having 11 wt % water, 9.3 wt % oil, and 79.7 wt % solids was treated according to a comparative process using a lab scale setup including a peptizer, an agitated direct thermal desorber, and a cyclone, but without adding any acid to the peptizer The desorber agitator speed was 115 rpm with a tip speed of 1.1 m/s and the residence time of the combustion effluent gas was about 3 seconds (27.7 m/min). The material from the peptizer was heated in the thermal desorber under high shear conditions using co-current fuel-rich combustion effluent gas at 920° C. to obtain an outlet temperature of 220° C., which was subject to cyclone separation to remove entrained solids, followed by condensation and decanting to recover oil and water streams. The substrate and liquid and solids product streams were measured and analyzed for oil, water and solid contents and the results are presented in Table 1.







TABLE 1







Mass Balance, Example 1 (Comparative)














Substrate

Desorber

Oil
Water


Stream/
feed,
Conc. H2SO4,
solids,
Fines,
Condensate,
Condensate,


Component
kg (wt %)
kg (wt % feed)
kg (wt %)
kg (wt %)
kg (wt %)
kg (wt %)
















Oil
6.7 (9.3)

3.1 (5.7)
0.21 (4.5)
3.0 (100)
0


Water
 8 (11)

3.12 (5.7) 
0.14 (3.1)
0
8.9 (100)


Solids
57.3 (79.7)

48.5 (88.6)
 4.16 (92.4)
0
0


Acid

0 (0)






Total
72
0
48.5
4.51
3.0
8.9









In Example 1, only 44 wt % of the oil present in the substrate was recovered as a condensate and the residual oil on the solids recovered from the desorber was 3 wt %. The additional water in the outputs is explained by the presence of water in the combustion gas, which was not included in the mass balance.
In Example 2, an OBDC substrate having 23.4 wt % water, 11.6 wt % oil, and 65.0 wt % solids was treated using the same lab scale setup as in Example 1, except that sulfuric acid was added to the peptizer at a rate of 5.2 wt % by weight of the OBDC. The peptizate was heated in the thermal desorber under the same high shear conditions and fuel-rich combustion effluent gas at 920° C. to produce dense phase and dilute phase outputs at a temperature of 300° C., and the dilute phase was also subjected to cyclone separation as before to remove entrained solids, followed by heat exchange, condensation and decanting to recover oil. The higher desorber outlet temperature is explained by the exotherm from the reaction of the OBDC with the acid in the peptizer. The results are presented in Table 2.







TABLE 2







Mass Balance, Example 2














Substrate

Desorber

Oil
Water


Stream/
feed,
Conc. H2SO4,
solids,
Fines,
Condensate,
Condensate,


Component
kg (wt %)
kg (wt % feed)
kg (wt %)
kg (wt %)
kg (wt %)
kg (wt %)
















Oil
11.6 (11.6)

1.1 (3) 
0.15 (5.1)
3.33 (100)
0


Water
12.64 (23.4) 

0.74 (2.2)
0.20 (6.7)
0
10.76 (98)


Solids
35.1 (65.0)

31.66 (94.8)
 2.65 (88.2)
0
0.21 (2)


Acid

2.8 (5.2)






Total
54
0
33.5
3.0
3.33
8.9









In Example 2, 53 wt % of the oil present in the substrate was recovered and the residual oil on the recovered dense phase solids was 3 wt %, which was an improvement for the peptizing embodiment over the high-shear direct thermal desorption without acid addition in Example 1. The excess solids reported in the outputs is believed to be due to the formation of sulfate salts and other solid compounds formed as the acid reaction products in the peptizer.
In Example 3, another OBDC substrate having 19 wt % water, 11.6 wt % oil, and 69.4 wt % solids was treated according to the inventive process using the same lab scale setup as in Examples 1 and 2, except that the concentrated sulfuric acid was added to the peptizer at a rate of 7.8 wt % by weight of the OBDC. The peptizate was heated in the desorber using combustion effluent gas at 900° C. to obtain products at a temperature of 275° C. The dilute phase was again subjected to cyclone separation to remove entrained solids, followed by heat exchange/condensation and decanting to recover oil. The results are shown in Table 3.







TABLE 3







Mass Balance, Example 3














Substrate

Desorber

Oil
Water


Stream/
feed,
Conc. H2SO4,
solids,
Fines,
Condensate,
Condensate,


Component
kg (wt %)
kg (wt % feed)
kg (wt %)
kg (wt %)
kg (wt %)
kg (wt %)





Oil
 4.18 (11.6)

0.26 (1.2)
0.25 (8.35) 
3.03 (100)
0  


Water
6.84 (19) 

0.48 (2.2)
0.12 (4)   
0
7.72 (100) 


Solids
24.98 (69.4)

 21.5 (96.6)
2.63 (87.65)
0
0.05 (>0.1)


Acid

2.8 (7.8)






Total
36
2.8
22
3
3.03
7.77









In Example 3, when the amount of acid was increased to about 8 wt % by weight of the OBDC, 72.5 wt % of the oil present in the substrate was recovered and the residual oil on the recovered dense phase solids was nearly 1 wt %.
In Example 4, a test was conducted on a commercial scale (portable size) unit for a total time of operation of 7.25 hours using a 2.3 m diameter by 3 m long thermal desorber with paddles on 195 mm (7.68-in.) spacing at 40 rpm. The test was conducted at a rate of 3.54 metric tons/hr using OBDC obtained from a well site wherein the oil utilized was mainly diesel fuel with an aromatic content of up to about 30 wt % according to the spec sheet. A total of 2066 L of oil were recovered (82.3%) and the dense phase had a final wt % oil of 2.2%, reduced from 10.72 in the substrate feed. A total of 1030 L of diesel fuel were fed to the entire system including the burner and the diesel generator used to operate the equipment, to produce a net recovery of 1036 L of oil from the process above fuel requirements. During the process, 2.37 L/min of diesel fuel was supplied to the burner to produce the combustion effluent gas utilized in the desorber. A total of 19,000 L of water were used in the scrubber columns. The average residence time of the solids was 40 seconds in the peptizer and 3 minutes in the thermal desorber. The peptizing zone volume was 1.8 m3 and the thermal desorption zone volume was 22.8 m3.
In this test, the substrate feed was supplied to the peptizer along with concentrated sulfuric acid at an average of 3.7 wt % by weight of the OBDC. The peptizer outlet temperature was between 80° and 100° C. The peptizate was fed into the desorber co-currently with a combustion effluent gas supplied at a temperature of 1000° C. The temperature at the outlets of the thermal desorption zone was maintained between 240° and 260° C. by adjusting the acid rate to the peptizer as needed. The dense phase solids were recovered through a rotary valve. The dilute phase exited the thermal desorption zone and entered a cyclone separator and entrained solids were recovered. Mechanical rodding of the transfer line to the cyclone was used as needed to avoid plugging. The solids-lean gas exited the cyclone separator at a temperature between 150° and 180° C. and entered a knock-out drum to further remove entrained solids. The gas exited the knock-out drum at a temperature of 120° to 140° C. and was directed into a high temperature heat exchanger wherein oil and water were recovered. The uncondensed vapors exited the heat exchanger at a temperature between 40 and 60° C. and were then directed into a low temperature condenser using cooling tower water ( ̃30° C.) as the cooling medium. The condensate from the low temperature condenser was gravity separated to recover the oil. The uncondensed vapors exited the scrubber column at a temperature between 33° and 35° C. and were vented.
The outputs were measured and analyzed, and the results are shown in Table 4. Note additional water recovery from the combustion effluent in the outputs and additional solids believed to be due to sulfate addition salts and other products from the acid added to the OBDC in the peptizer.







TABLE 4







Mass Balance, Example 4
















Substrate

Desorber
Cyclone

High Temp.
Low Temp.
Total Liquids


Stream/
feed,
Conc. H2SO4,
solids,
fines,
Knock-out,
Cond.,
Cond.,
Recovered, kg


Component
kg (wt %)
kg (wt % feed)
kg (wt %)
kg (wt %)
kg (wt %)
kg (wt %)
kg (wt %)
(% Recovered)





Oil
 2744.3 (10.7)

446 (2.2)
118.4 (6.3)
310.25 (38.8) 
871.5 (8.4) 
  512 (27.1)
1693.75 (61.7)


Water
 1920 (7.5)

360 (1.8)
 26.3 (1.4)
408.8 (51.1)
9544 (91.6)
1366.5 (72.4)
11705.6 (610) 


Solids
20935.7 (81.8)

19194 (96.0) 
1735.2 (92.3)
80.95 (10.1)
 0 (0)
 9.9 (0.5)



Acid

940 (3.7)








Total
25600
940
20000
1879.9
800
10416
1888.4









The solids recovered from the desorber had the particle size distribution given in Table 5.







TABLE 5







Desorber Solids Size Distribution, Example 4










Mesh Size
Solids Retained, Wt %














40
16.4



60
12.4



80
8.0



200
56.0



−200 (Fines)
7.2










The oil recovered from the process was analyzed and the results are presented in Table 6.







TABLE 6







High Quality Oil Recovered, Example 4












Recovered Oil
Recovered Oil




(High Temp.
(Low Temp.


Parameter
Test Method
Condensate)
Condensate)













Specific Gravity
ASTM-D1298
0.855
0.822


@ 60° F.


API Gravity
API
33.82
—


Flash Point Temp.
ASTM-D93
133
95


ICOC, ° C.


Ignition Temp.
ASTM-D56
146
—


ICOC, ° C.


Pour Point, ° C.
ASTM-D92
—
−15


Total Ash, ppm
ASTM-D482
460
6


Heat Value, cal/g
Calorimetry
10,982
—


Viscosity @
ASTM-D88
5.61
3.45


40° C., cSt


Viscosity @
ASTM-D88
—
1.42


100° C., cSt


Sulfur, wt %
ASTM-1552
0.08
0.95


Carbon, wt %

86.43
—


Hydrogen, wt %

13.23
—


Nitrogen, wt %

0.10
—


Oxygen, wt %

0.114
—


Aniline Point, ° C.
ASTM-D611
69
68


Distillation
ASTM-D88


Temp. @ 10%

—
238.8


evaporated, ° C.


Temp. @ 50%

—
268.7


evaporated, ° C.


Temp. @ 90%

—
321.3


evaporated, ° C.


Saybolt Color
ASTM-D156-07
—
−16


Cloud Point, ° C.
ASTM-2500-09
—
−13


BTEX


Benzene, mg/L
EPA 8260
—
0.282


Toluene, mg/L
EPA 8260
—
0.242


Ethylbenzene, mg/L
EPA 8260
—
0.125


Xylenes, mg/L
EPA 8260
—
0.348









As the data show, 61.7 wt % of the available oil was recovered as a liquid from the substrate. A rather unexpected result was the improvement in the properties of the oil recovered. The composition of the oil recovered by the instant process is markedly different from that of normal diesel fuel that was present in the oil based drill cuttings used as substrate in the instant test. In fact, in view of the viscosity and aniline point, the recovered oil is suitable for use in a variety of functions including oilfield functions, household/industrial cleaning products, metal rolling oil, paints and coatings, pesticide formulations, paper and milling chemicals, water treatment chemicals, and the like, consistent with other known refined mineral oils having similar properties.
The uncondensed gases from the stack in Example 4 were analyzed and determined to contain 92-134 ppm CO, 7.3 vol % CO2, 1 ppm NOx as NO, no detectable H2S, and had an explosivity (lower explosive limit in air) of 40 to 80 vol %.
The invention has been described above with reference to numerous embodiments and specific examples. Many variations will suggest themselves to those skilled in this art in light of the above detailed description. All such obvious variations are within the full intended scope of the appended claims.

## Claims

1. A method comprising:
heating an oil containing material with a catalyst in a turbulent environment comprising less than about 1 volume percent oxygen within a reactor at a temperature, pressure, and for a period of time sufficient to produce a vapor phase at an exit of the reactor comprising an upgraded oil, wherein the vapor phase exits the reactor at a temperature of greater than or equal to about 150° C.;
the upgraded oil comprising at least one of (1) a lower aromatic content relative to the oil present in the oil containing material; (2) a lower sulfur content relative to the oil present in the oil containing material; (3) a lower functional group content relative to the oil present in the oil containing material; and (4) a higher viscosity, a higher viscosity index, or both, relative to the oil present in the oil containing material;
the catalyst comprising particulates recovered from a thermal desorption process in which an oil contaminated substrate has been contacted with an acidic reagent to form a peptizate and the peptizate mixed with a combustion effluent gas comprising less than about 1 volume percent oxygen under turbulent conditions at a temperature above 200° C. to form a light phase comprising desorbed oil and a dense phase from which the catalyst is recovered, the substrate comprising a peptizable matrix component selected from acid-reactive clays and minerals.

2. The method of claim 1, wherein the upgraded oil comprises a lower aromatic content relative to the oil present in the oil containing material.

3. The method of claim 1, wherein the upgraded oil comprises a lower sulfur content relative to the oil present in the oil containing material.

4. The method of claim 1, wherein the upgraded oil comprises a lower functional group content relative to the oil present in the oil containing material.

5. The method of claim 1, wherein the upgraded oil comprises a higher viscosity, a higher viscosity index, or both, relative to the oil present in the oil containing material.

6. The method of claim 1, wherein the oil containing material comprises water.

7. The method of claim 1, wherein the oil containing material is combined with water, catalyst, or both prior to said heating of the oil containing material.

8. The method of claim 1, wherein water, steam, and/or catalyst is injected into the reactor simultaneous with said heating of the oil containing material.

9. The method of claim 1, wherein the vapor phase exits the reactor at a temperature of greater than about 180° C. and less than 500° C.

10. The method of claim 1, wherein the pressure in the reactor is from about 0.9 to about 1.25 atmospheres, absolute.

11. The method of claim 1, wherein the oil containing material is a waste oil.

12. The method of claim 1, wherein the oil containing material is an emulsion.

13. The method of claim 1, wherein the oil containing material is a petroleum fraction.

14. The method of claim 1, wherein the oil containing material is a sludge.

15. The method of claim 1, wherein the oil containing material is a drilling fluid.

16. The method of claim 1, further comprising condensing the vapor phase to recover the upgraded oil.

17. A method comprising:
recovering catalyst as particulates from a dense phase of a thermal desorption process comprising contacting an oil contaminated substrate with an acidic reagent to form a peptizate, and mixing the peptizate with a combustion effluent gas comprising less than about 1 volume percent oxygen under turbulent conditions at a temperature above 200° C. to form a light phase comprising desorbed oil and the dense phase from which the catalyst is recovered, wherein the substrate comprises a peptizable matrix component selected from acid-reactive clays and minerals; and
heating an oil containing material with the recovered catalyst in a turbulent environment comprising less than about 1 volume percent oxygen within a reactor at a temperature, pressure, and for a period of time sufficient to produce a vapor phase at an exit of the reactor comprising an upgraded oil;
wherein the vapor phase exits the reactor at a temperature of greater than or equal to about 150° C.; and
wherein the upgraded oil comprises at least one of (1) a lower aromatic content relative to the oil present in the oil containing material; (2) a lower sulfur content relative to the oil present in the oil containing material; (3) a lower functional group content relative to the oil present in the oil containing material; and (4) a higher viscosity, a higher viscosity index, or both, relative to the oil present in the oil containing material.

18. The method of claim 17, wherein at least a portion of the catalyst is recovered from the light phase of the thermal desorption process.

19. The method of claim 17, wherein the oil contaminated substrate utilized in the thermal desorption process comprises oil based drill cuttings.

20. The method of claim 17, wherein the pressure in the reactor is less than about 0.1 MPa gauge (14.7 psig).