FIELD OF THE INVENTION This invention relates to the treatment of waste oil 'Sludges (classified as hazardous by the Resource Conservation and Recovery Act of 1976) for the recovery of valuable oil products. In its more specific aspect, this invention relates to the treatment of hazardous waste oil sludges containing substantial amounts of solids and/or water for the recovery of valuable oil products which can be utilized as refinery feed stock, or otherwise refined, while producing nonhazardous aqueous and solid waste byproducts.

BACKGROUND AND PRIOR ART

For many years, waste materials such as hazardous waste oil sludges from petroleum refineries were impounded in basins with little thought to their final disposition. These waste sludges occur as American Petroleum Institute (API) and Dissolved Air Flotation (DAF) separator bottoms, tank bottoms, spills, heat exchanger sludge, secondary emulsions, slop oil, and the like. Such waste materials have been classified by the Environmental Protection Agency as hazardous wastes, which therefore restricts their removal from the generation site for treatment and/or disposal. (See for example. Industry and EPA hazardous waste No.'s K048-K052, 40 CFR, Section 261.32, 1985). It is presently acceptable to land farm the wastes using especially developed strains of bacteria for decomposition of the oil. However, the heavy metal contents of the oil left behind in the soil presents potential groundwater and controlled run off contamination to the environment. Furthermore, the oil contained in the sludge is not recovered for reuse or recycling. Presently, some refineries recycle the waste and sludges to delayed cokers. However, the addition of the waste and sludges to the coke is deleterious to coke quality and lowers the value of the coke to a lower-priced fuel coke.

There is a need for the treatment of such hazardous

waste materials with a high solids content which is capable of recovering the oil for reuse, such as a high-grade refinery feed, while producing nonhazardous waste materials suitable for conventional and safe disposal. In U. S. Patent 3,791,965 to Fitzsimons et al, the process disclosed is specific to re-refining of used petroleum products and not to waste sludges. The petroleum products treated by the Fitzsimons et al include crank case oil and transmission fluid collected at service stations and used cutting oils, rolling mill oils, and petroleum based cleaning solvents. The process is only capable of handling a raw feed stock of used liquid petroleum products with a viscosity ranging between that of mineral spirits to about SAE 60 weight oil, which is the method used for determining the viscosity of essentially solids-free liquids. The process handles only solids of small particle size and therefore, solids in excess 100 mesh (105 microns) must be removed prior to treating the feed stock.

The process disclosed in U. S. Patent 3,923,643 to Lewis et al is intended for the exclusive purpose of the purification of used hydrocarbon lubricating oil, and is directed to the removal of suspended lead and other dispersed solids from used lubricating oil. As in Fitzsimons et al, this process is not capable of handling feed stocks containing more than minute amounts of solids or of producing nonhazardous waste by-products.

Additional prior art disclosing a process for cleaning low-solids-containing waste oil include U. S. Patent 3,954,602 to Troesch et al. The process is specific to volatilizing the light oils and water only, and the organic solids residue removed by filtration from the remaining heavy oil is combusted for reheating oil treated in the process leaving no unburned matter. Other similar prior art for treatment of low solids waste oil include such patents as U. S. Patent 4,512, 878 to Reid et al for reclaiming used lubricating oils for reuse and U. S. Patent 1,951,739 to C. J. Rodman et al for treating mineral hydrocarbon oil, especially those used in electrical apparatus.

SUBSTITUTE SHEET

This invention has as its purpose to provide for the treatment of hazardous waste oil sludge, which has essentially no upper limitation in solids content and with the solids particle size ranging from submicron to several inches (i.e. up to about six inches) . Coarser materials can be treated by the process of this invention after size reduction by any suitable means such as grinding, crushing, pug mills, disintegraters, etc. The oil recovered is essentially the equivalent of cracker or cutter oil feed stock (based on the carbon chain contents, boiling point ranges, flash points, sulfur contents, etc.) and is suitable for further refining as in a cracking unit or as cutter oil feed stock. The water-free and oil-free solids are nonhazardous when tested in accordance with EPA toxicity test procedures, and therefore are suitable for disposal in a conventional sanitary landfill. Also, the waste water generated by the process of this invention is nonhazardous and therefore can be further treated in a conventional refinery water treatment system.

SUMMARY OF THE INVENTION In accordance with this invention, oil is recovered from hazardous waste oil sludge material by a series of volatilizing and condensing steps, which may vary depending on the content of the sludge. The waste materials treated in this invention typically may have a substantial oil residue content which is valuable and worth recovering, but the waste also has a high solids and/or water content which renders known recovery processes extremely difficult and/or impractical. As used herein and in the appended claims, waste oil or waste oil sludge includes the typically impounded, highly emuls ⁱ fied refinery sludges as well as continuously generated API and DAF bottoms, spills, heat exchanger sludge, secondary emulsions, slop oil, and the like. The weight percent solids in the waste oil sludge typically ranges from 5 to 65%, but can approach 80 to 90% in certain situations. Because the waste oil sludges frequently contain substantial amounts of water and/or oil (typically 40-80%) as well as solids, these high-oil and/or

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high-water containing sludges, if sufficiently fluid, are first centrifuged to separate the free oil and water from the solids. The high-solids fraction from the centrifuge, still containing substantial amounts of oil and water, and therefore still hazardous materials as defined by the United States EPA, are then subjected to a series of volatilizing and condensing steps to recover the valuable oil fraction and produce nonhazardous water and solid waste by-products. Fluid, hazardous waste oil sludges not capable of being pre-separated by mechanical means, thick hazardous waste oil sludges, the still hazardous centrifuge solids, and other oily, hazardous sludges low in water and/or oil content which are highly viscous and contain (entrained) oil and water not removable by mechanical means, such as centrifuging, are processed directly in a volatilization stage, preferably multiple stages of volatilizing (with increasing temperature gradients) , and condensing unit operation. In accordance with one embodiment of the process, a two-stage volatilization may be useful to better insure the efficient recovery of the oil and water. In the first stage units of the volatilizing (desirably indirectly heated with recycled oil-water vapor from the second stage high-temperature volatilization units) and condensing operation, the temperature and retention time is sufficient to volatilize a major portion of the water and the light end fraction of the oil which is subsequently condensed and separated in the oil water separating apparatus. The remaining, still hazardous oil-water-solids sludge from the first low-temperature volatilization unit, which typically contains the bulk of the oil and solids in the hazardous waste oil sludge feed, is then conveyed to one or more higher temperature volatilizing-condensing unit operations to volatilize and condense the remaining oil and water and produce oil free and water free nonhazardous solid waste. In a preferred embodiment, a substantial quantity of the deoiled solids is recycled and mixed with the oily feed to the second stage to prevent sludge baking, agglomeration, and heat exchanger fouling.

The centrifuge effluent or centrate and the oil and water condensate from the volatilization steps are passed to a settler or other suitable apparatus to separate the water from the oil as by gravity. Final removal of entrained water and solids from the oil is accomplished in a second separator centrifuge. The dry, deoiled, nonhazardous waste solids are acceptable for disposal in a conventional sanitary landfill, and the nonhazardous waste water can be treated by common practices in a refinery water treatment system (or a water treatment system may be incorporated into the described process) . The oil recovered by this invention is essentially the equivalent of cracking or cutter oil feed stock and is suitable for further refining in such appropriate apparatus. The water generated or recovered from the described process may contain, or have entrained, organic hydrocarbons, hydrocarbon constituents, and/or inorganic salts carried over from the final centrifuging operation. The organic content is relatively low, typically 100 ppm or lower. Because of the low organic and/or inorganic salt content, any objectional chemical oxygen demand (COD) present in the waste water can be reduced by conventional means such as trickling filtration. Thus, for water (containing approximately 100 ppm organics) recovered from the process, conventional water treatment can reduce the organics and COD to 10 ppm or lower, which is well below the recognized discharge limit.

BRIEF DESCRIPTION OF THE ACCOMPANYING nRAWING Figure 1 is a block diagram r. resenting the processing steps of the present invention.

Figure 2 is a diagrammatic representation of a preferred embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION In accordance with one embodiment of the invention, waste oil sludge is dredged or pumped from storage to a surge tank. As illustrated in Figure 1, fluid, hazardous

SUBSTITUTE SHEET

waste oil sludge (a high water/oil content) , which typically may contain about 5 up to 20 weight percent of solids, which contains adequate oil and water so that it can be mechanically separated is pumped via conduit 10 to horizontal centrifuge 14 for separation of any free oil and water. The resulting centrifuge effluent or centrate of oil and water is then discharged through line 16 to settler 18. Fluid, hazardous waste oil sludge which does not contain sufficient free oil and/or free water so that it can be mechanically separated, and wet, oily, still- hazardous solids (i.e. solids with entrained oil and water) discharged from the horizontal centrifuge 14 are pumped through lines 12 and 15, respectively, and combined at line 22 with thick, hazardous waste oil sludge (containing up to 90% solids) mechanically conveyed via line 20 to a low- temperature, oil-water vaporization apparatus 23 (preferably heated with oil-water vapor passed via line 28 from the high-temperature apparatus 24a-24z, described below) . The low-temperature volatilization apparatus is operated between about 225" and 400 ^β F at atmospheric pressure or slight negative pressure. The partially deoiled and dewatered sludge from apparatus 23 is pumped or conveyed via line 25 to high-temperature, oil-water vaporization apparatus 24a-24z arranged in series and operated between about 400° and 1150°F at atmospheric pressure or slight negative pressure, preferably between about 675" and 950"F. It should be understood, however, that the temperature for the vaporization units can vary depending on such factors as the source and composition of the hazardous waste oil sludge. The high-temperature volatilization apparatus 24a-24z may comprise one or more units connected in series, and may be, for example, a high- temperature, oil-heated, continuously-fed, mechanical drier or heat transfer piece of equipment, a fluid bed reactor operating under reducing conditions, or other conventional heat exchange kilns or roasters available to the industry. The number of such units depends upon the quantity and rate of the oil-containing material being processed. The deoil¬ ed nonhazardous solids are discharged via line 26 for

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disposal in a sanitary landfill or other suitable waste disposal site (not shown) . Where required, the deoiled solids may be recirculated or recycled via line 26a to a suitable intake point of apparatus 24a-24z to maintain the material passed through line 25 relatively friable. The oil-water vapor from volatilization apparatus 24a-24z is transferred via line 28 to a heat exchanger of low- temperature apparatus 23 as an indirect heat source, and the oil and water vapor and condensate from all volatilization operations is transferred via lines 27 and 29 to condenser or scrubber 30. The resulting condensate is passed through line 32 to the oil-water settler 18 where the condensate is combined with the oil-water centrate or effluent passed through line 16 from horizontal centrifuge 14. The settler 18 overflow, composed of oil and entrained water and solids carried over from the centrifuge 14 and high-temperature volatilization operations, is pumped via line ? - o separator centrifuge 36 where the weak emulsion, consi rig of oil, water, and very fine solids, is easily broken as by mechanical means, de-emulsifying agent, or the like. The hazardous, wet, oily solids from separator centrifuge 36 are returned to low-temperature apparatus 23 via line 37, and the oil and water centrifuge effluent or centrate is discharged through line 38 to settler 40. The oil overflow from settler 40 is sent via line 42 to storage as product for further processing, and the nonhazardous water underflow from settlers 18 and 40 is discharcad via lines 44 and 46, respectively, and line 48 to a suitable water treatment facility (not shown) , or the like, to reduce any objectionable contained organic content or chemical oxygen demand.

The process of this invention and its advantages will be apparent in the following specific Examples illustrating the preferred embodiments of the process. Samples of several hazardous waste oil sludges for Examples 1-10 were tested to determine oil recovery, recovered oil quality, and waste material characteristics. The oil recovered in the Examples is commercially valuable as cracker or cutter oil feed stock based on such factors as carbon chain

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contents, boiling point ranges, flash points, and impurity contents determined by laboratory analyses.

Example 1 Thick, hazardous, strongly emulsified (naturally occurring or from previous refinery processing) waste oil sludge (130g) containing 33.6% oil, 56.7% water, and 9.7% solids was placed in a stainless steel boat and inserted in an electrically heated tube furnace fitted with a reflux condenser and graduated collection cylinder. The sample was initially heated at atmospheric pressure to 400°F to volatilize the water and finally to 700"F to volatilize the oil. The steam and oil vapor were purged from the tube furnace by applying a slight vacuum to the discharge side of the condenser.

The condensate consisted of 70g of water and 42g of oil for a recovery of 96%. The condensed water and the solid residue (lOg) were subjected to EPA toxicity tests, and the results were as follows: mc 1

Both the waste solids and condensed water were shown to be nonhazardous by EPA leachability test standards.

This feature is extremely significant for a process of this type, because the solids can be disposed of in a sanitary landfill, and the water can be easily handled in a conventional water treatment system.

SUBSTITUTE SHEET

Example 2 Thick, hazardous strongly emulsified (naturally emulsified or from previous refinery processing) waste oil sludge (150g) containing 37.2% oil, 52.5% water, and 10.3% solids was processed in equipment described in Example 1. The condensate consisted of 75g of water and 55g of oil for a recovery of 98.5%. The condensed water and the solid residue (12g) were subjected to EP toxicity tests, and the results showed both wastes to be nonhazardous. m 1

Fluid, hazardous waste oil sludge (300g) containing 21.1% oil, 73.5% water, and 5.4% solids was centrifuged in a batch laboratory centrifuge, and the reparated oil (38g) and water (llOg) were decanted from tϊ centrifuge tubes. The thick, strongly emulsified, oily, wtc, still hazardous solids from the centrifuge were processed in the equipment described in Example 1.

The condensed water (lOOg) and oil (35g) resulted in a total recovery of 99.5%. The combined centrifuge and condensed water and the solid residue (17g) were subjected to EP toxicity testing, and tne results showed both the waste water and the solids to be nonhazardous.

SUBSTITUTE SHEET

m /i

Condensed

Constituent Water Cr 1.13 Ba 4.6 As 0.67 Se 0.30 Hg 0.005

Fluid, hazardous waste oil sludge (16,908g) containing 24.7% oil, 68.4% water, and 4.8% solids (and unknown uncombustibles) was continuously processed in a 4-inch- diameter, electrically heated (700°F) fluid bed reactor using a fluidizing gas consisting of 79% nitrogen, 20% carbon dioxide, and 1% oxygen preheated to approximately 700*F. The vaporized water and oil were, continuously condensed and collected in a recirculating packed-tower water scrubber. Prior to quenching in the water scrubber, the solids were removed from the gases leaving the fluid bed via a dry cyclone.

The condensed oil (4,110g) resulted in 98.4% recovery of the oil. The scrubber water and the waste solids (890g) were subjected to EP toxicity tests, and the results showed both the water and the solids to be nonhazardous. m i

Condensed

Constituent Water

Ag 0. 005 Pb 0.08 Cd 0. 06 Cr 0. 07 Ba 0. 06 As 0. 03 Se 0. 04 Hg Nil

Thick, hazardous waste oil sludge ( 163 lb . ) containing 20. 0% oil , 28.3% water, and 49. 1% solids (and unknown

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uncombustibles) was processed in the equipment shown in Figure 2. Heat transfer fluid is heated in oil heater 100 to 500*F to volatilize the water and then to 750"F to volatilize the oil. The heat transfer fluid was circulated via line 102, pump 104 and line 106 through the hot oil sludge processor 108 maintained at about 500" and 750 ^β F while the material was mechanically agitated with slowly rotating paddles in the processor. A return for the heat transfer fluid is provided via line 109. The oil-water vapor was then passed through line 110 where it was condensed in condenser 112, and collected in vessel 114.

The condensed oil (30 lb.) and water collected from line 116 resulted in 92.1% recovery of the oil, but the solid material 35 taken at line 118 baked into hard chunks restricting more complete volatilization. A blower at 119 releases the gases by providing a slight negative pressure to purge the oil and water vapor through the recovery system. The condensed water (45 lb.) and the waste solids (83 lb.) still containing 3.1% oil were subjected to EP toxicity tests, and the results showed the water and solids to be nonhazardous. m i

To prevent the sludge baking, agglomeration, and the heat exchanger surface from fouling as experienced in Example 5, 90 lb. of thick oil sludge as used in Example 5 was mixed in the hot oil sludge processor with recycled, ground, dry, friable waste solids taken from line 118 (Figure 2) of Example 5 and 30 lb. of sand as previously

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described in Example 5. The sand was added to increase the solids ratio and to facilitate startup. However, the sand addition and amount was optional.

Thick, hazardous waste oil sludge (90 lb.) containing 20.0% oil, 28.3% water, and 49.1% solids was mixed with dry, friable solids (60 lb.) containing 3.1% oil from Example 5 and sand (30 lb.) in the hot oil processor as previously describe in Example 5. Heat transfer fluid (first heated to 600"F to volatilize the water and 750"F to volatilize the oil) was circulated through the hot oil processor while the material was slowly mechanically agitated. The condensed oil (19 lb.) resulted in 95.5% recovery of the oil. The condensed water (25 lb.) and fluffy, friable waste solids (133 lb.) were subjected to EP Toxicity tests, and the results showed both the water and solids to be nonhazardous. m

In the following Examples 7-10, sample charges were taken from a waste sludge pit in Tulsa, Oklahoma which had been abandoned since about 1949.

Example 7

Thick, hazardous, strongly emulsified (emulsified naturally or from previous refinery processing) waste oil sludge containing approximately 27% oil, 68% water, and 5% solids was processed in an electrically heated retort fitted with a reflux condenser and graduated cylinder. The 658g sample was initially heated at atmospheric pressure to

SUBSTITUTE SHEET

400"F to volatilize the water and finally to 700"F to volatilize the oil. The condensate consisted of 450g of water and 115g of oil. Approximately 60g of uncondensed gas (determined by difference between the charge weight and the total of condensed water and oil and residual solids

[33g] weights) was combusted at the discharge end of the condenser. The condensed oil and uncondensed combusted gas resulted in 98% volatilization of the contained organic material.

Example 8 The procedure of Example 7 was followed except that the hazardous waste oil sludge charge was 754g, and contained approximately 18% oil, 29% water, and 53% solids. The processing products consisted of 218g of water, 117g of oil, approximately 17g of uncondensed combusted gas, and 402g of dry friable solids. The condensed oil and uncondensed combusted gas resulted in 98.5% volatilization of the contained orαnnic material.

Example 9

The procedure of Example 7 was followed except that the hazardous waste oil sludge charge was 417g, and contained approximately 43% oil, 30% water, and 27% solids.

The processing products consisted of 128 g of water, lOOg of oil, approximately 76g of uncondensed combusted gas, and

113g of dry friable solids. The condensed oil and uncondensed combusted gas resulted in 98.3% volatilization of the contained organic material.

Example 10

Thick, hazardous, strongly emulsified (emulsified naturally or from previous refinery processing) waste oil sludge containing approximately 27% oil, 68% water, and 5% solids was processed in an electrically heated retort fitted with a reflux condenser and graduated collection cylinder. The 643g sample was initially heated at atmospheric pressure to 400"F to volatilize the water and finally to 700"F to volatilize the oil. The condensate

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consisted of 400g of water and 112g of oil. Approximately 59g of uncondensed gas (determined by the difference between the charge weight and the total of the condensed water and oil and residual solids [32] weights) was combusted at the discharge end of the condenser. The condensed oil and uncondensed combusted gas resulted in 98% volatilization of the contained organic material. The somewhat sticky solids from the 700 ^β F volatilization step were gradually heated to 1100"F where volatilization ceased and an additional 4g of waxy material was volatilized and condensed resulting in an additional 2% recovery of the organic material and a final dry, friable solids weight of 28g.

An admixture of the solids and water recovered in the Examples 7-10 was tested for EP toxicity, and the results showed both the solids and water to be nonhazardous.

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