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WO2002060609A2 - Appareil et procede de conversion de dechets de raffinerie et de dechets a base de petrole en carburants standard - Google Patents

Appareil et procede de conversion de dechets de raffinerie et de dechets a base de petrole en carburants standard Download PDF

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Publication number
WO2002060609A2
WO2002060609A2 PCT/US2002/002551 US0202551W WO02060609A2 WO 2002060609 A2 WO2002060609 A2 WO 2002060609A2 US 0202551 W US0202551 W US 0202551W WO 02060609 A2 WO02060609 A2 WO 02060609A2
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Prior art keywords
dewatering
water
oil
sludge
catalyst
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PCT/US2002/002551
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WO2002060609A3 (fr
Inventor
Alexander P. Bronshtein
Moshe Gewertz
Vladimir M. Rozhansky
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IPSON Ltd
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IPSON Ltd
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Priority to AU2002245347A priority Critical patent/AU2002245347A1/en
Publication of WO2002060609A2 publication Critical patent/WO2002060609A2/fr
Publication of WO2002060609A3 publication Critical patent/WO2002060609A3/fr
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09C—RECLAMATION OF CONTAMINATED SOIL
    • B09C1/00—Reclamation of contaminated soil
    • B09C1/06—Reclamation of contaminated soil thermally
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/04—Dewatering or demulsification of hydrocarbon oils with chemical means
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G33/00—Dewatering or demulsification of hydrocarbon oils
    • C10G33/06—Dewatering or demulsification of hydrocarbon oils with mechanical means, e.g. by filtration

Definitions

  • the present invention relates to the process of making a useable product out of refinery and other petroleum based sludge, bottoms and/or used lubricants with minimum environmental impact and to using waste of type slow moving emulsions and suspensions, containing organic matter and water with dissolved substances and suspended particles.
  • the present invention also provides an apparatus for producing useful and standard fuels from refining and petroleum-based waste.
  • U.S. Patent 4,624,417 of Gangi, et al. discloses a method for converting sewage sludge into various energy sources such as steam or methane gas and non-energy by products such as cement board, gypsum fiberboard. and agricultural products.
  • U.S. Patent 4,750,274 of Erdman, et al. discloses a method for bettering the sludge drying by means of large scouring particles addition.
  • the scouring particles remove the particulate residue from the surfaces of heat exchanger, where the sludge is heated.
  • the heat transfer is also intensified.
  • U.S. Patent 4,897,205 of Landry is directed to petroleum sludge treatment by the use of steam and a re-circulating solvent with the purpose to decrease their viscosity and as a next step to separate the solid and the liquid components by settlement.
  • U.S. Patent 4,927,530 of Ueda, et al. is directed to sludge treatment in the special tank by the use of anaerobic bacteria.
  • GB Patent 2218256 and U.S. Patent 4,906,409 of Leister discloses a method in which sludge is dried in a fluid bed of preheated glass frit suspensed in nitrogen. The dried sludge and glass is conveyed pneumatically (by nitrogen) to the verification device.
  • U.S. Patent 4,990,237 of Heuer, et al. discloses a method for oil recovery from waste oil sludge (pump-able, low viscosity, high oil and/or water-content sludge) by centrifugation of this type sludge. After that the centrifuge solids with low oil and water content are heated to volatize the contained water and oil. The oil and water are condensed and separated by settling. The separated oil is centrifuged again and refined; the solids can be disposed.
  • U.S. Patent 5,022,992 of Looker discloses an apparatus for sludge separating by flotation for the floatable sludge.
  • U.S. Patent 5,246,599 of Aicher discloses a method and arrangement for sewage sludge treatment in closed system, where the .treatment steps are connected by continuous passages in a closed system.
  • the sludge is dried, converted by 250-350°C and finally sintered at least by 1250 C.
  • the vapors removed in the drying stage and in conversion stage are condensed.
  • U.S. Patent 5,259,945 of Johnson, et al. is directed to the bottom waste processing by means of the vapor rapid stripping and by treatment of the heavy part of waste in a pyrolytic reactor for producing vapors, gases and solid residue, which may be used as fuels.
  • U.S. Patent 5,271,851 of Nelson, et al. discloses a treatment system for refining oily sludge.
  • the sludge is mixed with a particulate filter aid and with solvent selected from refinery products.
  • the mixture contacts with a plate filter.
  • a mixture of oil, water and solvent is produced as a filtrate.
  • the filtrate is separated into an oil and water fraction.
  • the oil fraction is directed to refinery.
  • the produced water is routed to a refinery water treatment system.
  • the filter coke residue is washed with a solvent, stripped to remove hydrocarbons and is removed for disposal.
  • U.S. Patent 5,324,417 of Harandi discloses a method for refinery sludge and slop oils upgrading over hot equilibrium catalyst removed from FCC regenerator.
  • the hot catalyst demetallized and/or demulsifies sludge and slop streams in an auxiliary reactor and converts the sludge and slop oil hydrocarbons to more light products.
  • U.S. Patent 5,389,234 of Bhargava, et al. discloses a method for waste sludge disposal in a delayed coking process.
  • the waste at first is diluted with light hydrocarbons produced by delayed coking (naphtha or gas oil) to minimize fouling and foaming.
  • the mixture stream is heated; the water and the light hydrocarbons are evaporated.
  • the more heavy residue stream is heated to a coking temperature and is introduced into a coking drum.
  • U.S. Patent 5,428,904 of Rutz discloses a method for drying sewage by a gas with temperature up to 50°C.
  • the drying gas itself is reconditioned by reducing its moisture in a separate circuit and is returned to the start of the process.
  • the gas-drying agent (a hygroscopic material) is regenerated by withdrawing moisture there from.
  • U.S. Patent 5,466,383 of Lee is disclosed to treating dried sludge, also containing heavy metals.
  • This process comprises indirectly heating the sludge in the absence of oxygen, up to temperature 300-550°C for organic material volatilization and heating the residue up to 750-1000°C together with steam for the non-volatile organic material gasification.
  • the heavy metals remain in the ash as metal-sulf ⁇ de complexes, which aren't soluble in acidic water.
  • U.S. Patent 5,573,672 of Rappas, et al. discloses a process for separating extractable organic material intermixed with solids and water by dewatering the mixture with dehydration additives in common with organic solvent and following separation the organic solvent containing extractable organic material from the solids and hydrated additive.
  • U.S. Patent 5,580,391 of Franco discloses a process for the thermo-chemical cleaning of storage tanlcs by combined action of an organic solvent and the generation of nitrogen gas and heat, whereby produced heating in city, agitation and flotation of the fluidized sludge and its transfer to tanlcs or desalting units. It is assumed the matter can be reintroduced after that in the usual refining flow.
  • U.S. Patent 5,681,449 and Japan Patent of Yokoyama, et al. discloses a method for treating an organic material containing solid sludge with water by means of heating the material up to 150-240°C by pressure to obtain a fluidized sludge and processing the fluidized sludge up to 350°C by 30-200 atm to convert the organic material to oil and after discharging separating oil from rest.
  • U.S. Patent 5,827,432 of Huhtamaki et al. is directed to sludge dewatering by electrically ionizing or by ultrasound treating and adding coagulant to the sludge to effect coagulation.
  • RU Patent 2106313 of Fokin, et al. discloses a method of drying petroleum sludge under vacuum at heat carrier temperature 120-140 C. Drying is performed in three steps: stripping water and part of sludge hydrocarbons, continuously feeding organic solvent (toluene, gasoline fraction etc.) and stripping excess solvent.
  • U.S. Patent 5,882,506 of Ohsol, et al. discloses a process for recovering oil from refinery waste emulsion by adding a sufficient amount of a light hydrocarbon diluent to the emulsion to lower its viscosity and specific gravity. The diluted emulsions are subjected to flashing at emulsion-breaking conditions after the oil is recovered.
  • U.S. Patent 5,961,786 of Freel, et al. discloses a apparatus for a fast pyrolytic system. The feedstock, non-oxidative transport gas and inorganic particulate heated material are rapidly mixed, than transported upward through an entrained-bed tubular reactor. The system includes a cyclonic hot solids re-circulation system and the vapor quenching system.
  • U.S. Patent 4,342,645 of Fletcher et al. discloses a method of used lubricating oil re-refining by distillation to remove a volatile forecut and by further distillation with re-circulation to obtain the desired fractions of lubricating oil products while reducing the vaporization temperature.
  • the recycle reduced coking and cracking.
  • the used equipment is evaporator of three stages. The gasoline and the fuel oil are removed in the first and second stage evaporators. A light lube oil fraction is obtained then by distillation with a third stage wiped-f ⁇ lm evaporator. A heavy lube fraction is obtained by distillation of the bottoms with evaporator too.
  • U.S. Patent 4,435,270 of Audeh is directed to reclaiming usable stock from used lubricating oil by passing the used oil through a bed of oil shale.
  • the shale removes impurities from the used oil.
  • the shale is then heated to convert the kerogens to shale oil in the presence of hydrogen donor compounds contained in the lubricating oil remaining in the shale. These enhance hydrogen transfer during shale oil production.
  • U.S. Patent 4,512,878 of Reid, et al. discloses a method for used-oil re- refining involving: heat soaking the used oil; distilling the heat soaked oil; passing the distillate through a guard bed of activated material; hydro treating the distillate guard bed teeated under standard hydro treating conditions. If the used oil contained water and/or fuel fraction the used oil may be dewatered and defueled prior to heat soaked.
  • U.S. Patent 4,833,185 of horrini is directed to utilizing the sludge obtained from reclaiming lubricating oils by treating with acids or solvents.
  • the sludge utilizing is proposed by the addition of elastomers and hardeners to obtain a compound usable in conjunction with bituminous conglomerates.
  • FR. Patent 2690924 of Digilio discloses a process for recycling of contaminated oil, particularly for re-processing lubricants comprises heating in autoclave reactor the used oil (lubricant) in common with added clarifier clay, 1-2% of water with dissolved S-based catalyst and 2% of filtration aid such on a diatonite. The heating temperatures are 100-150°C and 300-320°C for 2 hours. After that the product is distillated during 3 hours, filtered by pressure, treated repeatedly with clarified clay, catalyst in water, filtration aid and distillated.
  • Patent 4240860 of Moskau is directed to creation apparatuses for physical-chemical treatment of used water-lubricant cooling emulsions, including a mobile cracking.
  • U.S. Patent 5,384,037 of Kalnes discloses a process for production of hydrocarbons from waste lubricant by contacting waste lubricant stream with a hydrogen-rich gaseous stream in the flash conditions and producing a hydrocarbonaceous vapor stream comprising hydrogen, admixing the stream and contacting with a hydrogenation catalyst at hydrogenation conditions, production the hydrocarbon products.
  • U.S. Patent 5,458,765 of West discloses a process of drying and removing solids from waste oil includes heating up to temperatures 180-200°F, adding of aqueous solution of carbodihydrazide and emulsifier. After that the precipitated solids and water are separated from the liquid hydrocarbon.
  • U.S. Patent 5,582,271 of Mielo is directed to removing moisture, air and dirt from lubricating oil by apparatus contains two plates interposed and two flows of lubricant oil superimposed vertically by plates.
  • the upper flow contains gas bubbles and the lower flow contains water and heavy particles. The two flows settle from water and heavy particles in a tank.
  • DE. Patent 19716436 of Matschiner is directed for used cooling lubricants reprocessing comprising: treating the lubricants with peroxo-di-sulphuric acid or their salts at 50-90°C, concentrating the sulphate-containing aqueous phase liberated from organics. The concentrate is used for electrochemical production of peroxo-di- sulphate and the water is recycled back to the process.
  • U.S. Patent 5,672,277 of Parker, et al. discloses a method extraction of water by means of water-sorbing material that covers an inner surface of bag and presents in the bag as filaments.
  • U.S. Patent 5,676,711 of Kuzara discloses a process of conversion used oil to a low-sulfur diesel fuel processing the used oil with coal as an oil-coal slurry by 850°F and ⁇ 100 atm in a time more than 1 hour.
  • U.S. Patent 5,755,955 of Benham, et al. uses a hydro-cracking process with preliminary addition to the feed coke as an inhibitor and iron compound.
  • U.S. Patent 5,938,935 of Shimion discloses method and apparatus for purifying and treating cooling agents and/or lubricants used in the metallurgical industry. The solid particles are removed from the liquid by sedimentation on the plates, which are placed in specific manner, and additionally by magnetic force.
  • U.S. Patent 6,013,174 of Kovacs is directed to remove ash-forming contaminations from used oil by adding a demulsifier, heating up to temperature 190- 200°F, separating the used oil in demulsified used oil, water and sediment layers, heating the demulsified oil up to 500-650°F, cooling the heat-treated oil, recycling 10- 30% of this oil to demulsified used oil.
  • Patent 4240860 June 09, 1994; Kalnes T.N. U.S. Patent 5,384,037, June 29, 1993; West P.E. U.S. Patent 5,458,765, Oct. 17, 1995; Mielo A. U.S. Patent 5,582,271, July 3, 1995; Matschiner H., Rehbock B. DE Patent 19716436, Aug. 13, 1998; Parker S.C., Cubert R.M. U.S. Patent 5,672,277, Oct. 17, 1994; Kuzara J.K., Klinger L.D. U.S. Patent 5,676,711, Feb. 21, 1996; Benham N.K., Praden B.B., Roy M. U.S. Patent 5,755,955, Dec. 21, 1995; Shimion W. U.S. Patent 5,938,935, Oct. 17, 1999; Kovacs G.L. U.S. Patent 6,013,174, Jan. 11, 2000.
  • the primary object of this invention is to provide a process and apparatus able to handle variable waste loads in an economically viable manner.
  • Fig. 1 represent a flow diagram describing one embodiment of the apparatus and process of the present invention, and comprises of a dewatering mixer unit (1), a first sieve (2), a dryer (3), a reactor (4), a second sieve (5), a regenerator (6), a fractional column (7), a flow-forming chamber (8) and a blower (9).
  • Fig. 2 represent a flow diagram describing a second embodiment of the apparatus and process of the present invention, and comprises of a dewatering mixer unit (21), a first sieve (22), a reactor (23), a second sieve (24), a regenerator (25), a fractional column (26), a flow-forming chamber (27) and a blower (28).
  • Fig 3. represents a diagram detailing the inner workings of the reactor for the petroleum-based waste, the reactor (41), comprising a heating jacket (42), a set of hoppers for the catalyst (43), a plurality of mixing elements (44), a petroleum-based waste charge pipe (45), a pipe for skimming vapors evacuation (46), pipes for cracking gases and vapors evacuation (47), pipes for cracking gases and vapors evacuation (48), a chamber for gas-vapor and solid product separation (49), a heat gas distribution pipe (50), and burners (51).
  • the invention provides the process of making a useable product out of refinery and other petroleum-based sludge, bottoms and used lubricants with minimum environmental impact.
  • the treatment relates to the processing of slow moving emulsions and suspensions, containing organic matter and water with dissolved substances and suspended particles.
  • the overall process for treating the petroleum-based wastes comprises of the following steps: a. removing the water by the use of solid grain dewatering materials derived from industrial waste or recycled materials (oil shale ash, FCC spent catalyst with the addition of lime, coal ash etc.); b. removing the water from the petroleum-based waste by water selective sorption into the dewatering additives, as well as protection of the dewatering additives from contamination by oils by the controlled introduction of the additives in accordance with the moisture' of the raw material and with the kinetics of the water adsorption by the used additives; c. recycling the dewatering additives while the adsorbed water is evaporated without expulsion thereby resulting in elimination of complicated and expensive equipment for the operation; d.
  • the peteoleum-based sludges generally contain, up to 70% water. For example, in the samples that has been taken from sludge reservoirs at one refinery of the water content ranged within 57-68%.
  • the sludge also contained 15-25% oil and 15-20% mineral particles.
  • the lubricants generally contain moisture levels up to 5% water with mineral particles having a content up to 3%.
  • the sludge and used lubricants are stable oil-water emulsions and the mineral particles are suspended in the emulsions. The components of the sludge exhibit insignificant levels of settling, and therefore pose problems, for the dewatering step.
  • dewatering materials An additional problem regarding the use of dewatering materials is that once the dewatering materials and peteoleum-based waste are mixed, both the water and oils are adsorbed. As a result the water adsorption capacity of the dewatering additives is decreased and after several cycles becomes negligible. So, the dehydrating materials (CaO, CaCl 2 , A1 2 0 3 , silica gel, etc.) are added to watered material and mixed. However, these dehydrating materials rapidly lose the ability to adsorb, and at the same time, cannot be recycled. Hence, the overall consumption for dehydrating materials is increased.
  • the present invention bypasses these problems by creating a situation of selective adsorption of the water from the oil emulsion, while simultaneously utilizing inexpensive and reusable materials, by using solid dewatering recyclable grain materials.
  • the present invention is able to achieve selective adsoiption due to the adsorption kinetics of the water and oil components.
  • the adsorption capacity and rate is higher for the water component than for the oil component. So if the dewatering additive is linked to a variable feed mechanism then the optimal rate of application can be calculated.
  • the advantage of this is that all of the additives are not applied at once and the water will be completely adsorbed while the oil layer persists untouched.
  • the dewatering material can then be introduced depending on the program developed and is changed by varying the screw-feeder rotation speed.
  • the present invention also provides the procedure to determine the adequacy of a given material as a dewatering additive by the petroleum-based processing. So some by-products of other processes were also found to be suitable dewatering additives. These by-products include:
  • oil shale ash oil shale coke-ash residue after the oil shale thermal processing - half-coking or retorting, gasification, etc.;
  • Modified bentonite, marls, sepiolite, grain materials and some cellulose-contained materials that are formed in the presence of an oxidant are suitable and are of low cost. These and other like materials adsorb not only water selectively, but also oils. However the selective adsorption of water can be achieved by the procedure of the present invention.
  • the oil shale ash adsorption capacity to water is 65-70% on the mass.
  • the oil shale coke-ash residue adsorbs up to 55% water.
  • the grain material Sepiolsa (98%, 0.5-6.0 mm) includes sepiolite 80%, dolomite 15%, other materials 5% and sorbs up to 90% water.
  • the dewatering grain material granularity ranges within 1.0-6.0 mm that allows for separation of the material from the dewatered raw matter, and its mineral particles.
  • the size of the mineral particles in processed peteoleum-based waste is generally smaller than 100 ⁇ m. Therefore, variants of the conditions of the dewatering stage can be used depending on the dewatering material granularity.
  • Variant 1 the dewatering material is coarser than the mineral component in the raw material and is separated after tire water adsorption
  • the dewatering material is introduced into the mixer in a controlled manner, where the peteoleum-based waste is located, and the water is adsorbed under suitable conditions.
  • the mixture then consists of coarse dewatering particles impregnated by water, and the dewatered raw material.
  • the raw material is sludge
  • the dewatered matter has two components : the mineral (the sludge mineral particles) and oil component.
  • the mineral-oil particles can stick together and form small aggregates. But the aggregates aren't durable and easily break up. In any event all particles can be efficiently separated by sieving (using a wire sieve) due to the particle size of sludge are less than 1 mm.
  • the experiments have shown if the dewatering particles size is 1.5-2 mm and more they can be separated without problem.
  • a raw material which is a liquid lubricant
  • the matter represents a mixture of coarse dewatering particles saturated by water, and the dewatered liquid oil with dispersed small particles.
  • the dewatering material particles are easily separated from dewatered oil.
  • the peteoleum-based raw material is directed to the following processing.
  • the dewatering material is directed into a jacketed dryer, dried and recycled to the raw material ready to be used again to dewater.
  • the steam formed during drying is directed into the catalyst regenerator and is treated there at a temperature of ⁇ 750 C.
  • the organic substances which can be captured by steam (contained in the adsorbed water and other) are decomposed and burned at this temperature.
  • the amount of captured organic substance by this operation does not equal more than 0.5% of the total. This mechanism may be used to successfully remove the organic based wastewater in form of pure and disinfected steam therefore avoiding the expulsion of the watered matter by the heating process.
  • Variant 2 the dewatering material cannot be separated after the water adsorption and heating in common dries all matter. This procedure of drying also runs without the danger of the expulsion of matter by heating, because of the adsorbed water evaporation from solid particles. In this case the water-oil emulsion is desteoyed by water adsoiption prior to evaporation. This separation of the emulsion is the key to successful evaporation.
  • the steam formed contains organic vapors at concentrations in the range of 1-2%, which are then directed into the catalyst regenerator. Here they are burned, and reused, giving additional heat to the process.
  • This procedure can be used for example if the dewatering material is oleo- phobic. In this case the dewatered petroleum-based matter is heated up to higher temperatures. Consequently, this saves heat in the next stage of processing. After the mixture has undergone heating and drying, the coarse dewatering material is separated by sieving, and once again recycled for water removal. The operations of mixing and drying can be carried out in one mixer-dryer with jacket heating.
  • This procedure is also used if the dewatering material is not needed in large amounts because it does not disturb the subsequent processing of the dewatered raw matter while in catalytic cracking conditions.
  • the present invention provides procedures in which the oil shale ash and the coke-ash residue are catalytically active under hydrocarbon catalytic cracking conditions.
  • the natural combination of the aluminum silicate matrix with calcium oxide creates the catalytic activity. Therefore the oil-shale ash used as a dewatering material can also be dried in common with the raw material. In the later stages it is used as a catalytically active material, being heated up to 450-500 C and then separated after the cracking process.
  • Variant 3 the dewatering material is finely grained and cannot be separated from the dewatered raw matter particles. This procedure is possible if the dewatering material is also catalytically active and can be used as a catalyst on the next stage of the process. This material, as in the previous example, can be the oil shale ash.
  • the dewatering and catalytically active material is mixed (under controlled conditions) with the peteoleum-based waste, the water is then adsorbed by the dewatering material, then the whole mixture is heated up to the drying temperature, and subsequently the dewatered material is directed into the reactor.
  • the reactor After the dewatering stage the reactor processes the raw material.
  • the reactor carries out several operations as enumerated below.
  • the raw material is skimmed in conditions depending on the process objectives. If the objective is to produce maximum gasoline yield, the cut off point for heating is up to 210 C and after that the residue is cracked. If the objective is to produce maximum gas-oil yield the cut point is 350°C.
  • the heat for the skimming is provided by the addition of the required amount of the hot catalyst.
  • the catalyst serves as a direct heat carrier. If a surplus of heat is formed in the regenerator, (by sufficient cracking coke yield) the matter to be skimmed is jacket heated by the regenerator flue gases.
  • the treated matter is transported (by means of the mixing elements of the reactor) into its activation zone.
  • the hot catalyst is added into the activation zone for mixing with the skimmed material, at temperatures of 350-380°C.
  • the lubricant additives and acidic sulfur and oxygen compounds of the sludge are decomposed.
  • the activated matter is then transported into the cracking zone where it is teeated by the catalyst at a temperature appropriate for catalytic cracking.
  • the preliminary adsorbing of the organic matter into the catalyst grains, and the subsequent activation of matter increases the intensity of the process thereby reducing the total heat consumption.
  • the vapors and gases formed move out from the reactor and enter into the vortex chamber where they are cleaned to remove the captured catalytic dust.
  • the dust is directed into catalyst regenerator and recycled to cracking process.
  • the cleaned vapors and gases are separated by means of the fractional column, the gases are cooled, and the vapors condensed and cooled.
  • the catalyst with the addition of formed coke (that deposits in the catalyst grains) is removed from the reactor by means of the same mixer elements performing the task of both mixing and discharging.
  • the removed catalyst is directed into the fluidized bed regenerator, where the coke is burned out, and the catalyst grains are heated up to 750°C.
  • the regenerated and heated catalyst is recycled to the raw materials, to act as a catalyst and as a heat-carrier.
  • Suitable catalytically active materials are generally spent materials from other processes such as: oil shale ash, FCC spent catalyst, sweet clays, and spent clays after their treating, series of specially prepared materials, including a silica-alumina, and calcium oxide containing additives. Presence of the calcium oxide also helps with the decomposition of the additives in the lubricants and to neutralizing and decomposing of the acidic components that may be present in the peteoleum-based sludge and waste. Oil shale ash contains suitable combination of the silica-alumina (up to 30%), and calcium oxide and carbonate. This composition makes it possible to carry out the thermo-catalytic cracking and to also prevent the sulfur oxide emission (into the atmosphere), by the coke burning out in the catalyst regenerator. This combination allows for the cracking reaction, while still considering environmental safety.
  • the acid sprayed clays (and in particular the activated montmorillonite acid) are useful materials for the catalytic cracking reactions.
  • the activated zeolite granules activated by acid are also suitable for the cracking process.
  • a silica-alumina FCC catalyst in mixture with activated clays is found to absorb the metals.
  • the coarse catalytically active materials are used. They can be separated from the sludge dust during the sieving stage, after the reactor stage, or after the regenerator stage, depending on further application the sludge mineral component
  • the dust mineral component of a refinery sludge coated with coke was tested with a positive result as a substance useful to the cement industry. Its coke gives an added heat in the cement kiln, and its particles size and composition (Si0 , A1 2 0 3 , CaO, Fe 2 0 3 , etc.) are acceptable for cement production. It is clear that the dust and coarse catalyst separation after cracking process are suitable for this alternative application, when the dust particles are coated with the coke. In other cases it is reasonable to burn out the coke in the dust to use the dusty minerals depending on their composition and properties as filling or covering materials, etc. When processing used lubricants the dusty mineral component amounts to less than 2-3%. The mineral component contains metals and metals oxide particles, and after their separation from the catalyst they can be used in metallurgy.
  • the gases formed during sludge processing basically contain hydrogen, hydrocarbons, hydrosulfide and a very small amount of carbon monoxide and dioxides. All of the gases are burned in the catalyst regenerator. If the oil shale ash is used as a catalytic active material the sulfur oxide formed by the burning of H 2 S (like by the coke burning) is caught by the calcium oxide and calcium carbonate contained within in the oil shale ash. The emission of sulfur oxide is prevented by using a plant (20 kg/h) operated at temperatures of 750-800 C in the regenerator. In other cases the materials containing calcium carbonate are added to aid in the trapping of the S0 2 . Their presence, positively affects the cracking process and the desulfurization of the formed fuels. The heat created from the burning gases increases the heat potential of the process, where part of the heat obtained in regenerator is used for raw material dewatering.
  • the watery petroleum-based waste (sludge, etc.) is mixed with the dewatering additive, which is introduced by the controlled regime into horizontal mixer 1 with paddle mixing elements and jacket heating possibility.
  • the dewatering additive After the water adsorption by the additive grains the matter is separated by the wire sieve 2, into coarser dewatering grains and other matter that looks to be in the case of sludge, as small mineral particles oiled by petroleum based material.
  • the dewatering grains are dried by the jacket heating dryer-mixer 3 and recycled to the raw material dewatering stage.
  • the formed vapors are directed in the catalyst regenerator 6.
  • the second variation in Fig.2 shows the vapors formed in the dewatering mixer 21 can be directed to the regenerator 25 if the sludge is dewatered and the drying temperature is 100-150°C. If the temperature is more than the or if waste is comprised of used lubricant oil and dewatered, the formed vapors are directed to the system of condensation, cooling and oil-water separation. The separated water is teeated in the catalyst regenerator 25.
  • the dewatered sludge or lubricant is directed into reactor 4 (Fig.l).
  • the reactor is a horizontal mixer with paddle mixer and discharge elements (Fig.3). It is equipped with heating jacket 42 (Fig.3) and system able to control hot catalyst introduction 43.
  • the system consists of a bunker and screw feeder with variable rotation speeds to three heating zones of the reactor.
  • the catalyst-feeding regulator controls the screw feeder rotation speed, which corresponds to the temperature in each appropriate zone.
  • the petroleum-based material is carried out with cut off point up to 350°C. As a rule this is controlled by means of the added hot catalyst.
  • the vapors are evacuated through the fractional column 7 (Fig.l) that separate two fractions: (a) up to 210°C (gasoline) and (b) up to 350°C (gas oil).
  • the non-hydrocarbon component are decomposed (such as additives in the lubricants, etc.) and the activation of all remaining reaction matter (catalyst impregnated by remainder of the processed material) is carried on. Furthermore, the hot catalyst is also added as a direct heat carrier.
  • the catalytic cracking of the remaining material is carried out and the formed vapors and gases are evacuated through the fractional column 7.
  • the coke covered catalyst and mineral part of the processed sludge are discharged from the reactor 4 by the same mixer elements and are separated by means of sieves 5 (Fig.l).
  • the catalysts that are coarser are directed to the fluidized bed regenerator and from this are recycled to the reactor.
  • the dusty mineral part of the processed material, also coke covered is not separated from catalyst and is directed into the regenerator. After the coke is burned out, the catalyst and the mineral components of the process material are separated.
  • the flue gases from the regenerator 6 are evacuated through the cyclone or vortex chamber that cleans the gases from the dust more effectively.
  • the flue gases heat is utilized for dewatering and the dewatered materials processing.
  • the peteoleum-based waste processing can be organized as a batch process. Its advantage lies in the ability of the process to carry on the basic operation on the principle of "all operation in one reactor". It means by one jacket heated reactor- mixer the dewatering stage can by carried out, and after production of enough of the dewatered matter, thermal processing (skimming, reaction matter activation, catalytic cracking) can be realized in the same reactor (one after another). Only the catalyst regenerator must be operated in continuous regime of treating the coke-covered catalyst accordingly to the reactor output (the regenerator must be provided for the feeder-bunker). The batch process is convenient for the small plants processing up to 2-3 tons per hour on the basis of raw materials formed in the concrete region. 6. Examples
  • the equipment used for the process development and testing includes:
  • the metal content in the ash from the sludge, (mass %>) is: vanadium 0.2 nickel 1.1 iron 12.3 ⁇ silicon 7.45 aluminum 10.71 sodium 1.31 calcium 14.7.
  • the oil shale ash was used as a dewatering additive and as a catalytically active material.
  • the oil shale ash composition (mass %) is:
  • Oil shale ash has a water adsorption capacity of 64.9%.
  • the sludge dewatering was carried out in a batch regime feeding the sludge, which allows for reliable water selective adsorption during the controlled introduction of the dewatering grain matter.
  • the cell (zone) model is suitable for a mathematical description of the materials flow.
  • the total volume (of the mixer) can be represented as a series cell with individual types of flow in each cell.
  • the Markov's chains is employed for the distribution process in the cells. Assuming all cells have equal volumes V; and the material passed through them at a rate Q then:
  • the partially dewatered matter of the new water concentration enters into the first zone.
  • the dewatering sorbent must be introduced in sufficient amounts that conform to a new water concenteation.
  • V(t) V ⁇ +V 2 total reactor volume [1]
  • the sludge contains 60% (vol.) of H 2 0. 2.
  • the adsorbent is capable of adsorbing 65% of H 2 0 (mass). Therefore, the adsorbent bulk density 0.7 should be taken into consideration when calculating the effective volume percentage of adsorption. It will be assumed therefore that the adsorbent is capable of adsorbing 45.5% of H 2 0 (vol).
  • the adsorbent throughput is decreased linearly from an initial value of Q S; o to 0 so that the total volume of the injected adsorbent would constitute 133.3% (vol.) of the sludge (90% of the sludge mass).
  • Q s (t) are a continuous-time volumetric throughput function (the discretization is precise, since ⁇ « T), and its integral on [0,T] determines the total volume of the injected adsorbent.
  • the volume of the oiled adsorbent (which has adsorbed a certain volume of organic components) can be easily calculated.
  • Vw(t) be the volume of water in zone 1 (it is determined from the concenteation C ⁇ (t) and the volume V ⁇ (t)). Assume that Vt e S ; Vyy (t) - 0.455 • ⁇ • Q s (t) ⁇ 0 , i.e. the condition does not hold for a certain
  • the total volume of the oiled adsorbent is obtained by the following discrete sum (which can be approximated by a continuous-time integral):
  • V M - ⁇ v w (t) -0.455 -A - Q g (t) tes
  • the linear function Qs(t) can be replaced with a' non-linear (e.g. an exponential) one with respective parameters.
  • a' non-linear e.g. an exponential
  • ⁇ 1 sec is the agreed interval of discrete time between measures.
  • Ni 5.5 liters - initial sludge volume in the injection zone 1;
  • N 2 16.5 liters - initial sludge volume in zone 2;
  • N 22 liters - initial total sludge volume.
  • the zones of the total charge volume (22 liters) are selected to maintain a ratio of
  • the separated two portions of the dewatered sludge were charged into the reactor- mixer and heated up to .350°C by the addition and mixing of the catalytic active material, which was previously heated up to 750°C. It was assumed that the catalytically active material heated the oil shale ash. The catalytically active material had a granularity of 1.4-2.8 mm. By heating the mixture up to 350°C the oil component was skimmed successfully.
  • reaction matter was activated by temperatures of 375°C (by added hot catalyst) and was catalytically cracked by the addition of the next portion of the catalytically active material (oil shale grains) heated up to 750°C.
  • the catalytic cracking average temperature was 480°C.
  • product yield was, mass %: water 59.2 oil 19.4 solid product
  • the produced oil conforms to standard for fuel oil of type light mazout.
  • Sepiolsa (sepiolite 80%, dolomite 15%, others 5%) was used as a dewatering additive. Its bulk density is 0.65 kg/liter; 0.5-6 mm is the grain size of 98% of the particles. Sepiolsa is not selectively water adsorbent and under ordinary conditions adsorbs oil as well. Therefore, controlled introduction was applied. The dewatering process calculation was carried out by the same algorithm that by Example 1, also talcing into consideration the other properties of Sepiolsa. The mixer (with a volume of 45 liters) was charged with 30 liters of the used oil. After the completion of the dewatering stage the water concenteation in the used oil was 0.2% and the oil content in the sorbent was ⁇ 0.1%.
  • the watered Sepiolsa was separated from the oil by sieve and dried. Its adsorption capacity was not affected due to the drying and reuse.
  • the dewatered used lubricant was charged into the same reactor-mixer and skimmed using temperatures up to 350°C (by means of added FCC E-catalyst with admixed 5% of the teeated clay preliminary heated in the catalyst regenerator up to 750°C).
  • the remaining reaction matter (the catalyst impregnated by the material) was activated by temperatures of 350°C.
  • the next step uses the regenerated FCC E- catalyst with admixed regenerated spent clay (750°C), which is added to the reaction matter and the remaining used lubricant material that was cracked in catalytic cracking conditions.
  • the liquid phase cracking residence time was five minutes; the vapors average contact time with the catalyst was four seconds
  • the product yield was, mass %: water 1.6 oil 85.2 gas 6.5 coke 5.6 mineral! ? 1.1.
  • the produced gas oil properties are: density (15°C) 0.868 metals, ppm: viscosity(40°C),cSt 3.3 phosphorus 0.00 sulfur 0.1 calcium '0.00 distillate up to magnesium 0.00

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Abstract

La présente invention concerne un procédé économe en énergie permettant de traiter des déchets à base de pétrole, notamment les boues, les dépôts de fond ou les lubrifiants usagés, et de les convertir en produits finis utilisables, tels que du gaz et des fractions de gaz/huile. Ce procédé ne produit pas des sous-produits entraînant des déchets comme les eaux usées polluées, les asphaltèniques lourds et les sous-produits du goudron. Au lieu de cela, ce procédé permet d'éliminer l'eau par une adsorption sélective au moyen d'additifs de déshydratation. Ces additifs de déshydratation sont recyclés et peuvent être réutilisés. Après écrémage du volume déshydraté, le produit restant est traité par craquage thermocatalytique. Quelques uns des matériaux actifs utilisés dans la réaction de craquage sont des produits de déchets d'autres procédés. Le gaz et les fractions de gaz/huile obtenus par ce procédé sont conformes aux spécifications standard. Ce procédé utilise un équipement rentable, dont une grande partie est produite de manière courante. Le procédé et l'appareil selon la présente invention offrent une solution pour le traitement des déchets de raffinerie et des déchets à base de pétrole, et pour la production de carburants liquides standard et utiles.
PCT/US2002/002551 2001-01-29 2002-01-29 Appareil et procede de conversion de dechets de raffinerie et de dechets a base de petrole en carburants standard Ceased WO2002060609A2 (fr)

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Cited By (2)

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ES2338207A1 (es) * 2006-09-18 2010-05-04 Pablo Martin De Julian Proceso de recuperacion de aceites lubricantes usados con arcillas y centrifugacion.
WO2015132807A3 (fr) * 2014-03-06 2016-03-24 Shubho-Tech Private Limited Appareil et procédé pour éliminer l'eau (à la fois liée et non liée) des boues et des émulsions de pétrole par application de chaleur seule, en vue de récupérer les hydrocarbures entiers qu'elles contiennent

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US20040040174A1 (en) * 2002-08-29 2004-03-04 Wayne Childs System and method for processing sewage sludge and other wet organic based feedstocks to generate useful end products
AR058345A1 (es) 2005-12-16 2008-01-30 Petrobeam Inc Craqueo autosostenido en frio de hidrocarburos
CN100368053C (zh) * 2006-01-20 2008-02-13 中国矿业大学 疏水团聚造粒助滤的低灰煤脱水方法
US20100179080A1 (en) * 2006-09-18 2010-07-15 Martin De Julian Pablo Process for recovering used lubricating oils using clay and centrifugation
US8299001B1 (en) 2006-09-18 2012-10-30 Martin De Julian Pablo Process for recovering used lubricating oils using clay and centrifugation
EP3299405A1 (fr) * 2008-10-28 2018-03-28 Xyleco, Inc. Traitement de matériaux
DE102009043537B4 (de) 2009-09-30 2012-03-22 Siemens Aktiengesellschaft Verfahren und Anordnung zur Bestimmung von Zell-Vitalitäten
RU2490305C1 (ru) * 2012-07-06 2013-08-20 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Уфимский государственный нефтяной технический университет" Способ переработки устойчивых нефтяных эмульсий и застарелых нефтешламов
CN105295877B (zh) * 2015-10-10 2018-03-13 中国石油天然气股份有限公司 一种利用油渣或含油污泥配制的堵水剂及其制备方法
RU174039U1 (ru) * 2017-01-09 2017-09-26 Федеральное государственное бюджетное образовательное учреждение высшего образования "Волжский государственный университет водного транспорта" (ФГБОУ ВО "ВГУВТ") Судовой сепаратор нефтесодержащих вод
IT202000001357A1 (it) * 2020-01-24 2021-07-24 Itelyum Regeneration S P A Valorizzazione dei sottoprodotti di un processo di rigenerazione di olii usati
CN112710002A (zh) * 2021-02-04 2021-04-27 国家电投集团贵州金元绥阳产业有限公司 一种利用煤粉锅炉处理油基岩屑的方法
CN113234480B (zh) * 2021-05-25 2022-06-17 山东交通学院 一种将废弃机油残留物转化为沥青的方法

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US5259945A (en) * 1992-04-15 1993-11-09 Johnson Jr Lyle A Process for recovery of tank bottom wastes
CA2116639A1 (fr) * 1993-05-24 1994-11-25 Alkis S. Rappas Procede pour extraire les dechets organiques dans un melange aqueux, avec l'aide d'un solvant

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2338207A1 (es) * 2006-09-18 2010-05-04 Pablo Martin De Julian Proceso de recuperacion de aceites lubricantes usados con arcillas y centrifugacion.
ES2338207B2 (es) * 2006-09-18 2011-01-24 Pablo Martin De Julian Proceso de recuperacion de aceites lubricantes usados con arcilla y centrifugacion.
WO2015132807A3 (fr) * 2014-03-06 2016-03-24 Shubho-Tech Private Limited Appareil et procédé pour éliminer l'eau (à la fois liée et non liée) des boues et des émulsions de pétrole par application de chaleur seule, en vue de récupérer les hydrocarbures entiers qu'elles contiennent
GB2538914A (en) * 2014-03-06 2016-11-30 Nagaarjuna Shubho Green Tech Private Ltd Apparatus and process for removal of water (both bound and unbound) from petroleum sludges and emulsions through application of heat alone, with view to

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