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WO1996000273A1 - Procede de recuperation d'huiles lubrifiantes usees - Google Patents

Procede de recuperation d'huiles lubrifiantes usees Download PDF

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Publication number
WO1996000273A1
WO1996000273A1 PCT/US1995/007987 US9507987W WO9600273A1 WO 1996000273 A1 WO1996000273 A1 WO 1996000273A1 US 9507987 W US9507987 W US 9507987W WO 9600273 A1 WO9600273 A1 WO 9600273A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
process according
oxalic acid
diammonium phosphate
solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1995/007987
Other languages
English (en)
Inventor
Giora HÖNIG
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corex Technologies 1993 Ltd
Original Assignee
Corex Technologies 1993 Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Corex Technologies 1993 Ltd filed Critical Corex Technologies 1993 Ltd
Priority to AU31246/95A priority Critical patent/AU3124695A/en
Publication of WO1996000273A1 publication Critical patent/WO1996000273A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C10M175/0033—Working-up used lubricants to recover useful products ; Cleaning by thermal processes using distillation processes; devices therefor
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal processes
    • C10M175/0041—Working-up used lubricants to recover useful products ; Cleaning by thermal processes by hydrogenation processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M175/00—Working-up used lubricants to recover useful products ; Cleaning
    • C10M175/0058—Working-up used lubricants to recover useful products ; Cleaning by filtration and centrifugation processes; apparatus therefor

Definitions

  • This invention relates to a process for the reclamation of used oils, particularly lubricating oils, viz. for the removal of impurities contained therein as a result of their use and/or of the additives, such as generally used in the lubricating oil art.
  • waste oils poses important practical problems, in view of the very large amount in which they are generated in technology and industry.
  • the most desirable way of disposing of these oils is, of course, reclaiming them so that they can be reused, thereby on the one hand recovering valuable products and on the other hand removing environmental contamination.
  • solvents are used in place of acid to precipitate the contaminants.
  • British Patent Specification 1598723 discloses an oil reclamation process which comprises compacting the used lubricating oil with an aqueous solution of a treating agent, consisting essentially of an ammonium salt, under conditions of temperature, pressure and time sufficient to disperse the agent in the used lubricating oil and to react the agent with the ash- forming components of the used oil, removing a major portion of water from the resulting mixture by distillation, separating the oil phase from the mixture resulting from the last-mentioned step, and thereafter recovering the resulting oil phase as a product of the process.
  • This process involves operations at high temperature and pressure, long treating times, and a high consumption of energy for water distillation. It does not remove all the additives and no organometallic disconnection occurs.
  • Portuguese Patent Specification No. 94502 discloses a process for demetallizing oils which comprises heating the oil to a temperature from about 70°C-130°C, heating an aqueous solution containing 3-6% by weight of ammonium bisulfate (NH 4 )HS0 , adding ethoxynonane heated to at least 80°C to the said solution, mixing the oil and the resulting solution, and separating the oily from the aqueous phase while the solution is maintained at a temperature higher than 80°C.
  • NH 4 ammonium bisulfate
  • This process does not permit to demetallize the oils to the required degree and does not remove organic compounds (such as succinic acid, sulfonates, esters, and the like) that are usually present and have a negative effect on the conventional after-treatments of the recovered oils. Further, it requires to maintain the oil at a relatively high temperature.
  • organic compounds such as succinic acid, sulfonates, esters, and the like
  • U.S. P. 4,250,021 discloses a treatment of used oils which comprises treating the oil with an aqueous solution containing a surfactant and anions which form an insoluble salt with at least one metal present in the oil.
  • Said treatment has the disadvantage of requiring the use of a surfactant.
  • Metal removal is not fully satisfactory unless multi-step contacting of the oil with the treating solution, preferably followed by washing, is not resorted to. Further, there takes place dilution of the aqueous solution, separated from the oil after treatment, by the water present in the oil, which requires the addition of treating chemicals to maintain the desired concentrations, thereby causing build-up of the treating solution in its repeated use and waste of chemicals. It is a purpose of the invention to provide a process for the reclamation of used oils that is free from the drawbacks of previously known processes.
  • the first, centrifugation step is carried out by two-phase or, preferably, three-phase centrifuges, capable of separating particles of less than 0.5 ⁇ dimensions.
  • the oxalic acid and diammonium phosphate when both are used in the second step of the process, may be contacted with the used oil by dissolving them in water and adding their solution to the oil, or two solutions, one of oxalic acid and one of diammonium phosphate, may be prepared and successively added to the oil, the two aqueous phases becoming mixed after their addition to the oil.
  • the mixture of the oil with the solution(s) of oxalic acid and diammonium phosphate is carried out at a temperature from 50 to 100°C and preferably at about 80-85°C.
  • the oil and the solution or solutions of treating agents may be previously heated to the desired mixing temperature and successively mixed at said temperature, or at least one of said components may be previously heated to a higher temperature, so that when they are mixed, the temperature will be lowered to the desired mixing temperature.
  • Oxalic acid and diammonium phosphate are used in amounts, by weight with respect to the oil, from 0.5 to 6%. and preferably from 2.5 to 5% for oxalic acid, and from 0.5 to 6% and preferably from 2.5 to 4.5% for diammonium phosphate. If only one of them is used, it is used in an amount of about 4 to 8%. If oxalic acid and diammonium phosphate are dissolved together in a single aqueous solution, their concentrations in said solution are respectively from 2 to 16% and from 2 to 17%.
  • the separation of the aqueous phase from the oil phase of the mixture of oil and solutions of treating agents is carried out either by dynamic means, e.g. centrifugation or filtration, e.g. membrane filtration, or by a combination of the addition, to said mixture of oil and solutions of treating agents, of an emulsion-breaking agent (hereinafter also "the third treating agent") and gravitational separation, e.g. decantation.
  • dynamic means two-phase or preferably three-phase centrifugation is employed, by the same means by which the first, centrifugation steps is carried out.
  • the emulsion- breaking agent when used, is an alkylphenol, preferably nonylphenol, which may be added to the solution of oxalic acid or of diammonium phosphate or to both, or may be added separately to the oil, the oil and aqueous phase being then separated by decantation.
  • reaction temperatures 60°C. and occasionally even lower, can be used.
  • the process can be carried out either continuously or batchwise, as desired.
  • the aqueous solution of treating agents may be reused with a small make-up.
  • the reuse eliminates disposal or reaction with metals from tap water.
  • the small amount of heavy sludge produced can be either used in the lead or nuclear industry, or disposed of in the cement industry.
  • the reclaimed oil may be further distilled in high vacuum distillation and hydrogenated to minimize halogen and sulfur content, and maximize yield.
  • FIG. 1 and 2 are two block diagrams illustrating two alternative ways of carrying out the process of the invention. Detailed Description of Preferred Embodiments
  • Ash content ASTM g/100g l.4 ⁇ 0.1 0 0 D482
  • the used oil is separated in a centrifuge, of the kind mentioned hereinafter, at ambient or higher temperature, to reduce water content to less than 1% and ash content to less than 2% (centrifuge velocity >4000 rpm).
  • a centrifuge of the kind mentioned hereinafter, at ambient or higher temperature, to reduce water content to less than 1% and ash content to less than 2% (centrifuge velocity >4000 rpm).
  • 500 ml oil is heated to 95°C.
  • 20 mg of oxalic acid >95%) is dissolved and heated to 85°C in 200 ml of tap water.
  • the solution is added to the oil while continuously stirring.
  • the contents are mixed for five minutes for full contact, always at temperatures from about 80° to about 85°C .
  • the oil containing almost no additives, is charged into a fractional distillation column, or is evaporated in thin film under high vacuum conditions (50-500 MBAR stage I, 2-3 MBAR stage II).
  • Fig. 1 is a block diagram indicating a first way of carrying out the invention.
  • Solutions of oxalic acid and of diammonium phosphate are separately prepared, and are mixed and heated to the desired temperature.
  • a solution of the emulsion-breaking agent, preferably nonylphenol is prepared and mixed with that of the first two agents - this step being optional, especially if a three-phase centrifugation is used, as shown in the block diagram, and is therefore shown in the diagram in broken lines.
  • the used oil from the storage, after separation therefrom of water and ash by three-phase centrifugation, is mixed with the solution of agents.
  • the mixture is then separated into an oily phase, an aqueous phase and a sludge, by means of a three-phase centrifuge, which may be the same used for the separation of water and ash or a different one. Both centrifuges, as mentioned hereinbefore, must be able to separate particles having dimensions below 0.5 ⁇ . Examples of suitable industrial centrifuges available on the market are Krauss-Maffei AF 2000 SMO, Flottweg Z34-4/053 and Alfa Laval WHPX 413-G.
  • the aqueous phase can be reused by feeding it back to the mixture phase with a small make-up.
  • the oil phase is subjected to high vacuum distillation, to obtain from it gas oil, light oil and heavy oil, and this latter may be subjected to hydrogenation.
  • Fig. 2 shows an alternative process flow diagram, which is distinguished from that of Fig. 1 because the three treating agents - oxalic acid, diammonium phosphate and optionally nonylphenol - are added successively to the oil instead of being previously mixed and being added together.
  • the oil and the solutions of oxalic acid and diammonium phosphate are separately heated before mixing to the desired mixing temperature or slightly above it, and the emulsion- breaking additive is not used.
  • the physical conditions at which the mixing is carried out may be varied, and therefore it is possible to heat one of the components of the mixture, particularly the oil, to a higher temperature, and the other component or components to a lower temperature, as long as the appropriate temperature will be obtained when they are mixed together.
  • the process according to the invention has many advantages over the prior art. It is essentially a one-step process, which does not require multi-step contact or washings, and yet achieves better purification of the oil than prior art processes. It does not require the use of surfactants. It eliminates the build-up of the treating solution, caused by it mixing with the water (that is always present in the crude oil in amounts of 5-10%) which takes place in the prior art processes, and therefore significantly reduces the consumption of chemicals. It removes from the oil, water, metals and additives. It eliminates long term operations, such as hot gravity separation. Because of the said combination of advantages, it is more economical and constitutes a significant improvement over the prior art.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Lubricants (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé de récupération d'huiles lubrifiantes usées consistant à soumettre l'huile usée brute à une centrifugation, à mettre l'huile centrifugée en contact avec une solution aqueuse de phosphate monoacide d'ammonium et/ou une solution aqueuse d'acide oxalique, et finalement à séparer la phase organique et la phase aqueuse ainsi produites.
PCT/US1995/007987 1994-06-23 1995-06-23 Procede de recuperation d'huiles lubrifiantes usees Ceased WO1996000273A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU31246/95A AU3124695A (en) 1994-06-23 1995-06-23 Process for the reclamation of used lubricating oils

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IL110104 1994-06-23
IL11010494A IL110104A (en) 1994-06-23 1994-06-23 Process for the reclamation of used lubricating oils

Publications (1)

Publication Number Publication Date
WO1996000273A1 true WO1996000273A1 (fr) 1996-01-04

Family

ID=11066268

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1995/007987 Ceased WO1996000273A1 (fr) 1994-06-23 1995-06-23 Procede de recuperation d'huiles lubrifiantes usees

Country Status (4)

Country Link
AU (1) AU3124695A (fr)
IL (1) IL110104A (fr)
WO (1) WO1996000273A1 (fr)
ZA (1) ZA955135B (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2743570A1 (fr) * 1996-01-17 1997-07-18 Deutsch Richard Erwin Procede de traitement des huiles de lubrification usagees en phase aqueuse dispersee pour leur recyclage
EP3098290A1 (fr) 2015-05-28 2016-11-30 Viscolube S.r.l. Procédé pour la régénération des huiles utilisées
EP3098291A1 (fr) 2015-05-28 2016-11-30 Viscolube S.r.l. Procede de regeneration d'huiles usees
CN110747050A (zh) * 2019-11-06 2020-02-04 沈阳理工大学 一种用于废机油再生的酸洗剂及酸洗处理方法
US10961466B2 (en) * 2017-07-27 2021-03-30 Basis Energy Purification, Llc Purification of renewable oils
CN114250106A (zh) * 2021-12-28 2022-03-29 安徽国孚生态工程技术有限公司 一种废内燃机油蒸馏脱金属方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1698257A (en) * 1926-05-05 1929-01-08 Laval Separator Co De Process of reclaiming used lubricating oil
GB409522A (en) * 1933-06-12 1934-05-03 Cornelis Van Grondelle Process of preparing purified lubricating and electrical resistance oil from used or waste oils
GB783033A (en) * 1954-12-20 1957-09-18 Exxon Research Engineering Co Method for reducing corrosion in lubricating systems
US3879282A (en) * 1974-02-26 1975-04-22 Phillips Petroleum Co Reclaiming used motor oil by chemical treatment with ammonium phosphate
US4250021A (en) * 1978-09-28 1981-02-10 Salusinszky Andor L Treating used hydrocarbon lubricating oils
US4381992A (en) * 1981-06-15 1983-05-03 Phillips Petroleum Company Reclaiming used lubricating oil
JPS59112808A (ja) * 1982-12-20 1984-06-29 Sanyo Sekiyu Kagaku Kk 汚泥油の処理方法
WO1992001033A1 (fr) * 1990-07-04 1992-01-23 Freed, Arthur, Woolf Procede de demetallisation d'huiles

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1698257A (en) * 1926-05-05 1929-01-08 Laval Separator Co De Process of reclaiming used lubricating oil
GB409522A (en) * 1933-06-12 1934-05-03 Cornelis Van Grondelle Process of preparing purified lubricating and electrical resistance oil from used or waste oils
GB783033A (en) * 1954-12-20 1957-09-18 Exxon Research Engineering Co Method for reducing corrosion in lubricating systems
US3879282A (en) * 1974-02-26 1975-04-22 Phillips Petroleum Co Reclaiming used motor oil by chemical treatment with ammonium phosphate
US4250021A (en) * 1978-09-28 1981-02-10 Salusinszky Andor L Treating used hydrocarbon lubricating oils
US4381992A (en) * 1981-06-15 1983-05-03 Phillips Petroleum Company Reclaiming used lubricating oil
JPS59112808A (ja) * 1982-12-20 1984-06-29 Sanyo Sekiyu Kagaku Kk 汚泥油の処理方法
WO1992001033A1 (fr) * 1990-07-04 1992-01-23 Freed, Arthur, Woolf Procede de demetallisation d'huiles

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 008, no. 225 (C - 247) 16 October 1984 (1984-10-16) *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2743570A1 (fr) * 1996-01-17 1997-07-18 Deutsch Richard Erwin Procede de traitement des huiles de lubrification usagees en phase aqueuse dispersee pour leur recyclage
WO1997026314A1 (fr) * 1996-01-17 1997-07-24 Richard Deutsch Procede de traitement des huiles de lubrification usagees en phase aqueuse dispersee pour leur recyclage
EP3098290A1 (fr) 2015-05-28 2016-11-30 Viscolube S.r.l. Procédé pour la régénération des huiles utilisées
EP3098291A1 (fr) 2015-05-28 2016-11-30 Viscolube S.r.l. Procede de regeneration d'huiles usees
US10961466B2 (en) * 2017-07-27 2021-03-30 Basis Energy Purification, Llc Purification of renewable oils
CN110747050A (zh) * 2019-11-06 2020-02-04 沈阳理工大学 一种用于废机油再生的酸洗剂及酸洗处理方法
CN110747050B (zh) * 2019-11-06 2022-02-11 沈阳理工大学 一种用于废机油再生的酸洗剂及酸洗处理方法
CN114250106A (zh) * 2021-12-28 2022-03-29 安徽国孚生态工程技术有限公司 一种废内燃机油蒸馏脱金属方法

Also Published As

Publication number Publication date
IL110104A0 (en) 1994-10-07
ZA955135B (en) 1996-01-31
IL110104A (en) 1999-07-14
AU3124695A (en) 1996-01-19

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