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WO1994001519A1 - Process for removing metals from waste oil - Google Patents

Process for removing metals from waste oil Download PDF

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Publication number
WO1994001519A1
WO1994001519A1 PCT/FI1993/000280 FI9300280W WO9401519A1 WO 1994001519 A1 WO1994001519 A1 WO 1994001519A1 FI 9300280 W FI9300280 W FI 9300280W WO 9401519 A1 WO9401519 A1 WO 9401519A1
Authority
WO
WIPO (PCT)
Prior art keywords
oil
edta
waste oil
water
metals
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/FI1993/000280
Other languages
French (fr)
Inventor
Olof Verner LINDSJÖ
Hannu Sakari Saarikoski
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.)
EKOKEM Oy AB
Original Assignee
EKOKEM Oy AB
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 EKOKEM Oy AB filed Critical EKOKEM Oy AB
Priority to AU45028/93A priority Critical patent/AU4502893A/en
Publication of WO1994001519A1 publication Critical patent/WO1994001519A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C10M175/0025—Working-up used lubricants to recover useful products ; Cleaning by thermal 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
    • C10M175/0016—Working-up used lubricants to recover useful products ; Cleaning with the use of chemical agents

Definitions

  • the present invention relates to a process for removing metals from waste oil.
  • the waste oil can be treated to a reusable product by removing metals included in the oil, especially lead, from the oil.
  • Patent 4,411,774 waste lub ⁇ ricating oil is treated for removing contaminants included therein by adding to the oil chemicals, such as (NH 4 ) 2 S0 4 , NH 4 HS0 4 , NH 4 H 2 P0 4 , (NH 4 ) 2 HP0 4 , CaHP0 4 , H 3 P0 4 , CaS0 4 , A1 2 (S0 4 ) 3 and gS0 4 , at a high temperature of at least 340 °C. On account of distillations and high temperatures, the process is, however, unpractical and inconvenient.
  • Metals have been removed from waste oil also by adding an aqueous solution containing a surfactant and anions, which form insoluble salts with metals.
  • the aqueous phase and the oil phase are then separat ⁇ ed from each other and the oil is filtered (U.S. Patent 4,250,021).
  • Lead can also be removed from waste oil by ag- glomerating suspended oil in such a way that the oil is heated to a temperature of 260 to 370 °C. At least 90 % of the lead can be removed by this method dis ⁇ closed in U.S. Patent 3,923,643.
  • the object of the present invention is to pro- vide from waste oil such a product that can be re- utilized, for instance burned. This is achieved ac ⁇ cording to the invention in such a way that metals, especially lead, being detrimental to the reutiliza- tion of waste oil, are removed by adding a complex forming substance to the oil.
  • the process according to the invention is characterized in that the waste oil is at first pretreated for removing the water and solids included therein, after which this is dispers ⁇ ed with a sufficient amount of an EDTA solution at an elevated temperature under basic conditions, whereby metal complexes are formed, and finally the phases are separated from each other.
  • the process according to the invention is suit ⁇ able for used lubricating oils of good quality, which can be mineral oil based or synthetic.
  • Such waste oils can contain about 500 to 1000 ppm of lead, about 500 to 5000 ppm of zinc, about 1000 to 5000 ppm of calcium and about 200 to 2000 ppm of magnesium.
  • treated waste oil can sub- stitute for heavy oil, for instance.
  • the invention uses EDTA (ethylene diamine tet- racetic acid) as a complex forming substance. Also other complexing agents, such as DCTA (1,2-diamino cyclohexane tetracetic acid), can be used.
  • the process according to the invention is based on a capability of an NH 4 EDTA compound of complexing metals in a basic solution. Especially metals like Pb, Zn, Ca and Mg are concerned.
  • the stability of the EDTA metal complex depends above all on pH value. The optimum pH of lead is 9,5 while that of zinc is 5,5. Therefore it shall be attended to that the pH of the EDTA solution is within the range 5 to 10.
  • the volume between the NH 4 EDTA solution and the oil shall be 1:1 to 1:4, pre ⁇ ferably 1:3. If this proportion is larger, i.e. if there is too little water, the efficiency to separate metals becomes weaker and the risk of emulsification increases. On the other hand, if the proportion is smaller, disadvantageous amounts of waste water are produced.
  • An advantage of the process of the invention consists of its efficiency, favourableness and sim- plicity. Further advantages are that the EDTA can be recovered from the metal-EDTA-complex by precipitat ⁇ ing the EDTA with hydrochloric acid. The yield of EDTA recovered is about 75 to 90 %.
  • Prepurification procedure A a) waste oil batches to be purified are collected in a container for providing an even consistency, b) an emulsion dispersing chemical is added, c) the oil mixture is heated to a temperature of 60 to 70 °C, d) the mixture is separated for removing solids and water from it (water content after this 1 % at the maximum) .
  • Prepurification procedure B a) waste oil batches are collected in a container for providing an even consistency, b) the oil mixture is heated to 65 °C, c) the mixture is allowed to clarify for a time of 1 week to 2 months, d) the water separated is removed, e) an emulsion dispersing chemical is added, f) the mixture is allowed to clarify, g) a layer of water and soot settled on the bottom is removed (water content of oil after this 1 to 1,5 %), h) the mixture is possibly centrifuged for removing the solids.
  • the purpose of the pretreatment is to homogenize the oil and to remove the water and the solids from it.
  • Preparation of an EDTA reagent 650 1 of 25 % NH 3 are added to 1500 litres of water.
  • To this water solution are mixed 1000 kg of solid EDTA, after which the pH of the mixture is 6 to 6,5 (volume 3,5 m 3 ).
  • 350 litres of this solution are used per 5 m 3 of the oil to be purified, i.e. the used amount of reagent calculated to EDTA is 20 kg of EDTA per m 3 oil.
  • the next example describes the present inven ⁇ tion.
  • Example 1 5 m 3 of prepurified oil are pumped into a 7 m 3 container.
  • 50 1 of the 25 % NH 3 solu ⁇ tion are added to the oil.
  • the mixture is stirred for 2 minutes.
  • 350 litres of the EDTA reagent prepared above are diluted with water to 1,5 m 3 , which are then added to the oil mixture.
  • the mixture thus obtained is stirred for 4 minutes by a propeller mixer at a speed of 750 rpm at a temperature of 40 to 50 °C.
  • the pH is then about 9. After this the mixture is pumped into a clarification container. During pumping the temperature rises to 80 °C.
  • the mixture is allowed to clarify for 1 to 2 days.
  • the water content of the oil is at this stage 1 to 2 %.
  • the metal contents of the unpurified oil, which has been prepurified by remov- ing water and solids from it, and the contents of metal residues of the oil obtained after the purifi ⁇ cation are presented in Table 1 for ten oil batches of 5 m 3 .
  • the mean value X and the standard deviation SD of these 10 tests are also given.

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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)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention relates to a process for removing metals from waste oil, whereby the waste oil is at first pretreated for removing the water and solids included therein, after which this is dispersed with a sufficient amount of an EDTA solution at an elevated temperature under basic conditions, whereby metal complexes are formed, and finally the phases are separated from each other.

Description

Process for removing metals from waste oil
The present invention relates to a process for removing metals from waste oil. By means of the pro- cess of the invention the waste oil can be treated to a reusable product by removing metals included in the oil, especially lead, from the oil.
From the literature of the field are known var¬ ious methods of treating waste oil for removing met- als from the oil. According to U.S. Patent 3,763,036, methyl ethyl ketone is added to waste oil for remov¬ ing lead. A coagulated insoluble layer provided in this manner and the purified oil can be separated from each other. According to U.S. Patent 4,411,774, waste lub¬ ricating oil is treated for removing contaminants included therein by adding to the oil chemicals, such as (NH4)2S04, NH4HS04, NH4H2P04, (NH4)2HP04, CaHP04, H3P04, CaS04, A12(S04)3 and gS04, at a high temperature of at least 340 °C. On account of distillations and high temperatures, the process is, however, unpractical and inconvenient.
Metals have been removed from waste oil also by adding an aqueous solution containing a surfactant and anions, which form insoluble salts with metals. The aqueous phase and the oil phase are then separat¬ ed from each other and the oil is filtered (U.S. Patent 4,250,021).
Lead can also be removed from waste oil by ag- glomerating suspended oil in such a way that the oil is heated to a temperature of 260 to 370 °C. At least 90 % of the lead can be removed by this method dis¬ closed in U.S. Patent 3,923,643.
The object of the present invention is to pro- vide from waste oil such a product that can be re- utilized, for instance burned. This is achieved ac¬ cording to the invention in such a way that metals, especially lead, being detrimental to the reutiliza- tion of waste oil, are removed by adding a complex forming substance to the oil. The process according to the invention is characterized in that the waste oil is at first pretreated for removing the water and solids included therein, after which this is dispers¬ ed with a sufficient amount of an EDTA solution at an elevated temperature under basic conditions, whereby metal complexes are formed, and finally the phases are separated from each other.
The process according to the invention is suit¬ able for used lubricating oils of good quality, which can be mineral oil based or synthetic. Such waste oils can contain about 500 to 1000 ppm of lead, about 500 to 5000 ppm of zinc, about 1000 to 5000 ppm of calcium and about 200 to 2000 ppm of magnesium. Ac¬ cording to the invention, treated waste oil can sub- stitute for heavy oil, for instance.
The invention uses EDTA (ethylene diamine tet- racetic acid) as a complex forming substance. Also other complexing agents, such as DCTA (1,2-diamino cyclohexane tetracetic acid), can be used. The process according to the invention is based on a capability of an NH4EDTA compound of complexing metals in a basic solution. Especially metals like Pb, Zn, Ca and Mg are concerned. The stability of the EDTA metal complex depends above all on pH value. The optimum pH of lead is 9,5 while that of zinc is 5,5. Therefore it shall be attended to that the pH of the EDTA solution is within the range 5 to 10.
In the process of the invention, the EDTA re¬ mains in an aqueous phase and is not transferred to the oil. It is then necessary to attend to that there is a sufficient contact between the oil and the re¬ agent to make it possible for free EDTA molecules in an interface to bind a great amount of metals being in an oil phase. In practice this is realized in such a way that the mixing time is kept sufficiently long and the mixing efficient enough. However, the mixing must not be so strong as to change the oil-EDTA-mix- ture into an emulsion, whereby it is difficult to separate the phases from each other. To achieve a maximum demetallization, the volume between the NH4EDTA solution and the oil shall be 1:1 to 1:4, pre¬ ferably 1:3. If this proportion is larger, i.e. if there is too little water, the efficiency to separate metals becomes weaker and the risk of emulsification increases. On the other hand, if the proportion is smaller, disadvantageous amounts of waste water are produced.
An advantage of the process of the invention consists of its efficiency, favourableness and sim- plicity. Further advantages are that the EDTA can be recovered from the metal-EDTA-complex by precipitat¬ ing the EDTA with hydrochloric acid. The yield of EDTA recovered is about 75 to 90 %.
Before treating the oil with EDTA, the oil is subjected to a prepurification performable in two different manners: Prepurification procedure A: a) waste oil batches to be purified are collected in a container for providing an even consistency, b) an emulsion dispersing chemical is added, c) the oil mixture is heated to a temperature of 60 to 70 °C, d) the mixture is separated for removing solids and water from it (water content after this 1 % at the maximum) . Prepurification procedure B: a) waste oil batches are collected in a container for providing an even consistency, b) the oil mixture is heated to 65 °C, c) the mixture is allowed to clarify for a time of 1 week to 2 months, d) the water separated is removed, e) an emulsion dispersing chemical is added, f) the mixture is allowed to clarify, g) a layer of water and soot settled on the bottom is removed (water content of oil after this 1 to 1,5 %), h) the mixture is possibly centrifuged for removing the solids.
Accordingly, the purpose of the pretreatment is to homogenize the oil and to remove the water and the solids from it. Experiments made on a pilot scale have proved that a separation of the phases of a dis¬ persed mixture succeeds best by clarifying. Preparation of an EDTA reagent: 650 1 of 25 % NH3 are added to 1500 litres of water. To this water solution are mixed 1000 kg of solid EDTA, after which the pH of the mixture is 6 to 6,5 (volume 3,5 m3). 350 litres of this solution are used per 5 m3 of the oil to be purified, i.e. the used amount of reagent calculated to EDTA is 20 kg of EDTA per m3 oil.
The next example describes the present inven¬ tion.
Example 1 5 m3 of prepurified oil are pumped into a 7 m3 container. For neutralizing the acids included in the oil and for raising the pH, 50 1 of the 25 % NH3 solu¬ tion are added to the oil. The mixture is stirred for 2 minutes. 350 litres of the EDTA reagent prepared above are diluted with water to 1,5 m3, which are then added to the oil mixture. The mixture thus obtained is stirred for 4 minutes by a propeller mixer at a speed of 750 rpm at a temperature of 40 to 50 °C. The pH is then about 9. After this the mixture is pumped into a clarification container. During pumping the temperature rises to 80 °C. The mixture is allowed to clarify for 1 to 2 days. The water content of the oil is at this stage 1 to 2 %. The metal contents of the unpurified oil, which has been prepurified by remov- ing water and solids from it, and the contents of metal residues of the oil obtained after the purifi¬ cation are presented in Table 1 for ten oil batches of 5 m3. The mean value X and the standard deviation SD of these 10 tests are also given.
Table 1
Figure imgf000007_0001
Figure imgf000008_0001

Claims

Claims:
1. A process for removing metals from waste oil, c h a r a c t e r i z e d in that the waste oil is at first pretreated for removing the water and solids included therein, after which this is dispers¬ ed with a sufficient amount of an EDTA solution at an elevated temperature under basic conditions, whereby metal complexes are formed, and finally the phases are separated from each other.
2. A process according to claim 1, c h a r¬ a c t e r i z e d in that the dispersion is per¬ formed at a temperature of 40 to 50 °C.
3. A process according to claim 1 or 2, c h a r a c t e r i z e d in that the amount of the added aqueous solution of NH4EDTA is 15 to 20 kg of EDTA per m3 oil, preferably 20 kg of EDTA per m3 oil.
4. A process according to any of the claims 1 to 3, c h a r a c t e r i z e d in that the pH of the NH4EDTA solution is 5 to 10, preferably about 9.
5. A process according to any of the claims 1 to 4, c h a r a c t e r i z e d in that NH4EDTA so¬ lution is added to waste oil in the proportion 1:3 to 1:4, preferably in the proportion 1:3.
PCT/FI1993/000280 1992-07-10 1993-07-01 Process for removing metals from waste oil Ceased WO1994001519A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU45028/93A AU4502893A (en) 1992-07-10 1993-07-01 Process for removing metals from waste oil

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FI923206 1992-07-10
FI923206A FI90252C (en) 1992-07-10 1992-07-10 Procedure for removal of metals from waste oil

Publications (1)

Publication Number Publication Date
WO1994001519A1 true WO1994001519A1 (en) 1994-01-20

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Family Applications (1)

Application Number Title Priority Date Filing Date
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AU (1) AU4502893A (en)
FI (1) FI90252C (en)
WO (1) WO1994001519A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2787118A1 (en) * 1998-12-09 2000-06-16 Richard Deutsch Process for the recycling of used lubricating oil from automobiles, comprises the removal of contaminant metals followed by low temperature vacuum distillation stages
FR2795421A1 (en) * 1999-06-23 2000-12-29 Richard Deutsch Decontamination of waste semi-synthetic or synthetic mineral oils comprises treatment with glycol, chelating agents, and barium hydroxide before ultimate fractional distillation and possible decoloration treatment
CN113430044A (en) * 2021-07-23 2021-09-24 西安热工研究院有限公司 Method for removing metal impurity elements in wind power gear oil

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4359093A (en) * 1980-11-21 1982-11-16 Union Oil Co. Of California Method for enhanced oil recovery in reservoirs containing dissolved divalent metal cations
SU1384607A1 (en) * 1986-07-04 1988-03-30 Научно-Производственное Объединение По Кузнечно-Прессовому Оборудованию И Гибким Производственным Системам Для Обработки Давлением "Эникмаш" Lubricant for cold forming of metals
US4778590A (en) * 1985-10-30 1988-10-18 Chevron Research Company Decalcification of hydrocarbonaceous feedstocks using amino-carboxylic acids and salts thereof
US4788375A (en) * 1987-11-27 1988-11-29 Mobil Oil Corporation Olefin conversion to lubricant range hydrocarbons
US5042617A (en) * 1989-09-07 1991-08-27 Exxon Research & Engineering Company Method of reducing the presence of sludge in lubricating oils
JPH059492A (en) * 1991-07-05 1993-01-19 Mitsubishi Kakoki Kaisha Ltd Treatment of waste lubricating oil

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4359093A (en) * 1980-11-21 1982-11-16 Union Oil Co. Of California Method for enhanced oil recovery in reservoirs containing dissolved divalent metal cations
US4778590A (en) * 1985-10-30 1988-10-18 Chevron Research Company Decalcification of hydrocarbonaceous feedstocks using amino-carboxylic acids and salts thereof
SU1384607A1 (en) * 1986-07-04 1988-03-30 Научно-Производственное Объединение По Кузнечно-Прессовому Оборудованию И Гибким Производственным Системам Для Обработки Давлением "Эникмаш" Lubricant for cold forming of metals
US4788375A (en) * 1987-11-27 1988-11-29 Mobil Oil Corporation Olefin conversion to lubricant range hydrocarbons
US5042617A (en) * 1989-09-07 1991-08-27 Exxon Research & Engineering Company Method of reducing the presence of sludge in lubricating oils
JPH059492A (en) * 1991-07-05 1993-01-19 Mitsubishi Kakoki Kaisha Ltd Treatment of waste lubricating oil

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
CHEMICAL ABSTRACTS, Volume 106, No. 8, 23 February 1987, (Columbus, Ohio, USA), ESSINGTON, M.E. et al., "Extraction of Inorganic Chemical Constituents from Retorted Oil Shale by Complexometric Agents", page 328, the Abstract No. 55273d, & ENERGY RES. ABSTR., 1986, 11, (20), (Eng.). *
CHEMICAL ABSTRACTS, Volume 109, No. 2, 11 July 1988, (Columbus, Ohio, USA), page 162, the Abstract No. 9253m; & SU,A,1 384 607, 30 March 1988. *
CHEMICAL ABSTRACTS, Volume 118, No. 22, 31 May 1993, (Columbus, Ohio, USA), page 201, the Abstract No. 216301b; & JP,A,5 009 492, (MITSUBISHI KAKOKI KAISHA, LTD.), 19 January 1993. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2787118A1 (en) * 1998-12-09 2000-06-16 Richard Deutsch Process for the recycling of used lubricating oil from automobiles, comprises the removal of contaminant metals followed by low temperature vacuum distillation stages
FR2795421A1 (en) * 1999-06-23 2000-12-29 Richard Deutsch Decontamination of waste semi-synthetic or synthetic mineral oils comprises treatment with glycol, chelating agents, and barium hydroxide before ultimate fractional distillation and possible decoloration treatment
WO2001000756A1 (en) * 1999-06-23 2001-01-04 Richard Deutsch Method for decontaminating waste semi-synthetic or synthetic mineral oils
CN113430044A (en) * 2021-07-23 2021-09-24 西安热工研究院有限公司 Method for removing metal impurity elements in wind power gear oil

Also Published As

Publication number Publication date
AU4502893A (en) 1994-01-31
FI90252C (en) 1994-01-10
FI90252B (en) 1993-09-30
FI923206A0 (en) 1992-07-10

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