[go: up one dir, main page]

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

Process for removing metals from waste oil Download PDF

Info

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
Application number
PCT/FI1993/000280
Other languages
English (en)
French (fr)
Inventor
Olof Verner LINDSJÖ
Hannu Sakari Saarikoski
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

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
    • 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.

Landscapes

  • 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)
PCT/FI1993/000280 1992-07-10 1993-07-01 Process for removing metals from waste oil 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
FI923206A FI90252C (fi) 1992-07-10 1992-07-10 Menetelmä metallien poistamiseksi jäteöljystä
FI923206 1992-07-10

Publications (1)

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

Family

ID=8535605

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/FI1993/000280 WO1994001519A1 (en) 1992-07-10 1993-07-01 Process for removing metals from waste oil

Country Status (3)

Country Link
AU (1) AU4502893A (fi)
FI (1) FI90252C (fi)
WO (1) WO1994001519A1 (fi)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2787118A1 (fr) * 1998-12-09 2000-06-16 Richard Deutsch Procede de recuperation des huiles de synthese et d'elaboration d'huiles a haut indice de viscosite a partir d'huiles de lubrification usagees
FR2795421A1 (fr) * 1999-06-23 2000-12-29 Richard Deutsch Procede de decontamination des huiles minerales semi synthetiques et synthetiques usagees
CN113430044A (zh) * 2021-07-23 2021-09-24 西安热工研究院有限公司 一种风电齿轮油中金属杂质元素的脱除方法

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 (ru) * 1986-07-04 1988-03-30 Научно-Производственное Объединение По Кузнечно-Прессовому Оборудованию И Гибким Производственным Системам Для Обработки Давлением "Эникмаш" Смазка дл холодной обработки металлов давлением
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 (ja) * 1991-07-05 1993-01-19 Mitsubishi Kakoki Kaisha Ltd 廃潤滑油の処理方法

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 (ru) * 1986-07-04 1988-03-30 Научно-Производственное Объединение По Кузнечно-Прессовому Оборудованию И Гибким Производственным Системам Для Обработки Давлением "Эникмаш" Смазка дл холодной обработки металлов давлением
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 (ja) * 1991-07-05 1993-01-19 Mitsubishi Kakoki Kaisha Ltd 廃潤滑油の処理方法

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 (fr) * 1998-12-09 2000-06-16 Richard Deutsch Procede de recuperation des huiles de synthese et d'elaboration d'huiles a haut indice de viscosite a partir d'huiles de lubrification usagees
FR2795421A1 (fr) * 1999-06-23 2000-12-29 Richard Deutsch Procede de decontamination des huiles minerales semi synthetiques et synthetiques usagees
WO2001000756A1 (fr) * 1999-06-23 2001-01-04 Richard Deutsch Procede de decontamination des huiles minerales semi-synthetiques et synthetiques usagees
CN113430044A (zh) * 2021-07-23 2021-09-24 西安热工研究院有限公司 一种风电齿轮油中金属杂质元素的脱除方法

Also Published As

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

Similar Documents

Publication Publication Date Title
US2761563A (en) Method of treating water
EP0009935B1 (en) Process for removing metals and water from used hydrocarbon lubricating oil
US4505839A (en) Polyalkanolamines
CA1069626A (en) Colloid-free precipitation of heavy metal sulfides
CN108865398A (zh) 一种废润滑油预处理方法
US4466885A (en) Method for removing solids and water from petroleum crudes
EP0586468A1 (en) Treatment of emulsions
DE3137341A1 (de) Verfahren zur regenerierung von waessrigen entfettungs- und reinigungsloesungen
US3790474A (en) Method of purifying oils containing liquid and solid impurities
US4383933A (en) Organo titanium complexes
EP0291174B1 (en) Process for treatment of contaminated emulsion
WO1994001519A1 (en) Process for removing metals from waste oil
KR920000525B1 (ko) 갈륨의 정제방법
US4731481A (en) Polyalkanolamines
CN1028537C (zh) 用复合剂从烃原料中脱除金属
US3607731A (en) Re-refined waste crankcase oils and method
JPH01275692A (ja) 廃エンジン油の処理方法
CN1055552A (zh) 用硫酸和它的盐脱除烃原料中的金属
WO2002018523A9 (en) A method of reclaiming used motor oil for further use
US3620967A (en) Rerefining of waste crankcase and like oils
DE69101233T2 (de) Verfahren für die Entfernung von Fluoriden aus Abwasser.
US4840748A (en) Polyalkanolamines
US5002745A (en) Method of separating and recovering phosphorus from phosphorus sludge
US4124504A (en) Process for treating caustic wash solutions
WO1996000273A1 (en) Process for the reclamation of used lubricating oils

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AT AU BB BG BR BY CA CH CZ DE DK ES FI GB HU JP KP KR KZ LK LU MG MN MW NL NO NZ PL PT RO RU SD SE SK UA US VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA