EP3078730A1 - Verfahren zur erhöhung der ausbeute von schmierölbasen bei der regeneration von altölen - Google Patents

Verfahren zur erhöhung der ausbeute von schmierölbasen bei der regeneration von altölen Download PDF

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Publication number
EP3078730A1
EP3078730A1 EP13896967.0A EP13896967A EP3078730A1 EP 3078730 A1 EP3078730 A1 EP 3078730A1 EP 13896967 A EP13896967 A EP 13896967A EP 3078730 A1 EP3078730 A1 EP 3078730A1
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EP
European Patent Office
Prior art keywords
process according
evaporation
distillation
heavy
base oil
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.)
Withdrawn
Application number
EP13896967.0A
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English (en)
French (fr)
Other versions
EP3078730A4 (de
Inventor
Jerónimo ANGULO ARAMBURU
Jorge CONTRERAS BORNEZ
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.)
Sener Ingenieria y Sistemas SA
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Sener Ingenieria y Sistemas SA
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Publication of EP3078730A1 publication Critical patent/EP3078730A1/de
Publication of EP3078730A4 publication Critical patent/EP3078730A4/de
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    • 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
    • C10M175/02—Working-up used lubricants to recover useful products ; Cleaning mineral-oil based
    • 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

Definitions

  • the invention is related, in general, with used oil rerefining, an industrial operation that consists in recovering the lubricant base oils, by separating them from the other products and contaminants, so that they can be reformulated and used again as lubricants.
  • the invention describes a method to increase the yields of the rerefining process by improving the recovery of the higher boiling, more viscous base oils contained in the used oils.
  • Lubricant bases which are used to manufacture lubricants and other industrial oils, are called lubricant bases, base oils, or lube oil bases.
  • Lubricants and other industrial oils are produced by mixing lubricant bases with additives.
  • oils discarded after having been used in engines or other machines, are called used oils. They contain, lubricant bases and additives and their breakdown products (lighter petroleum fractions such as naphtha and gas-oil, and heavier ones such as asphalt and coke). They also contain contaminants acquired during their collection from garages and petrol stations, such as water, glycol and solvents.
  • the vacuum systems of these processes may be designed to provide very low pressures at the head of the distillation towers and special packing or plates may be used to provide low pressure drop in the fractionating column, the operating conditions of pressure and temperatures, prevailing in the flash zone of the tower, determine that part of the heavier bases will not boil and will be lost with the bottom product, which is usually valued as a low price component of asphalt or fuel-oil.
  • These losses of lube bases are significative when the fractionation column runs at moderate temperature (e.g. below 340°C at the flash zone) to avoid quality deterioration of the base oils; and when no steam injections are used in the distillation, to avoid producing contaminated waste water.
  • the present invention describes a simple and economic process for recovering part of the heavier lube bases that are normally lost in the rerefining operation.
  • the main objective of the invention is to increase the yield of lube bases, in used oil rerefining, by recovering the heavier and more viscous lube bases that are lost during the fractionation and purification of the different lube bases by distillation.
  • Another objective of the invention is to obtain high yields of lube bases of the same quality as the virgin bases produced by first refining of crude oil.
  • Another objective of the invention is to obtain high yields of high quality lube bases without the need of catalytic hydrogenation technologies.
  • the present invention defines a process to rerefine used petroleum oils, thereafter "the process of the invention", comprising the following steps:
  • used petroleum oils refers to lubricant or industrial petroleum oils discarded after their use in engines or other machines, and also to other petroleum oils such as contaminated lubricant oils or waste from petroleum oils not being characterized as lubricant oils.
  • the term “moderate temperatures” refers to temperatures less than 350 °C and the term “low pressure” refers to absolute pressures below 15 mbar (1.5 kPa).
  • the present invention consists of a rerefining process, characterized in that the distillation and fractionation stage to separate and purify the lube bases is carried in two interconnected steps as shown in Fig. 3 .
  • the fraction containing the lube base oils (1) is firstly fractionated in a continuous fractionation column (B) operated at low pressure provided by the vacuum system (D) and at moderate temperatures, separating, as lateral extractions, the light (2), medium (3) and part of the heavy base oils (4) contained in said fraction, and as bottom product (5) a stream containing the heavier lube base oils.
  • the distillation at the flash zone of the fractionation column is preferably carried out at a temperature of 310-335 °C; being the pressure in the head preferably of 2-8 mbar (0.2-0.8 kPa) and in the flash zone of 15-20 mbar (1.5-2.0 kPa).
  • the bottom of the distillation tower (5) containing part of the heavy lube base oils, suffers an adiabatic expansion by a pressure reduction in valve (X) and flows to the vapor-liquid separator (C), where heavy lube base oil vapors are separated from the liquid asphaltic products (8) that are obtained at the bottom of separator (C).
  • the heavy lube base oils vapors are condensed in cooler (F) and collected in vessel (G) as a liquid heavy lube base oil (6).
  • the vapor-liquid separator (C) is connected to the vacuum system (D).
  • step (c) the evaporation of step (c) is produced by adiabatic expansion of the bottom product of step (b) to a lower pressure.
  • Heavier lube bases that do not boil at the higher pressure of the column flash zone (E), will boil in separator (C) at a lower pressure, while keeping in both places the moderate temperatures required to avoid deterioration of the lube oil base quality.
  • Gentle heating is provided to this effect by thermal fluid (7) in preheater (A).
  • a different embodiment of the invention intended to increase even more the base oil recovery, consists of providing a lower pressure in (C) by a different vacuum system (S), showed in Fig. 3-4 in dotted lines, where the system (S) provides a lower pressure than system (D).
  • step (c) the lower pressure of the evaporation in step (c) is obtained with the same vacuum system employed in step (b).
  • the lower pressure of the evaporation in step (c) is obtained by a vacuum system supplying a lower pressure than that supplied by the vacuum system of step (b).
  • FIG. 4 A different embodiment of the invention is shown in Fig. 4 where the vapor-liquid separator (C) of Fig. 3 has been substituted by a thin film evaporator (C).
  • This thin film evaporator could be replaced with any other low pressure drop evaporation equipment known in the art.
  • an additional evaporation is carried out in a low pressure drop evaporation equipment such as a thin film, falling film or short path evaporator.
  • the additional evaporation is carried out in a thin film evaporator.
  • the temperature is preferably comprised between 320 and 345 °C and the pressure is preferably comprised between 2 and 8 mbar (0.2-0.8 kPa).
  • the bottom of the distillation tower, (5) containing part of the heavy lube base oil flows to the thin film evaporator (C) through pressure reducing valve (X).
  • the thin film evaporator (C) is connected to the vacuum system (D) and not as in prior art technology to the flash zone (E) of the column as described in Fig. 2 . Consequently the pressure in the thin film evaporator (C) is lower than the pressure in the flash zone (E), since the vapors from the thin film evaporator do not travel through the packings or plates of the distillation column to the vacuum system.
  • the difference of the pressure in the flash zone in respect to the pressure at the head of the thin film evaporator (C) is approximately equivalent to the pressure loss of the distillation column.
  • Heavier lube bases that do not boil at the higher pressure of the column flash zone, will boil in the thin film evaporator at a lower pressure, while keeping in both places the moderate temperatures required to avoid deterioration of the lube base quality.
  • Both the distillation column preheater (A) and the thin film evaporator (C) are heated with a thermal fluid (7).
  • the heavy base oils vapors evaporated in film evaporator (C) are condensed in (F) and collected in (G) as liquid heavy base oils (6).
  • the residue (8) left after evaporating the heavy lube base oils is collected at the bottom of the evaporator (C).
  • Prior technology may use a thin film evaporator as a column feed preheater or as a column reboiler (see Fig. 2 ) but in that case the thin film evaporator supports the pressure drop of the distillation column and the heavier base oils will not distill, being lost with the bottom of the column (B).
  • the thin film evaporator (C) of the invention in Fig. 4 supports a lower pressure, which favours the evaporation of the heavier base oils that are consequently recovered. It has a much smaller size than the one used in prior technology, since it deals with a smaller flow rate and has to evaporate much less amount of base oil. This is important since thin film evaporators are considerably more expensive than tubular exchangers normally used as column feed preheaters or reboilers.
  • FIG. 5 A different embodiment of the invention is depicted in Fig. 5 .
  • the vacuum system (S) provides an even lower pressure to the evaporator (C), which will give more flexibility to the process since the pressure difference between the flash zone of the distillation tower and the boiling liquid at the evaporator can be made higher.
  • Fig 5 also illustrates another embodiment of the invention consisting of a very simple rectification device (H) introduced between the evaporator (C) and the condenser (F), having a very low pressure loss, to improve the quality of the heavier oils (6) recovered in the thin film evaporator.
  • This simple rectification device (H) is a low pressure drop rectification device consisting of at least a distillation plate or a simple packing bed.
  • the heavy lube base oils vapors obtained in (C) are condensed in cooler (F) and collected in vessel (G) as a liquid heavy lube base oil. A part of this liquid heavy lube base oil is recirculated and put into contact in the low pressure drop rectification device (H) with the vapors exiting from (C).
  • step (c) before being condensed are contacted in a low pressure drop rectification device, consisting of at least a distillation plate or a simple packing bed, with part of the liquid heavy base oil obtained subsequently in step (c) which is recirculated after condensation.
  • a low pressure drop rectification device consisting of at least a distillation plate or a simple packing bed
  • the bottom product (8) obtained in the evaporator (C) is a high viscosity asphaltic oil and sometimes is mixed with a fluxing fluid for flowing it through the pipes. Therefore, in other particular embodiment of the process of the invention, the viscosity of the bottom product obtained in step (c) is reduced by mixing it with a fluxing fluid.
  • the fluxing fluid is a part or the total of the light fraction obtained in step (b) as first side cut of the fractionation column.
  • Fig. 5 also illustrates this embodiment of the invention consisting of modifying the column conditions to obtain as top column side product a heavy gas-oil and a light base oil (2), being partly (11) or totally used as a fluxing fluid to reduce the viscosity of the bottom product (8) of the evaporator (C).
  • FIG 6 An alternative to obtain a fluxing fluid from the top of column (B) is shown in Fig 6 .
  • the temperature at the top of column (B) is allowed to raise in such a way that the heavy gas-oil, contained in the light side cut, distills over the top of the column, is condensed in heat exchanger (K) and collected at the bottom of separator (L), as fluxing fluid to be mixed with the bottom product (8), shown in any of the Figs. 3 to 5 .
  • the fluxing fluid is the heavy gas-oil contained in the light base oil as first side cut in step (b) that is obtained by increasing the temperature at the top of the fractionation column and condensing the vapors that distill over.
  • the recovery of heavier oils is enhanced by reducing its partial pressure in the distillation or evaporation steps.
  • an inert gas is introduced in the distillation step (b), in the evaporation step (c) or both in the distillation step (b) and in the evaporation step (c).
  • nitrogen gas is introduced in the distillation step (b), in the evaporation step (c) or in both, in the distillation step (b) and in the evaporation step (c).
  • nitrogen gas is introduced in the evaporation step (c).
  • the nitrogen gas can be mixed with the lube fraction (1) obtained in the step (a) before being distilled in step (b), or bubbled at the bottom of column (B) or at the bottom of separator and/or evaporator (C) in Figures 3 to 6 or simultaneously in more than one of the places indicated above.
  • the quality of the base oils recovered in the process of the invention can be improved when a basic compound is added. So that, in a particular embodiment of the process of the invention, the distillation of step (b), or the evaporation of step (c) or both are carried out in the presence of a basic compound.
  • the basic compound is an alkaline hydroxide or a mixture of alkaline hydroxides, preferably in an amount below 12 kg per metric ton of base oil fraction fed to the distillation step (b).
  • One of the preferred alkaline hydroxides to be used is KOH.
  • step (a) of the process on the invention the separation of water, light hydrocarbons and asphalts from used petroleum oils is carried out for obtaining a fraction that contains the lube base oils (1).
  • These lube base oils (1) will be later separated and purified by fractionation (step b) and evaporation (step c), as previously stated.
  • step (a) is carried out by solvent extraction.
  • the separation of step (a) is carried out by solvent extraction with liquid propane.
  • Water, light hydrocarbons and asphalts are separated by means of a solvent extraction, wherein the solvent rejects the water and the asphalt and dissolves the base oils and light hydrocarbons.
  • This extract produces the lube base oil fraction after separating the solvent and the light hydrocarbons by vaporization.
  • step (a) is carried out by chemical demetallization.
  • step (a) is carried out by thin film vacuum evaporation.
  • the distillation was carried out in the presence of 7 kg of potassium hydroxide per hour.
  • the lube bases had a colour of 1.5 - (ASTM D 500) and acidity of 0.01 mg KOH/g (ASTM D 6644).
  • Example 2 The same used oil as indicated in Example 1 was extracted with propane at a rate of 1000 kg/h After eliminating the water, asphalts and light hydrocarbons, 858 kg/h of a fraction containing the lube bases were obtained and heated to 330°C, before being introduced in the fractionating column.
  • the pressure at the head of the column was 5 mbar (0.5 kPa) and 16 mbar (1.6 kPa) in the flash zone.
  • the lube bases had a color of 1.5 - and an acidity of 0.01 mg KOH/g.
  • the bottom product was expanded through valve (X) in Fig. 3 from 16 mbar (1.6 kPa) to about 5 mbar (0.5 kPa) in separator (C).
  • An additional lube oil base (6) was recovered as distillate in vessel (G) at a rate of 86 kg/h, characterized as an SN-500, having a colour of 1.5+ and an acidity of 0.02 mg KOH/g. Both the distillation and the evaporation were carried out in the presence of 8 kg/h of potassium hydroxide.
  • Example 1 The same used oil indicated in Example 1 was extracted with propane at a rate of 1000 kg/h, as indicated in said example.
  • the bottom product (5) of the distillation tower (630 kg/h) was expanded trough valve (X) and evaporated in a thin film evaporator as shown in Fig. 4 at 340°C and 3 mbars (0.3 kPa).
  • An additional lube base oil was recovered in (G) as distillate at a rate of 377 kg/h, characterized as a SN-500, having a colour of 2.0 - and an acidity of 0.03 mgr/l. Both the distillation and the evaporation were carried out in the presence of 8 kg/h of potassium hydroxide.
  • the bottom product (5) of the distillation tower (630 kg/h) was expanded through valve (X) to about 5 mbar (0.5 KPa) into separator (C), while bubbling nitrogen at the bottom of separator (C) at a rate of 10 Nm3/h.
  • An additional lube oil base (6) was recovered as distillate in vessel (G) at a rate of 109 kg/h.

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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)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP13896967.0A 2013-11-08 2013-11-08 Verfahren zur erhöhung der ausbeute von schmierölbasen bei der regeneration von altölen Withdrawn EP3078730A4 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/ES2013/070770 WO2015067828A1 (es) 2013-11-08 2013-11-08 Proceso para aumentar el rendimiento de bases lubricantes en la regeneración de aceites usados

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Publication Number Publication Date
EP3078730A1 true EP3078730A1 (de) 2016-10-12
EP3078730A4 EP3078730A4 (de) 2017-07-19

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EP13896967.0A Withdrawn EP3078730A4 (de) 2013-11-08 2013-11-08 Verfahren zur erhöhung der ausbeute von schmierölbasen bei der regeneration von altölen

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EP (1) EP3078730A4 (de)
MX (1) MX2016005893A (de)
WO (1) WO2015067828A1 (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108485790A (zh) * 2018-03-26 2018-09-04 福斯特惠勒（河北）工程设计有限公司 一种提高废机油再生处理量的方法
US10954468B2 (en) 2017-10-20 2021-03-23 Qingdao Institute Of Bioenergy And Bioprocess Technology, Chinese Academy Of Sciences Method for regeneration of used lubricating oils

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2629851B1 (es) * 2016-02-15 2018-04-25 José Antonio GÓMEZ MIÑANA Procedimiento de triple destilación para la regeneración de aceites usados incluyendo tratamiento cáustico en línea en la segunda destilación
CN112159705A (zh) * 2020-09-29 2021-01-01 甘肃环馨新能源科技有限公司 一种废矿物油再生生产工艺

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Publication number Priority date Publication date Assignee Title
IT1091961B (it) 1978-01-12 1985-07-06 Snam Progetti Procedimento per la rigenerazione degli oli esausti
NL8304023A (nl) * 1983-11-23 1985-06-17 Kinetics Technology Werkwijze voor het zuiveren van afgewerkte smeerolie.
ATE191496T1 (de) 1992-06-12 2000-04-15 Chemical Engineering Partners Verbessertes verfahren zur produktion von grundölen aus altöl
IT1255534B (it) 1992-09-30 1995-11-09 Processo di riraffinazione di oli usati
FR2703067B1 (fr) 1993-03-22 1995-08-04 Sotulub Procédé et installation de régénération d'huiles lubrifiantes.
FR2725725B1 (fr) * 1994-10-17 1996-12-13 Inst Francais Du Petrole Procede et installation pour la purification des huiles usagees
FR2757175B1 (fr) 1996-12-13 1999-03-05 Tunisienne De Lubrifiants Sotu Procede et installation de regeneration d'huiles lubrifiantes a hautes performances
DE19852007C2 (de) * 1998-11-11 2002-06-13 Mineraloel Raffinerie Dollberg Verfahren zur Wiederaufarbeitung von Altölen
US7226553B2 (en) 2003-07-30 2007-06-05 E. I. Du Pont De Nemours And Company Polymer underwater pelletizer apparatus and process incorporating same
ES2199697B1 (es) 2003-09-23 2005-02-01 Sener Grupo De Ingenieria, S.A. Procedimiento para regenerar aceites usados por desmetalizacion y destilacion.
SG161129A1 (en) * 2008-10-31 2010-05-27 Annda Energy Pte Ltd Process and system for regeneration of spent lubrication oil

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10954468B2 (en) 2017-10-20 2021-03-23 Qingdao Institute Of Bioenergy And Bioprocess Technology, Chinese Academy Of Sciences Method for regeneration of used lubricating oils
CN108485790A (zh) * 2018-03-26 2018-09-04 福斯特惠勒（河北）工程设计有限公司 一种提高废机油再生处理量的方法
CN108485790B (zh) * 2018-03-26 2021-03-16 福斯特惠勒（河北）工程设计有限公司 一种提高废机油再生处理量的方法

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MX2016005893A (es) 2016-08-17
WO2015067828A1 (es) 2015-05-14
EP3078730A4 (de) 2017-07-19

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