EP2657324A1 - Verfahren zur Herstellung von Bio-Schnmiermittel aus Methyl-Biodiesel und mit diesem Verfahren hergestelltes Bio-Schmiermittel - Google Patents

Verfahren zur Herstellung von Bio-Schnmiermittel aus Methyl-Biodiesel und mit diesem Verfahren hergestelltes Bio-Schmiermittel Download PDF

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Publication number
EP2657324A1
EP2657324A1 EP13164145.8A EP13164145A EP2657324A1 EP 2657324 A1 EP2657324 A1 EP 2657324A1 EP 13164145 A EP13164145 A EP 13164145A EP 2657324 A1 EP2657324 A1 EP 2657324A1
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EP
European Patent Office
Prior art keywords
biodiesel
methyl
bio
lubricant
production
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Withdrawn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
EP13164145.8A
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English (en)
French (fr)
Inventor
Jose Da Silva
Denise Freire
Alberto Habert
Valeria Soares
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.)
Universidade Federal do Rio de Janeiro UFRJ
Petroleo Brasileiro SA Petrobras
Original Assignee
Universidade Federal do Rio de Janeiro UFRJ
Petroleo Brasileiro SA Petrobras
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Publication date
Application filed by Universidade Federal do Rio de Janeiro UFRJ, Petroleo Brasileiro SA Petrobras filed Critical Universidade Federal do Rio de Janeiro UFRJ
Publication of EP2657324A1 publication Critical patent/EP2657324A1/de
Withdrawn legal-status Critical Current

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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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/38—Esters of polyhydroxy compounds
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • C10M2207/2815—Esters of (cyclo)aliphatic monocarboxylic acids used as base material
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/02—Pour-point; Viscosity index
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/64—Environmental friendly compositions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention describes a process for the production of bio-lubricant from castor oil methyl biodiesel (methyl ricinoleate) and/or from Jatropha oil methyl biodiesel (mixture of methyl oleate and linoleate) as well as the following products: basic oil, methylolpropane trioleate and methylolpropane triricinoleate obtained by the respective processes.
  • Castor or ricin is the seed of Ricinus communis L., a species of the Euphorbiaceae family.
  • the main product derived from this plant is castor bean oil, or castor oil.
  • Brazil is the third largest grower and producer of castor beans, behind only India and China.
  • the composition of castor bean oil or castor oil is approximately 90% ricinoleic acid, which differentiates it from all other vegetable oils.
  • Ricinoleic acid ( Figure 1A ) is a fatty acid comprising 18 carbon atoms with a double bond between carbon 9 and 10 and a hydroxyl in carbon 12 of its chain.
  • Jatropha comprises an oilseed rich in oleic and linoleic acids, from which biodiesel can be produced.
  • Oleic acid ( Figure 1 B) is also a fatty acid comprising 18 carbon atoms having a double bond in carbon 9. However, it does not have a hydroxyl in carbon 12.
  • Linoleic acid is an unsaturated fatty acid with 18 carbons having two unsaturates.
  • Jatropha has great potential as a raw material for the synthesis of bio-lubricants, with the great advantage that neither are foodstuffs, that is to say that there is no competition from food usage, as is the case with Soya, canola, sunflower and other oilseeds.
  • Brazilian patent application PI 0520104-7 concerns a process for preparation of a bio-fuel mixture comprising a fraction of fatty acid alkyl ester and at least one fraction of glycerine containing substituents forming mono and/or diglycerides and/or triglycerides and also a device for preparation of said mixture.
  • the glycerine fraction corresponds to at least 1% by weight of the fuel mixture.
  • the bio-fuel mixture can be used as a fuel in diesel engines without additional cooling, and/or can be added to a conventional diesel fuel mixture.
  • Application MU 8902161-4 concerns the use of Jatropha oil, extracted from the seeds and purified, as a replacement for naphthenic and paraffinic oils, derived from petroleum, as an insulating fluid for high voltage transformers.
  • the present invention deals with the synthesis of lubricants from Jatropha oil biodiesel, and not an insulating oil.
  • the focus is solely on the extraction and purification of vegetable oil and the subsequent mixing with additives, while with the present invention there is a chemical reaction.
  • the technology developed and described in the present invention has the main benefit that the bio-lubricants obtained from the castor oil methyl biodiesel and the Jatropha oil methyl biodiesel are biodegradable.
  • bio-lubricants obtained from castor oil methyl biodiesel and from Jatropha oil methyl biodiesel, by the enzymatic route represent new products and processes which are important and responsible for the diversification of the line of lubricants previously existing in the market.
  • bio-lubricants from castor oil methyl biodiesel (methyl ricinoleate) and from Jatropha oil methyl biodiesel (mixture of methyl oleate and linoleate) proposed in the invention takes place through enzymatic catalysis and has as the principal step the transesterification reaction of the biodiesel with a polyhydroxylated alcohol, with subsequent purification and separation of the product: methanol (D) and bio-lubricant (E, F).
  • the reaction is performed in batch type reactors, thermostatically controlled and with agitation of 700 rpm. Removal of the alcohol formed as a by-product takes place under a vacuum of 0.01 bar (1 kPa) to increase the reaction conversion.
  • TMP trimethylolpropane
  • the reaction mixture is heated to a temperature that may vary between 40°C and 55°C, and then the lipase is added, in a proportion of 1% - 4% w/w in relation to the weight of the mixture of biodiesel plus TMP.
  • the system is agitated at 700 rpm and a vacuum of 0.01 bar (1 kPa) is created.
  • the reactor is unloaded and the mixture is filtered and centrifuged to separate the enzyme and stored in the freezer at a temperature of -10°C.
  • the methanol (D) formed is collected during the process by means of a gas condensation system. Separation of the methanol from the reaction medium increases the conversion of the process.
  • Figure 2 shows the transesterification reaction of the methyl ricinoleate (A) with the TMP, in the presence of the enzymatic catalyst (C) with methanol (D) and the basic lubricating oil methylolpropane tri-ricinoleate (E) being obtained.
  • TMP the neopentyl glycol and pentaerithrytol alcohols.
  • Candida rugosa Lipomod 34P - Biocatalysts
  • Candida antarctica Novozym 435 - Novozymes
  • Rhizomucor miehei Lipozym IM RM - Novozymes
  • Table 1 Typical properties of the enzyme Lipomod 34P (biocatalysts). TABLE 1 PROPERTIES VALUES Activity 115 000 Lipase U/g (typical) 65 000 Esterase U/g (approx.) Biological source Candida rugosa Form White powder Working pH 5-8 Working temperature 40°C - 55°C Table 2: Typical properties of the enzyme Novozym 435 (Novozymes).
  • the reaction is performed in batch type reactors with agitation at 700 rpm. These reactors have a volume of 50 ml and are thermostatically controlled. When removal of the alcohol formed as a by-product is necessary, the system is placed under a vacuum of 0.01 bar (1 kPa) with the consequence that the conversion is increased.
  • Trimethylolpropane - TMP (5% - 12% w/w with regard to the weight of the biodiesel plus TMP) and water, in a proportion of 1% - 11 % w/w with regard to the weight of the biodiesel plus TMP are initially added to the reactor.
  • the reaction temperature is between 40°C and 55°C.
  • the lipase is added when the reactor is at the reaction temperature, in a proportion of 1% - 4% w/w with regard to the weight of reagents: biodiesel plus TMP. Agitation is maintained at a speed of 700 rpm and the pressure in the range 0.01 bar (1 kPa).
  • the reactor is unloaded and the mixture is filtered and centrifuged to separate the enzyme and stored at a temperature of - 10°C.
  • the reactions can occur in a range of pressures of between 0.01 bar and 1 bar (10 3 and 10 5 Pa).
  • the methanol (D) formed is collected during the reaction by means of a gas condensation system.
  • Figure 3 illustrates the transesterification reaction of the methyl oleate (B) with the TMP, in the presence of the enzymatic catalyst (C) with methanol (D) and the basic oil methylolpropane trioleate (F) being obtained.
  • neopentyl glycol and pentaerithrytol alcohols and the enzymatic catalysts mentioned above are used.
  • the viscosity (VI) and pour point values of the bio-lubricant obtained in the chemical process are equivalent to those of the bio-lubricant obtained in the enzymatic process. But the oxidation stability of the bio-lubricant provides a better result when the catalysis is enzymatic.
  • the process developed uses commercial enzymatic catalysts and milder process conditions and in this way makes it possible to obtain bio-lubricants with excellent physico-chemical and performance properties, with less energy expenditure, which makes the process described here viable.
EP13164145.8A 2012-04-26 2013-04-17 Verfahren zur Herstellung von Bio-Schnmiermittel aus Methyl-Biodiesel und mit diesem Verfahren hergestelltes Bio-Schmiermittel Withdrawn EP2657324A1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
BRPI1209727 2012-04-26

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210189442A1 (en) * 2017-10-20 2021-06-24 Petróleo Brasileiro S. A. - Petrobras Process for producing esters and biolubricants, catalysed by fermented solid

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996007751A1 (en) * 1994-09-07 1996-03-14 Raision Tehtaat Oy Ab An enzymatic process for preparing a synthetic ester from a vegetable oil
BRPI0520104A (pt) 2005-02-17 2008-06-10 Fraunhofer Ges Forschung mistura de bio-combustìvel, e, processo e dispositivo para a preparação da mesma
CN101475467A (zh) * 2009-01-16 2009-07-08 刘阳 脂肪酶催化合成多元醇酯的新工艺
CN101519847A (zh) * 2009-03-31 2009-09-02 中国石油化工集团公司 一种芳香族聚酰胺纤维用短纤油剂
EP2336277A1 (de) * 2008-10-06 2011-06-22 JX Nippon Oil & Energy Corporation Schmierölzusammensetzung

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1996007751A1 (en) * 1994-09-07 1996-03-14 Raision Tehtaat Oy Ab An enzymatic process for preparing a synthetic ester from a vegetable oil
BRPI0520104A (pt) 2005-02-17 2008-06-10 Fraunhofer Ges Forschung mistura de bio-combustìvel, e, processo e dispositivo para a preparação da mesma
EP2336277A1 (de) * 2008-10-06 2011-06-22 JX Nippon Oil & Energy Corporation Schmierölzusammensetzung
CN101475467A (zh) * 2009-01-16 2009-07-08 刘阳 脂肪酶催化合成多元醇酯的新工艺
CN101519847A (zh) * 2009-03-31 2009-09-02 中国石油化工集团公司 一种芳香族聚酰胺纤维用短纤油剂

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
CECILIA ORELLANA KERMAN ET AL: "Biolubricant synthesis using immobilised lipase: Process optimisation of trimethylolpropane oleate production", PROCESS BIOCHEMISTRY, ELSEVIER, NL, vol. 46, no. 12, 8 August 2011 (2011-08-08), pages 2225 - 2231, XP028328596, ISSN: 1359-5113, [retrieved on 20110817], DOI: 10.1016/J.PROCBIO.2011.08.006 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; PAN, CUI-ZHEN ET AL: "Preparation of oleic acid trimethylolpropane ester", XP002699156, retrieved from STN Database accession no. 2011:380762 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; YIN, SHU-HUA ET AL: "Study on synthesis and application of green lubricating trimethylolpropane oleic acid ester", XP002699155, retrieved from STN Database accession no. 2009:1600302 *
DATABASE CA [online] CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; ZHANG, RUIBO ET AL: "Oiling agent for aromatic polyamide staple fiber", XP002699154, retrieved from STN Database accession no. 2009:1079993 *
PAN, CUI-ZHEN ET AL: "Preparation of oleic acid trimethylolpropane ester", TIANJIN GONGYE DAXUE XUEBAO , 29(6), 47-49 CODEN: TGDXAV; ISSN: 1671-024X, 2010 *
SILVA, J. A. C.: "Desenvolvimento de um Lubrificante Biodegradavel a partir de Esteres do Biodiesel da Mamona", MSC DISSERTATION, 2006
YIN, SHU-HUA ET AL: "Study on synthesis and application of green lubricating trimethylolpropane oleic acid ester", HUAXUE GONGCHENGSHI , 23(10), 60-62 CODEN: HGUOAP; ISSN: 1002-1124, 2009 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20210189442A1 (en) * 2017-10-20 2021-06-24 Petróleo Brasileiro S. A. - Petrobras Process for producing esters and biolubricants, catalysed by fermented solid
AU2018351874B2 (en) * 2017-10-20 2023-09-14 Petróleo Brasileiro S. A. - Petrobras Process for producing esters and biolubricants, catalysed by fermented solid
US11866761B2 (en) * 2017-10-20 2024-01-09 Petróleo Brasileiro S.A.—Petrobras Process for producing esters and biolubricants, catalysed by fermented solid

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