Title: Metaloxide--ZrO2 catalysts for the esterification and transesterification of free fatty acids and triglycerides to obtain bio-diesel

Abstract

Mixed metal oxide catalysts (ZnO, CeO, La2O3, NiO, Al203, SiO2, TiO2, Nd2O3, Yb2O3, or any combination of these) supported on zirconia (ZrO2) or hydrous zirconia are provided. These mixed metal oxide catalysts can be prepared via coprecipitation, impregnation, or sol-gel methods from metal salt precursors with/without a Zirconium salt precursor. Metal oxides/ZrO2 catalyzes both esterification and transesterification of oil containing free fatty acids in one batch or in single stage. In particular, these mixed metal oxides supported or added on zirconium oxide exhibit good activity and selectivity for esterification and transesterification. The low acid strength of this catalyst can avoid undesirable side reaction such as alcohol dehydration or cracking of fatty acids. Metal oxides/ZrO2 catalysts are not sensitive to any water generated from esterification. Thus, esterification does not require a water free condition or the presence of excess methanol to occur when using the mixed metal oxide catalyst. The FAME yield obtained with metal oxides/ZrO2 is higher than that obtained with homogeneous sulfuric acid catalyst. Metal oxides/ZrO2 catalasts can be prepared as strong pellets and in various shapes for use directly in a flow reactor. Furthermore, the pellet has a strong resistance toward dissolution to aqueous or oil phases.

Inventors:

Kim, Manhoe; Salley, Steven O.; Ng, K. Y. Simon

Issue Date:

Tue Sep 06 00:00:00 EDT 2016

Research Org.:

Wayne State Univ., Detroit, MI (United States)

Sponsoring Org.:

USDOE

OSTI Identifier:

1322103

Patent Number(s):

9433924

Application Number:

13/508,738

Assignee:

WAYNE STATE UNIVERSITY (Detroit, MI)

Patent Classifications (CPCs):

B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

C - CHEMISTRY C10 - PETROLEUM, GAS OR COKE INDUSTRIES C10G - CRACKING HYDROCARBON OILS

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B - PERFORMING OPERATIONS B01 - PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL B01J - CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY

B01J21/063 - {Titanium
B01J21/066 - {Zirconium or hafnium
B01J23/002 - {Mixed oxides other than spinels, e.g. perovskite}
B01J23/06 - of zinc, cadmium or mercury
B01J23/10 - of rare earths
B01J23/80 - with zinc, cadmium or mercury
B01J2523/00 - Constitutive chemical elements of heterogeneous catalysts
B01J2523/27 - Zinc
B01J2523/3725 - Neodymium
B01J2523/3743 - Europium
B01J2523/3787 - Ytterbium
B01J2523/41 - Silicon
B01J2523/47 - Titanium
B01J2523/48 - Zirconium
B01J2523/847 - Nickel
B01J37/031 - {Precipitation}
B01J37/036 - {to form a gel or a cogel}

C - CHEMISTRY C10 - PETROLEUM, GAS OR COKE INDUSTRIES C10G - CRACKING HYDROCARBON OILS

C10G2300/1003 - Waste materials
C10G2300/1011 - Biomass

C - CHEMISTRY C11 - ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES C11C - FATTY ACIDS FROM FATS, OILS OR WAXES

C11C3/003 - {by esterification of fatty acids with alcohols

Y - NEW / CROSS SECTIONAL TECHNOLOGIES Y02 - TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE Y02E - REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

Y02E50/10 - Biofuels

Y - NEW / CROSS SECTIONAL TECHNOLOGIES Y02 - TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE Y02P - CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

Y02P30/20 - Bio-feedstock

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DOE Contract Number:  

FG36-05GO85005

Resource Type:

Patent

Resource Relation:

Patent File Date: 2010 Nov 08

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY