Skip to main content

NOVEL CATALYSTS FOR HYDRODENITRIFICATION OF HEAVY CUTS.

Objective

THE AIM OF THIS PROJECT IS TO DEVELOP NOVEL CATALYSTS FOR THE HYDRODENITRIFICATION OF HEAVY PETROLEUM CUTS THAT CAN BE INTEGRATED INTO EXISTING CATALYTIC SYSTEMS SO AS TO ACHIEVE THE SIMULTANEOUS CONVERSION AND REFINING OF SUCH CUTS.
A search was carried out to find new catalysts for the hydrodenitrification of heavy oil cuts.
Research on the search for denitrification catalysts of heavy cuts may be conducted at the laboratory level by using tests on mixtures of molecule models (quinoline + diethylaniline or phenanthridine + diethylaniline types).
Several active phases for the hydrogenation reactions which were more effective than the mixed nickel molybdenum sulphide were found. These phases were ruthenium based cobalt or nickel pyrite type sulphides).
The most active catalyst for the hydrogenolysis of the carbon nitrogen bond was still cobalt or nickel.
However, the inhibition of this reaction by the heterocyclic compounds may be more or less prevented by the use of mixtures of classic nickel molybdenum aluminium oxide based catalysts and ruthenium sulphide based catalysts. It was possible to replace the alumina carrier by other more neutral or basic carriers. Under these conditions, the same optimal concentrations of the molybdenum and nickel active phases per surface unit of carrier as for alumina were found.
Themost active catalyst was obtained by using the zirconia carrier stablized by additives. It yielded results comparable to those obtained with catalysts developed on alumina but with a higher loading density.
The development of higher performance hydrotreatment and hydroconversion catalysts is required for refining due to the increasingly severe specifications concerning contaminants in the various oil ends.
More advanced denitrification is also required for the stability of hydroconversion catalysts. Thus, continuing research work on denitrification catalysts is justified. The methodology developed has been perfected and it will enable continued research on this subject. Thus, the study of active phases such as nitrides and Chevrel phases must be abandoned, but those of ruthenium based pyrite phases,m at the bulk state and supported state, must be pursued. The study of catalyst mixtures as well as work enabling the development of a zirconia based carrier should lead to the discovery of much more active hydrodenitrification catalysts.
HYDRODENITRIFICATION IS THE MAJOR PROBLEM ENCOUNTERED IN THE REFINING OF HEAVY FRACTIONS. ACID SITES OF CONVENTIONAL CATALYSTS BECOME SOON POISONED BY ASPHALTENES SO THAT ONLY ABOUT 50% OF THE NITROGEN IS REMOVED. SEVEN UNIVERSITY LABORATORIES WILL CO-OPERATE WITH GERTH IN THE VARIOUS AREAS COVERED BY THE RESEARCH WORK. ACTIVE FORMULATIONS ARE TO BE SELECTED FROM AMONG TWO GROUPS OF CATALYSTS: NI OR MO SULPHIDES ON NON-ACIDIC SUPPORTS, AND METALLIC NITRIDES, BORIDES, PHOSPHIDES AND SULPHIDES. AS REGARDS THE FIRST GROUP, MGO, ZRO2, SPECIAL CLAYS AND MG ALUMINATE WILL BE TESTED AS SUPPORTS AFTER PREVIOUS EVALUATION OF THEIR SPECIFIC SURFACE AREA, POROSITY, ACIDIC/BASIC AND ION-EXCHANGE PROPERTIES AS WELL AS OF THEIR CRYSTALLOGRAPHIC STRUCTURE. PRECURSORS AND DEPOSITION TECHNIQUES WILL BE CAREFULLY SELECTED IN ORDER TO OBTAIN AN EXCELLENT DISPERSION OF THE SULPHIDES. AS REGARDS THE SECOND GROUP, CONSIDERATION WILL BE GIVEN BOTH TO UNSUPPORTED PURE COMPOUNDS AND TO NON-STOICHIOMETRIC FORMS AND DISPERSIONS ON THE SUPPORTS SELECTED IN THE EARLIER PHASE. AFTER PHYSICO-CHEMICAL CHARACTERIZATION, THE ACTIVITY OF EACH CATALYST WILL FIRST BE EVALUATED WITH MODEL COMPOUNDS (PYRIDINE, QUINOLINE, INDOLE) IN THE PRESENCE OF H2S AND SUBSEQUENTLY TESTED WITH REAL FEEDSTOCKS (LHVS 0.2, 430 DEGREES CELSIUS MAX, 160 BAR). A SUITABLE PROCEDURE FOR THE COMMERCIAL PRODUCTION OF THE SELECTED CATALYST(S) FROM THAT SCREENING WILL BE DIVISED AND SET UP. A SAMPLE OF 10 TO 50 LITRES WILL BE MADE AVAILABLE AND TESTED FOR STABILITY ON A PILOT PLANT WITH A REAL FEEDSTOCK. /.

Funding Scheme

CSC - Cost-sharing contracts

Coordinator

CENTRE NATIONAL DE LA RECHERCHE SCIENTIFIQUE
Address
Avenue Albert Einstein 2
69626 Villeurbanne
France

Participants (1)

GROUPEMENT EUROPÉEN DE RECHERCHES TECHNOLOGIQUES SUR LES HYDROCARBURES
France
Address
Avenue Napoléon Bonaparte 232
92500 Rueil Malmaison