Objectif
TO IMPROVE KNOWLEDGE OF THE REACTIONS THAT TAKE PLACE DURING THERMAL TREATMENT OF HEAVY PETROLEUM CUTS WITH A VIEW TO ENHANCING THE STABILITY OF PRODUCTS.
4 typical vacuum residues (IRANIAN HEAVY, VEGA, SARIR and KUWAIT) were submitted to thermogravimetric analysis in order to obtain the kinetic parameters. The accuracy and reliability of the experimental data were supported by the correlation coefficient (more than 99.5%). This facts helped to assume an overall kinetics of the 1st order. The activation energy values obtained for Arabian feedstock of 210 to 220 kJ/mol were fairly consistent with literature values.
The low energy value (E) of 170 kJ/mol from pyrolysis of VEGA feed may be explained by significant amounts of light fractions derived from dealkylation of asphaltene (ASPH) (28% in the feed). The Lybian SARIR gave an unusually high activation energy result probably due to the great amount of energy necessary to decompose the paraffinic chains.
The visbreaking process was applied to the North African feeds (AMMA, ESSIDER, SARIR). The main characteristic of paraffinic feedstocks after the thermal shock was the increasing viscosity of the residue as well as the severity of the process. This behaviour involved a limit in the raw or isoviscous yield, in order to avoid a concurrent coking in the coils at increasing severity.
Thermal stress induced a strong increase in ASPH with a decomposition and condensation of resins, aromatic and naphthenic groups showed small changes in size and properties.
An improvement in the yield can be obtained with a 50 50 blend of SARIR with the middle aromatic residue of ESSIDER. This result enabled an increase in the limit processing temperature to 490 C with a yield increase at the isoviscous state of the tar. The increment of coke in coils can be maintained under the critical limits. In this blend of high malthenic fraction, the ASPHs maintained their peptizability in the system for a large concentration range.
Middle East feeds (IRANIAN HEAVY, KIRKUK, KUWAIT) were also processed. The strong effect of increasing temperature from 450 C to 500 C on the cumulative yield in d istillate was coupled with a gradual shift to light fraction while coke formation in coils became critical, particularly for samples with high ASPH or resin content. The processability of these residues was therefore related to the ASPH level of the feedstocks. The tar stability of the visbroken residue depended on the reaction temperature and pressure; in the optimum range of reaction (485 to 490 C) the Arabian tar retained a margin of rheological stability sufficient for pumping and storage. The low paraffinic nature of the heavy ends caused a secondary thermal reaction similar to the condensation coke formation. An interesting behaviour has been found in the visbreaking of VEGA, which showed a peculiar feature for a high ASPH content with atomic ratio of hydrogen to carbon greater than 1.
TRADITIONAL TREATMENT OF HEAVY RESIDUES, SUCH AS COKING, THERMAL CRACKING AND VISBREAKING, RESULT IN GAS OILS AND VACUUM DISTILLATES OF MARKED INSTABILITY, AS IS SHOWN, FOR EXAMPLE, BY THE FORMATION OF INSOLUBLE IN THE FORMER AND BY VISCOSITY CHANGE AND PRECIPITATION OF ASPHALTENES IN THE LATTER. IN COMMERCIAL PLANTS, REDUCING THE SEVERITY AND USING SUITABLE SOLVENTS ARE THE COMMONEST WAYS OF MINIMIZING THESE PHENOMENA. IT IS INTENTED TO GAIN A BETTER INSIGHT INTO THE UNDERLYING REACTIONS AND DEVISE NEW MEANS OF MANAGING THEM THROUGH A COLLABORATIVE RESEARCH PROGRAMME INVOLVING SEPARATE CONTRACTS WITH AGIP PETROLI, SELM AND ERG SPA (SEE EN3C004100-I (A) AND EN3C004700-I (A)). SELM'S CONTRIBUTION WILL CONCERN THE FOLLOWING SUBPROGRAMMES:
- DEVELOPMENT OF ANALYSIS METHODS IN ORDER TO OBTAIN AN INSIGHT INTO FEEDSTOCKS AND DERIVED LIGHT FRACTIONS. HRGC, HPLC, GPC AND OTHER MODERN TECHNIQUES WILL BE USED.
- THERMOGRAVIMETRIC ANALYSIS ACCORDING TO SCHUKER AND JECS (1983) OF FRACTIONS OF DIFFERING CHEMICAL NATURE OBTAINED FROM VARIOUS RESIDUES BY CHROMATOGRAPHIC SEPARATION TECHNIQUES. VARIOUS H.R. IN THE TEMPERATURE RANGE 360 TO 450 CELSIUS DEGREES WILL BE USED . K APP., EA AND ORDER OF REACTION WILL BE CALCULATED BY USING THE FREEMAN AND CARR APPROACH.
- PILOT-PLANT VISBREAKING RUNS ON RESIDUES IN THE PRESENCE OF SUITABLE HYDROGEN DONORS, POSSIBLY SOURCED FROM PETROLEUM REFINING PROCESSES. SUCH COMPOUNDS, MAINLY OF HYBRID NAPHTENIC NATURE, ACTING ALSO AS RADICAL INITIATORS AND TERMINATORS, WILL BE SEPARATED BY DISTILLATION, HYDROGENATED AND THEN RECYCLED.
- AN ATTEMPT TO CONSTRUCT A MATHEMATICAL MODEL, USING ALL THE KINETIC DATA THUS OBTAINED AS WELL AS THOSE DERIVED BY THE OTHER COLLABORATING CONTRACTORS.
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CORDIS classe les projets avec EuroSciVoc, une taxonomie multilingue des domaines scientifiques, grâce à un processus semi-automatique basé sur des techniques TLN. Voir: Le vocabulaire scientifique européen.
- ingénierie et technologie génie de l'environnement énergie et combustibles énergie fossile pétrole
- ingénierie et technologie génie chimique technologies de séparation distillation
- sciences naturelles mathématiques mathématiques appliquées modèle mathématique
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