Catalyst – solid sorbent – or support therefor: product or process – Catalyst or precursor therefor – Sulfur or compound containing same
Reexamination Certificate
1999-06-25
2001-06-05
Wood, Elizabeth D. (Department: 1755)
Catalyst, solid sorbent, or support therefor: product or process
Catalyst or precursor therefor
Sulfur or compound containing same
C502S202000, C502S203000, C502S204000, C502S206000, C502S207000, C502S208000, C502S210000, C502S211000, C502S216000, C502S217000, C502S220000, C502S221000, C502S222000, C502S223000
Reexamination Certificate
active
06242378
ABSTRACT:
The present invention relates to a process for sulphurising a supported hydrorefining or hydroconverting catalyst containing at least one element selected from group IIIB, including the lanthanides and actinides, group IVB, group VB (groups 3, 4, 5 in the new notation for the periodic table: “Handbook of Chemistry and Physics, 76
th
edition, 1995-1996, inside front cover), associated with at least one porous matrix, generally an amorphous or low crystallinity oxide type matrix, and optionally at least one zeolitic or non zeolitic molecular sieve, optionally at least one group VIB metal and optionally at least one element from group VIII (groups 6, 8, 9, 10 in the new notation for the periodic table), optionally at least one element selected from the group formed by P, B, Si, and optionally at least one element from group VIIA (group 17). The invention is characterized in that the catalyst is sulphurised using a mixture containing at least one source of elemental sulphur and at least one source of carbon in an autogenous and/or inert atmosphere.
The present invention also relates to the sulphide catalysts obtained by the sulphurisation process of the present invention.
The present invention also relates to the use of sulphide catalysts for hydrorefining and hydrocracking hydrocarbon-containing feeds containing at least one aromatic and/or olefinic and/or naphthenic and/or paraffinic type compound, said feeds possibly containing metals and/or nitrogen and/or oxygen and/or sulphur.
Sulphides of transition metals and rare earths are also used in lubricants, pigments, battery electrodes, materials for sulphur detectors, materials with specific optical properties, additives for luminescent materials, and anti-corrosion coatings in sulphur-containing atmospheres.
The sulphides can be synthesised by a number of methods which are well known to the skilled person.
Crystallised transition metal or rare earth sulphides can be synthesised by reacting transition metal or rare earth type elements with elemental sulphur at high temperature in a process which is well known to the skilled person in the solid state chemistry field but is expensive, in particular as regards industrial application.
The synthesis of sulphides by reacting a suitable precursor in the form of a mixed oxide of transition metals or rare earths impregnated with a sulphur compound in the liquid phase followed by treatment in hydrogen in a traversed bed reactor is well known to the skilled person.
The synthesis of sulphide catalysts on a porous matrix by treatment of a bulk oxide precursor or an oxide precursor supported on a porous matrix in hydrogen with a sulphur-containing hydrocarbon feed, in particular sulphur-containing petroleum cuts such as gasoline, kerosene, or gas oil, to which a sulphur compound, for example dimethyldisulphide, can optionally be added, is also well known to the skilled person.
Bulk sulphides can also be synthesised by co-precipitation, in a basic medium, of sulphur-containing complexes in solution containing two cations. This method can be carried out at a controlled pH and is termed homogeneous sulphide precipitation. It has been used to prepare a mixed sulphide of cobalt and molybdenum (G. Hagenbach, P. Courty, B. Delmon, Journal of Catalysis, volume 31, page 264, 1973).
Synthesising bulk mixed sulphides on a porous matrix by treatment of a bulk oxide precursor or an oxide precursor supported on a porous matrix in a hydrogen/hydrogen sulphide mixture or nitrogen/hydrogen sulphide mixture is also well known to the skilled person.
United States patent U.S. Pat. No. 4,491,639 describes the preparation of a sulphur-containing compound by reacting elemental sulphur with V, Mo or W salts and in particular V, Mo or W sulphides optionally containing at least one of elements from the series C, Si, B, Ce, Th, Nb, Zr, Ta and U in combination with Co or Ni.
Other methods have been proposed for the synthesis of simple sulphides. As an example, the synthesis of crystallised simple sulphides of rare earths described in U.S. Pat. No. 3,748,095 and French patent FR-A-2 100 551 proceeds by reacting hydrogen sulphide or carbon disulphide with an amorphous rare earth oxide or oxycarbonate at a temperature of over 1000° C.
European patents EP-A-0 440 516 and U.S. Pat. No. 5,279,801 describe a process for synthesising simple transition metal or rare earth sulphur-containing compounds by reacting a transition metal or rare earth compound with a carbon-containing sulphur compound in the gaseous state, in a closed vessel at a moderate temperature of 350° C. to 600° C.
However, it is well known that certain elements such as group IIIB elements, including the lanthanides and actinides, group IVB elements, and group VB elements, are very difficult to sulphurise. The known sulphurisation methods which are routinely used industrially and in the laboratory, such as sulphurisation in a gaseous hydrogen/hydrogen sulphide mixture or liquid phase sulphurisation under hydrogen pressure using a mixture of a hydrocarbon feed and a sulphur-containing compound, such as dimethyldisulphide, are thus ineffective when sulphurising such solids.
The considerable amount of research carried out by the Applicant on preparing sulphide catalysts based on sulphides of elements from groups IIIB, IVB , VB and numerous other elements of the periodic table, used alone or as mixtures, associated with a matrix, have led to the discovery that, surprisingly, by simultaneously reacting elemental sulphur and carbon with a powder containing at least one element selected from group IIIB, including the lanthanides and actinides, group IVB, group VB, and optionally at least one element from group VIII, in a closed or open vessel in an autogenous or inert atmosphere, produces an amorphous or crystalline sulphide compound. Without wishing to be bound by any particular theory, it appears that sulphurisation is obtained by reducing a precursor compound containing the element or elements selected from group IIIB, including the lanthanides and actinides, group IVB, group VB, and optionally at least one group VIII element, with carbon with simultaneous sulphurisation of the reduced element by the sulphur until the precursor containing the element or elements selected from group IIIB, including the lanthanides and actinides, group IVB, group VB, optionally at least one group VIB element, and optionally at least one group VIII element, is exhausted.
The sulphurisation process of the present invention comprises the following steps:
a) Forming, in one or more steps, a reaction mixture which comprises: a powder or mixture of powders containing at least one element selected from group IIIB, including the lanthanides and actinides, group IVB and group VB, at least one porous matrix which is generally an amorphous or low crystallinity oxide type matrix, optionally associated with a zeolitic or non zeolitic molecular sieve, optionally at least one group VIB element, optionally at least one group VIII element, optionally at least one source of an element selected from the group formed by P, B and Si, optionally at least one source of anions from group VIIA, at least one source of elemental sulphur and at least one source of carbon, and optionally water;
b) maintaining the reaction mixture obtained after step a) at a heating temperature of more than 40° C. at a pressure of over 0.01 MPa in a reactor.
The reactor may be a closed reactor. In this case, it may be charged in the open air and after sealing and reacting, the pressure exerted is the autogenous pressure of the gases produced in the reduction and sulphurisation reactions. The reactor can also be charged in an atmosphere of an inert gas.
The reactor can optionally be a traversed bed reactor, such as a fixed bed, moving bed, ebullated bed, or fluidised bed reactor. In this case the pressure exerted is that of an inert gas.
Preferably, a closed reactor is used.
The catalyst can also be sulphurised ex-situ, for example in a zone which is outside the zone where the catalyst is to be used.
The sulphur source is elementa
Institut Francais du Pe'trole
Millen White Zelano & Branigan P.C.
Wood Elizabeth D.
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