Process for the preparation of a catalyst, catalyst and its use in a hydroconversion and/or hydrotreatment process

Abstract

The invention concerns a process for the preparation of a catalyst starting from a pre-catalyst comprising at least one catalytic metal and a support, said pre-catalyst having undergone a heat treatment at at least 60 C. without calcining, in which process said pre-catalyst is impregnated with a basic solution having a pH of more than 7.5 and containing at least one molecule in the zwitterionic form, and the impregnated pre-catalyst is dried at a temperature of at most 240 C. without subsequent calcining. The molecule in the zeolite form is selected from the group formed by amino-alcohol acids containing secondary or tertiary amine groups and containing at least one carboxylic acid function (and preferably only one) and at least one alcohol function. It is bicine or tricine, for example. The invention also concerns the catalyst prepared using this process, and its use in hydrotreatment and/or hydroconversion.

Claims

1. A process for the preparation of a catalyst starting from a pre-catalyst comprising at least one catalytic metal and a support, said pre-catalyst having undergone a heat treatment at at least 60 C. without calcining, in which process said pre-catalyst is impregnated with a basic solution having a pH of more than 7.5 and containing at least one molecule in the zwitterionic form, and the impregnated pre-catalyst is dried at a temperature of at most 240 C. without subsequent calcining, and the molecule in the zwitterionic form is selected from the group formed by amino-alcohol acids containing secondary or tertiary amine groups and containing at least one carboxylic acid function and at least one alcohol function.

2. The process according to claim 1, in which said molecule has a single carboxylic acid function.

3. The process according to claim 1, in which the molecule in the zwitterionic form is bicine.

4. The process according to claim 1, in which the molecule in the zwitterionic form is tricine.

5. The process according to claim 1, in which impregnation is carried out at a pH of more than 8.5.

6. The process according to claim 5, in which the base is ammonia.

7. The process according to claim 1, in which after impregnation, the pre-catalyst undergoes a maturation step.

8. The process according to claim 1, in which drying is carried out at a temperature in the range of 50 C. to 240 C.

9. The process according to claim 1, in which said pre-catalyst comprises at least one catalytic metal selected from the group formed by metals from group VIB and non-noble group VIII, and optionally comprises phosphorus.

10. The process according to claim 9, in which said pre-catalyst also comprises boron and/or silicon.

11. The process according to claim 1, in which said molecule is added in a quantity such that the molecule/GVIB molar ratio is in the range of 0.05 to 2.0.

12. The process according to claim 1, in which said pre-catalyst has been prepared by dry impregnation of said support with a solution of said catalytic metal.

13. The process according to claim 1, in which said pre-catalyst has been heat treated at a temperature in the range of 60 C. to 220 C.

14. The process according to claim 1, in which said catalyst undergoes sulphurization after said drying.

15. A catalyst which is susceptible of being prepared using the process in accordance with claim 1.

16. A process for the hydrotreatment and/or hydroconversion of a hydrocarbon feed by bringing said feed into contact with the catalyst according to claim 15, in which process said catalyst contains at least one metal from group VIB and at least one metal from group VIII and said metals are in the sulphide form.

17. The process according to claim 1, in which impregnation is carried out at a pH of more than 10.

18. The process according to claim 1, in which after impregnation, the pre-catalyst undergoes a maturation step for 0.1 to 10 h and at a temperature of 15 C. to 80 C.

19. The process according to claim 1, in which said pre-catalyst comprises at least one catalytic metal selected from the group formed by metals from group VIB and non-noble group VIII, and comprises phosphorus.

20. The process according to claim 1, in which said molecule is added in a quantity such that the molecule/Mo molar ratio is in the range of 0.05 to 2.0.

Description

DETAILED DESCRIPTION OF THE PROCESS FOR THE PREPARATION OF THE CATALYST IN ACCORDANCE WITH THE INVENTION

(1) The process for the preparation of the catalyst in accordance with the invention comprises the following steps in succession starting from a support based on at least one porous mineral matrix which has been shaped and which has undergone a heat treatment (this product will be termed the support):

(2) a) impregnation of the support with an impregnating solution containing at least one catalytic metal; preferably, the solution contains at least one catalytic metal from group VIB and at least one catalytic metal from non-noble group VIII; impregnation is followed by optional maturation; the product obtained will be termed the impregnated support.

(3) b) heat treatment at at least 60 C. without subsequent calcining, preferably at a temperature of at most 220 C.; the product obtained will be termed the pre-catalyst.

(4) c) impregnation of the pre-catalyst with a basic impregnating solution comprising at least one organic molecule termed a zwitterion as defined hereinabove, followed by optional maturation; the product obtained will be termed the impregnated pre-catalyst.

(5) e) drying at a temperature of at most 240 C. and usually less than 220 C., without subsequent calcining; the product obtained will be termed the catalyst.

(6) Process for Preparing the Support in Accordance with the Invention

(7) The support for the catalyst in accordance with the invention is advantageously prepared from a porous amorphous mineral matrix based on at least one refractory oxide containing or not containing a zeolite.

(8) The porous mineral matrix is advantageously selected from the group formed by alumina, silica, clays, titanium oxide, oxides of boron or phosphorus and zirconium, used alone or as a mixture. In the context of the invention, it is preferable to use matrices containing mainly alumina, in all of the forms known to the person skilled in the art, for example in the form of gamma alumina. It is also advantageous to use mixtures of alumina and silica, mixtures of alumina and silica-alumina, mixtures of aluminas and zeolites, or indeed mixtures of aluminas, silica-alumina and zeolites. Preferably, the support for the catalyst in accordance with the invention contains only alumina or silica-alumina, optionally with metal(s) and/or dopants(s) which have been introduced outside the impregnation steps (group VIB, group VIII, P, Si, F, etc.) before or during shaping of the support.

(9) The support may advantageously be shaped using any technique which is known to the person skilled in the art. Shaping may be carried out, for example, by extrusion, pelletization, by the oil drop method, by rotary plate granulation or using any other method which is well known to the person skilled in the art. The catalysts of the invention may optionally be manufactured and used in the form of crushed powder, extrudates, tablets, rings, beads or wheels. The advantageous method for shaping in accordance with the invention is extrusion and the preferred extrudate shape is that of a cylinder (which may or may not be hollow), twisted cylinder or multilobe (2, 3, 4 or 5 lobes, for example). It is also advantageous for the catalyst to be in the form of extrudates with a diameter in the range 0.4 to 5 mm, and more particularly in the range 0.9 to 2.5 mm. The shaped solid is then dried at a temperature in the range 60 C. to 250 C. and calcined at a temperature in the range 250 C. to 800 C. for a period in the range 30 minutes to 6 hours in order to provide a support as defined in the context of the invention.

(10) Process for the Preparation of the Impregnated Support in Accordance with the Invention

(11) The catalytic metal (metals) is (are) introduced by impregnation of an aqueous solution onto the support as defined in the context of the invention.

(12) Preferably, at least one metal from group VIB and at least one metal from non-noble group VIII of the periodic classification of the elements are introduced, and optionally at least one promoter element from group VIIA and optionally at least one element from group VB such as phosphorus.

(13) The impregnation of various metals/elements may be carried out in one or more steps. The impregnation of the solution may be carried out using any of the methods which are well known to the person skilled in the art, i.e. by one or more operations for impregnating a support as defined in the context of the invention using a solution containing precursors of the metal or metals and optionally containing the precursor of at least one promoter element such as phosphorus and optionally the precursor of at least one element from group VIIA and/or group VB.

(14) Any of the metals from group VIB may be used for the purposes of the invention. Preferably, the metals from group VIB used in accordance with the invention are tungsten and molybdenum, used alone or as a mixture. More preferably, the metal from group VIB in accordance with the invention is molybdenum.

(15) The sources of molybdenum and tungsten are advantageously selected from oxides and hydroxides, molybdic and tungstic acids and their salts, in particular their ammonium salts such as ammonium molybdate, ammonium heptamolybdate, ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid, silicotungstic acid and their salts. Preferably, the oxides and ammonium salts such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate are used.

(16) Any of the non-noble metals from group VIII may be used for the purposes of the invention. Preferably, the non-noble metals from group VIII used in accordance with the invention are nickel and cobalt, used alone or as a mixture.

(17) The catalytic metals are generally a combination of metals from group VIII (preferably Co and/or Ni) and metals from group VIB (preferably Mo). The sources of the non-noble metal from group VIII which may be used are well known to the person skilled in the art. As an example, for the non-noble metals, nitrates, sulphates, hydroxides, phosphates, halides, for example chlorides, bromides and fluorides, and carboxylates such as acetates and carbonates, for example, will be used.

(18) In general, the total content of the hydro-dehydrogenating elements, i.e. of metal(s) from group VIII and metal(s) from group VIB, is more than 6% by weight of metals from groups VIB and VIII (calculated with respect to the oxide) with respect to the total weight of pre-catalyst; preferably, it is in the range 5% to 50% by weight of the metals (calculated with respect to the oxide) from groups VIB and VIII with respect to the total weight of the pre-catalyst. The content of metal(s) from group VIB is in the range 4% to 40% of the weight of the metal(s) (calculated with respect to the oxide) from group VIB with respect to the total weight of pre-catalyst, preferably in the range 8% to 35% by weight and still more preferably in the range 10% to 30% by weight of metal(s) (calculated with respect to the oxide) from group VIB with respect to the total weight of the pre-catalyst. The content of metal(s) from group VIII is in the range 1% to 10% by weight of metal(s) (calculated with respect to the oxide) from group VIII with respect to the total weight of pre-catalyst, preferably in the range 1.5% to 9% by weight and more preferably in the range 2% to 8% by weight of metal(s) (calculated with respect to the oxide) from group VIII with respect to the total weight of pre-catalyst. The percentages by weight of metals from groups VIII and VIB indicated above are expressed with respect to the total weight of pre-catalyst for the preparation process in accordance with the invention.

(19) The molar ratio of metal(s) from group VIII to metal(s) from group VIB in the catalyst is preferably in the range 0.05 to 0.9, highly preferably in the range 0.1 to 0.8, and still more preferably in the range 0.2 to 0.6.

(20) A promoter element from group VB which is preferred for the purposes of the invention is phosphorus. The preferred source of phosphorus is orthophosphoric acid, H.sub.3PO.sub.4, but its salts and esters such as ammonium phosphates are also suitable. The phosphorus may, for example, be introduced in the form of a mixture of phosphoric acid and a basic organic compound containing nitrogen such as ammonia, primary and secondary amines, cyclic amines, compounds from the pyridine family and quinolines and compounds from the pyrrole family. Tungstophosphoric and tungstomolybdic acids may be employed.

(21) The phosphorus content is adjusted, although this does not limit the scope of the invention, in a manner such as to form a mixed compound in solution and/or on the support, for example tungsten-phosphorus or molybdenum-tungsten-phosphorus. These mixed compounds may be heteropolyanions. These compounds may be Anderson heteropolyanions, for example. The phosphorus may also be introduced at the same time as the element(s) from group VIB in the form of Keggin, lacunary Keggin, substituted Keggin or Strandberg type heteropolyanions.

(22) The phosphorus content is preferably in the range 0.1% to 20% by weight of P.sub.2O.sub.5, more preferably in the range 0.2% to 15% by weight of P.sub.2O.sub.5, highly preferably in the range 0.3% to 10% by weight of P.sub.2O.sub.5. The percentage is expressed with respect to the total weight of pre-catalyst for the preparation process in accordance with the invention. When the catalyst contains at least one metal from group VIB, the quantity of phosphorus is such that the molar ratio of phosphorus to metal(s) from group VIB in the pre-catalyst is 0.11 or more, preferably 0.25 or more, and more preferably 2 or even 1.4 or less.

(23) After impregnation, the sample is then matured for between 15 min and 10 h, preferably in the range 30 min to 5 h, and more preferably in the range 1 h to 4 h in order to obtain the impregnated support in accordance with the invention.

(24) After impregnation and optional maturation, the impregnated support is then dried at a temperature in the range 60 C. to 220 C. in order to obtain the pre-catalyst in accordance with the invention.

(25) Process for the Preparation of the Impregnated Pre-catalyst in Accordance with the Invention

(26) The pre-catalyst of the invention is then impregnated with a solution containing at least one organic molecule of the zwitterionic type (which will also be termed a zwitterion in the text) in a basic medium. In the context of the invention, zwitterions are amino-alcohol acids containing secondary or tertiary amine groups and containing at least one carboxylic acid function and at least one alcohol function. Preferably, the zwitterion has a single carboxylic acid function.

(27) More preferably, more specific preferred zwitterions are bicine and tricine. A spatial representation of bicine (A) and tricine (B) is given below:

(28) ##STR00001##

(29) The quantity of zwitterionic molecule added is adjusted to the quantity of metal from group VIB engaged in a manner such that the zwitterion/metal from group VIB molar ratio, and more particularly the zwitterionic molecule/Mo molar ratio, is in the range 0.05 to 2.0, preferably in the range 0.2 to 1.5.

(30) The pH for impregnation of the solution containing the zwitterions and the base must be more than 7.5, preferably more than 8.5 and more preferably more than 10.0. The base used is usually ammonia.

(31) In general, a single impregnation step is sufficient. This provides savings as regards industrialization, and simplifies the impregnation line, especially if an intermediate drying stage is necessary between the impregnation steps.

(32) Preferably, after the impregnation step, the impregnated pre-catalyst then undergoes a maturation step. Preferably, it is carried out for a period in the range 0.1 to 10 h, preferably in the range 0.5 to 7 h and more preferably in the range 1 to 5 h, and at a temperature in the range 15 C. to 80 C., preferably in the range 20 C. to 50 C.

(33) After impregnation and preferably after maturation, the impregnated pre-catalyst undergoes a drying step carried out at a temperature in the range 50 C. to 240 C., preferably in the range 65 C. to 220 C. and highly preferably in the range 75 C. to 200 C. The drying step may be carried out either in oxygen, air or nitrogen or a mixture of these gases. The catalyst is then obtained.

(34) There is no subsequent calcining step, i.e. a step carried out after drying. Clearly, in accordance with the invention, the drying temperatures are not calcining temperatures. The invention does not concern calcined or regenerated catalysts. It only concerns catalysts termed fresh catalysts or new (unused) catalysts and which are dried.

(35) Process for the Preparation of the Sulphurized Catalyst in Accordance with the Invention

(36) The process for the preparation of the catalyst in accordance with the invention advantageously comprises at least one sulphurization step.

(37) The active phase of the catalyst is in the sulphide form. The catalyst may then be used in a process for hydrotreatment and/or hydroconversion, as will be described below in the present description.

(38) This activation treatment by sulphurization is well known to the person skilled in the art and may be carried out using any method known to the person skilled in the art. Sulphurization is carried out by bringing the catalyst prepared in accordance with the process of the invention into contact with at least one decomposable sulphur-containing organic compound which generates H.sub.2S or by direct contact of the catalyst with a stream of gaseous H.sub.2S, for example diluted in hydrogen. The organic sulphur-containing compound is advantageously selected from alkyldisulphides such as dimethyldisulphide (DMDS), alkylsulphides such as dimethyl sulphide, mercaptans such as n-butylmercaptan, polysulphide compounds of the tertiononylpolysulphide type such as TPS-37 or TPS-54 sold by ARKEMA, or any other compound known to the person skilled in the art for obtaining good sulphurization of a catalyst. The sulphurization may be carried out in situ (i.e. after charging the catalyst into the reaction unit of the hydrotreatment and/or hydroconversion process) or ex-situ (i.e. before charging the catalyst into the reaction unit) at a temperature which is generally in the range 200 C. to 600 C., more preferably in the range 300 C. to 500 C.

(39) Processes Using the Catalyst of the Invention

(40) The catalysts obtained by the process of the invention are advantageously used for reactions for the hydrotreatment or hydroconversion of hydrocarbon feeds such as oil cuts, cuts obtained from coal or hydrocarbons produced from natural gas. The term hydrotreatment should be understood to mean hydrogenation, hydrodenitrogenation, hydrodearomatization, hydrodesulphurization, and hydrodemetallization reactions.

(41) These catalysts may advantageously be used during mild hydrocracking operated as a pre-treatment of catalytic cracking or hydrocracking feeds. They may also be used for the hydrodesulphurization of residues. These catalysts have remarkable performances in processes for the intense hydrodesulphurization of diesels (ULSDUltra Low Sulphur Diesel) or for processes intended to obtain an improved cetane number.

(42) When utilized in this manner, the catalysts obtained by the process in accordance with the invention have improved performances, in particular an improved activity, compared with prior art catalysts.

(43) The feeds employed in the hydrotreatment processes are, for example kerosenes, gas oils, vacuum gas oils, atmospheric residues, vacuum residues, atmospheric distillates, vacuum distillates, deasphalted residues or crudes, feeds obtained from thermal or catalytic conversion processes, feeds obtained from biomass, used alone or as a mixture. The feeds which are treated, in particular those mentioned above, generally contain heteroatoms such as sulphur, oxygen and nitrogen and, for the heavy feeds, they usually also contain metals originating from the treated feeds and which deactivate the catalyst.

(44) The operating conditions used in the processes for the hydrotreatment and/or hydroconversion of hydrocarbon feeds are generally as follows: the temperature is advantageously in the range 180 C. to 450 C., preferably in the range 250 C. to 440 C., the pressure is advantageously in the range 0.5 to 300 bar, preferably in the range 1 to 180 bar, the hourly space velocity is advantageously in the range 0.1 to 20 h.sup.1, preferably in the range 0.2 to 5 h.sup.1, and the hydrogen/feed ratio, expressed as the volume of hydrogen, measured under normal temperature and pressure conditions, per volume of liquid feed is advantageously in the range 50 L/L to 2000 L/L.

(45) The examples below demonstrate the large increase in activity with the utilization of the invention of catalysts prepared in accordance with the invention compared with prior art catalysts, and describe the invention without in any way limiting its scope.

EXAMPLE 1

Preparation of CoMoP Catalysts on Alumina A1 and A2 (Not in Accordance with the Invention)

(46) A matrix composed of alumina gel sold under the name SB3 by Conda Chemie GmbH was used. This gel was mixed with an aqueous solution containing 66% nitric acid (7% by weight of acid per gram of dry gel) then mixed for 15 minutes. At the end of this mixing, the paste obtained was passed through a die with cylindrical orifices with a diameter of 1.6 mm. The extrudates were then dried overnight at 120 C., and calcined at 600 C. for 2 hours in moist air containing 50 g of water per kg of dry air. Extrudates of a support were thus obtained which had a specific surface area of 300 m.sup.2/g. X-ray diffraction analysis revealed that the support was solely composed of low crystallinity cubic gamma alumina.

(47) Cobalt, molybdenum and phosphorus were added to the alumina support described above and in the form of extrudates. The impregnating solution was prepared by hot dissolution of molybdenum oxide (24.34 g) and cobalt hydroxide (5.34 g) to the solution of phosphoric acid (7.47 g) in aqueous solution. After dry impregnation, the extrudates were allowed to mature in a water-saturated atmosphere for 12 h, then dried overnight at 90 C. The dried pre-catalyst obtained thereby was denoted A1.

(48) Calcining of the catalytic precursor A1 at 450 C. for 2 hours produced a calcined pre-catalyst A2, which was not in accordance with the invention.

(49) The final composition of catalysts A1 and A2, expressed in the oxide form, was thus as follows: MoO.sub.3=21.8% by weight, CoO=4.6% by weight and P.sub.2O.sub.5=7.1% by weight.

(50) The calcined catalyst A2 was charged into a flushed bed unit and sulphurized using a straight run diesel supplemented with 2% by weight of dimethyldisulphide. A HDS test of a mixture of straight run diesel and diesel from catalytic cracking was then carried out for 300 h.

EXAMPLE 2

Preparation of Supplemented CoMoP Catalysts A3 to A8 (In Accordance with the Invention)

(51) The catalysts A3 to A8 were prepared by impregnation of the dried pre-catalyst A1 with an aqueous solution containing bicine or tricine mixed with ammonia. The composition of the impregnated solutions is given in Table 1.

(52) The impregnated pre-catalyst then underwent a maturation step for 3 h in air at ambient temperature, followed by a heat treatment step at 140 C. for 2 h in nitrogen (0.065 L/h/g of catalyst).

(53) TABLE-US-00001 TABLE 1 Composition of solutions impregnated onto catalysts A3 to A8. Zwitterionic molecule Bicine Tricine Sample ref A3 A4 A5 A6 A7 A8 Zwitterionic molecule/Mo 0.6 0.7 0.8 0.8 0.9 1 (mol/mol) Concentration of 2.2 2.6 3.0 3.0 3.4 3.7 zwitterionic molecule in the solution (mol/L) Mass of NH.sub.4OH (g) 0.24 0.24 0.24 0.24 0.24 0.24 pH of the solution >10

EXAMPLE 3

Comparative Test of Catalysts A1 to A8 in the Hydrogenation of Toluene in Cyclohexane under Pressure and in the Presence of Hydrogen Sulphide

(54) The catalysts described above were dynamically sulphurized in situ in the fixed flushed bed tube reactor of a pilot unit. The hydrogenating activity measurements were carried out immediately after sulphurization under pressure and without letting in air with the hydrocarbon feed which acted so sulphurize the catalysts.

(55) The sulphurization and test feed was composed of 5.8% of dimethyldisulphide (DMDS), 20% of toluene and 74.2% of cyclohexane (by weight). The sulphurization was carried out at ambient temperature to 350 C., with a temperature ramp-up of 2 C./min, a HSV=4 h.sup.1 and H.sub.2/HC=450 NL/L. The catalytic test was carried out at 350 C. at a HSV=2 h.sup.1 and H.sub.2/HC equivalent to that for sulphurization, with a minimum of 4 test samples being taken, which were analysed by gas phase chromatography.

(56) Thus, the stabilized catalytic activities of equal volumes of catalysts were measured for the toluene hydrogenation reaction. The detailed conditions for the activity measurement are given in Table 2.

(57) TABLE-US-00002 TABLE 2 Conditions of toluene hydrogenation test. Total pressure 6.0 MPa Pressure of toluene 0.37 MPa Pressure of cyclohexane 1.42 MPa Pressure of methane 0.22 MPa Pressure of hydrogen 3.68 MPa Pressure of H.sub.2S 0.22 MPa Hourly space velocity 2 h.sup.1 Temperature of sulphurization and test 350 C.
Liquid effluent samples were analysed by gas phase chromatography. Determining the molar concentrations of unconverted toluene (T) and the concentrations of its hydrogenation products (methylcyclohexane (MCC6), ethylcyclopentane (EtCC5) and the dimethylcyclopentanes (DMCC5)) allowed a percentage toluene hydrogenation value, X.sub.HYD, to be calculated, which is defined as follows:

(58) $X_{\mathrm{HYD}}\left(\%\right)=100\frac{\mathrm{MCC}6+\mathrm{EtCC}5+\mathrm{DMCC}5}{T+\mathrm{MCC}6+\mathrm{EtCC}5+\mathrm{DMCC}5}$

(59) Since the toluene hydrogenation reaction is first order under the test conditions employed and the reactor behaves as an ideal piston reactor, the hydrogenating activity A.sub.HYD for the catalysts is calculated by applying the following formula:

(60) $A_{\mathrm{HYD}}=\ln \left(\frac{100}{100-X_{\mathrm{HYD}}}\right)$

(61) Table 3 compares the relative hydrogenating activities of the catalysts, equal to the ratio of the activity of the supplemented catalyst over the activity of the calcined pre-catalyst A2 (not in accordance with the invention) taken as a reference (activity 100%).

(62) TABLE-US-00003 TABLE 3 Relative activities in toluene hydrogenation test compared with calcined catalyst A2 (not in accordance) for the hydrogenation of toluene using the supplemented catalysts A3 to A8 (in accordance). Relative A.sub.HYD compared with A2 Catalyst Composition of supplementing solution (% 5%) Calcined A2, 100 not in accordance A3 Bicine/NH.sub.4OH (Bicine/Mo = 0.6 mol/mol) 115 in accordance A4 Bicine/NH.sub.4OH (Bicine/Mo = 0.7 mol/mol) 117 in accordance A5 Bicine/NH.sub.4OH (Bicine/Mo = 0.8 mol/mol) 123 in accordance A6 Tricine/NH.sub.4OH (Tricine/Mo = 0.8 mol/mol) 113 in accordance A7 Tricine/NH.sub.4OH (Tricine/Mo = 0.9 mol/mol) 112 in accordance A8 Tricine/NH.sub.4OH (Tricine/Mo = 1.0 mol/mol) 131 in accordance

(63) The results summarized in Table 3 show that all of the catalysts supplemented with bicine or tricine in a basic medium prepared in accordance with the invention have improved performances in the toluene hydrogenation test, compared with the calcined reference, which is not in accordance with the invention.

EXAMPLE 4

Comparative Test of Calcined Catalysts A2 (Not in Accordance with the Invention) and Catalysts A1 to A8 (In Accordance with the Invention) in the HDS of Diesel of Catalysts

(64) The catalysts A2 (not in accordance) and A3 to A8 (in accordance) were tested using diesel HDS. The composition of the feed is given in Table 4.

(65) TABLE-US-00004 TABLE 4 Composition of diesel HDS feed. Density at 15 C. (g/cc) 0.8522 Sulphur (% by weight) 1.44 Simulated distillation IP 155 C. 10% 247 C. 50% 315 C. 90% 392 C. EP 444 C.

(66) The test was carried out in a flushed fixed bed isothermal pilot reactor, the fluids moving from bottom to top. After in situ sulphurization at 350 C. in the unit under pressure using the test diesel to which 2% by weight dimethyldisulphide had been added, the hydrodesulphurization test was carried out under the operating conditions shown in Table 5.

(67) TABLE-US-00005 TABLE 5 Conditions for diesel hydrotreatment tests. Total pressure 7 MPa Volume of catalyst 30 cm.sup.3 Flow rate of hydrogen 24 L/h Flow rate of feed 60 cm.sup.3/h

(68) The catalytic performances of the catalysts tested using diesel HDS are given in Table 6. They are expressed as the relative activity. The relative activity of the catalysts was measured by adjusting the temperature of the process in order to obtain a sulphur level of 10 ppm in the products formed. The lower this temperature is, the more active will the catalyst be. The activity of the calcined catalyst A2 was considered here to be the base performance.

(69) TABLE-US-00006 TABLE 6 Relative diesel HDS activities compared with calcined catalyst A2 (not in accordance) for the hydrotreatment of diesel for supplemented catalysts A3 to A8 (in accordance). Temperature to reach 10 ppm S in Catalyst Composition of supplementing solution the effluents Calcined A2, Base not in accordance A3 Bicine/NH.sub.4OH (Bicine/Mo = 0.6 mol/mol) Base - 5 C. in accordance A4 Bicine/NH.sub.4OH (Bicine/Mo = 0.7 mol/mol) Base - 5 C. in accordance A5 Bicine/NH.sub.4OH (Bicine/Mo = 0.8 mol/mol) Base - 6 C. in accordance A6 Tricine/NH.sub.4OH (Tricine/Mo = 0.8 mol/mol) Base - 4 C. in accordance A7 Tricine/NH.sub.4OH (Tricine/Mo = 0.9 mol/mol) Base - 5 C. in accordance A8 Tricine/NH.sub.4OH (Tricine/Mo = 1.0 mol/mol) Base - 7 C. in accordance

(70) In a manner similar to the results obtained for toluene hydrogenation, the results summarized in Table 6 show that all of the catalysts supplemented with bicine or tricine in a basic medium prepared in accordance with the invention have improved performances for diesel HDS compared with the calcined reference which was not in accordance with the invention.

(71) The examples show that the molecule in its zwitterionic form selected from the group formed by amino-alcohol acids containing secondary or tertiary amine groups and containing at least one carboxylic acid function and at least one alcohol function produce catalysts which are high performers by themselves without any need to add another molecule, for example a chelating agent.